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Oral Presentations
Table is hyperlinked, click to jump to any section or abstract.
Contents
A1. Atomic Level Characterization .................................................................................... 7
Ammoxidation of glycerol to acrylonitrile via acrolein as intermediate ........................ 7
Role of the micropore of orthorhombic Mo3VOx catalyst for the selective oxidation of
ethane .............................................................................................................................. 8
Kinetic modeling the new reaction network of the partial oxidation of o-xylene to
phthalic anhydride........................................................................................................... 9
Molecular design of metal oxide catalysts for carbon dioxide and methane activation 10
Silica-Supported Transition Metal Oxide Catalysts: Structural Analysis by DFT and Xray Absorption. ............................................................................................................. 11
In situ observation of Cl promoters modifying the active sites of Ag catalysts under
ethylene epoxidation ..................................................................................................... 12
Study of Reactive Intermediates in Methane to Methanol conversion over Cu-ZSM-5
....................................................................................................................................... 13
Catalytic cooperation between small and large noble supported nanoparticles
explaining the activity of nanocatalysts having heterogeneous particle size distribution
....................................................................................................................................... 14
Oscillation regimes performed over the flexible surfaces of the metal Pd nanoparticles:
Monte-Carlo modeling .................................................................................................. 15
Influence of palladium impurities and size of gold nanoparticles on catalytic H2O2
formation and dissociation: DFT approach................................................................... 16
A2. Kinetic Characterization ........................................................................................... 17
A new methodology to capture the complexity of catalytic materials systems:
combining precise manipulation of surface composition with intrinsic kinetic
characterization ............................................................................................................. 17
Equilibrium relationships for non-equilibrium chemical dependenies ......................... 18
Comparative study of the partial oxidation of methacrolein and acrolein on Mo/V/Woxides ............................................................................................................................ 21
Mechanistic studies of the selective oxidation of acrolein to acrylic acid on Mo/V/W
mixed oxides by isotopic transient kinetic analysis and DRIFTS ................................ 22
The role of water in methacrolein oxidation on heteropoly acids ................................ 23
On the mechanism of ethane ODH over highly selective Ni0.85Nb0.15Ox catalyst ... 24
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The curious case of benzaldehyde oxidation: active radicals Vs. Au catalyst and benzyl
alcohol ........................................................................................................................... 25
Insights in the Cobalt(II) Catalyzed Decomposition of Peroxide ................................. 26
A3. Nanostructured Catalysts ........................................................................................... 27
Preparation and Characterization of Metal-Loaded Titania Nanotubes for
Photocatalysis of Dyes and Environmental Hormones Contaminated Wastewaters .... 27
Fundamental Studies of Reactions on Nanoporuos Gold Under Well Defined
Conditions: Catalyst Activation and Oxygen-assisted Coupling .................................. 28
Influence of Fe addition on activity of Ag-containing catalysts in selective oxidation of
alcohols ......................................................................................................................... 29
Design and Application of Single-site Ti-containing Macro- and Meso- Porous Silica
for Selective Oxidations................................................................................................ 30
Effect of cerium doping on the morphology and activity of cobalt on SBA-15 catalysts
prepared by the two-solvent method ............................................................................. 31
Epoxidation of alkenes through oxygen activation over a bifunctional CuO/Al2O3
catalyst .......................................................................................................................... 32
One-step hydrothermal synthesis of ZnO-reducted graphene oxide using Zn powder for
photocatalysis ................................................................................................................ 33
New multicomponent catalysts for the selective aerobic oxidative condensation of
benzylamines to N-benzylidenbenzilimine ................................................................... 34
Aerogel-prepared nanocrystalline CoOx/MgO and VOx/MgO systems for oxidative
catalysis ......................................................................................................................... 35
Precise control of the microstructure and the catalytic properties of Sb2O4/VSbO4
catalsyts prepared by electron lithography. .................................................................. 36
The impact of microstructure geometry on the mass transport in artificial pores - a
numerical approach ....................................................................................................... 37
Adsorption phenomena in oxidation catalysis studied by microcalorimetry ................ 38
Metal-organic frameworks Cr- and Fe-MIL-101 as heterogeneous catalysts for liquidphase selective oxidations ............................................................................................. 40
Preparation of CuCr2O4 Spinel Nanoparticles Catalyst for Selective Oxidation of
Benzene to Phenol with Molecular Oxygen ................................................................. 41
Selective oxidation of glycerol to acrylic acid over Cu-nanoclusters supported on
nanocrystalline MnO2 ................................................................................................... 42
Oxidative activation of methane over Mn-Na-W/SiO2 catalysts: Products yield control
through the catalyst nanostructure design ..................................................................... 43
B1.Materials Synthesis ..................................................................................................... 45
Modification of vanadium phosphorus oxide catalyst synthesised via sesquihydrate
route .............................................................................................................................. 45
Modification of vanadium based oxide catalysts using low Ga/V molar ratio ............. 46
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Shaping of oxidation catalysts: a systematic molecular-level investigation of its role.
The case of vanadium-aluminium (hydr)oxides and bismuth molybdate ..................... 47
Importance of the aviation treatment on K free and K- containing MoVSbO catalysts
for propane selective oxidation. .................................................................................... 48
Hydrothermal Synthesis and Characterization of Bismuth Molybdate Catalysts for the
Selective Oxidation of Propene to Acrolein ................................................................. 49
Synthesis of Orthorhombic Mo-W-V-Ox and its Catalytic Application in Selective
Oxidation of Acrolein to Acrylic Acid ......................................................................... 50
Combinatorial design and preparation of transition metal doped MoVTe catalysts for
oxidation of propane to acrylic acid.............................................................................. 51
New look at the problem of three-way catalysts........................................................... 52
Particle size effects in selective oxidation of lactose with Pd/h-BN catalysts .............. 53
Physical Grinding of Metal Acetates to form Alloyed Bimetallic Catalysts ................ 54
Controlling oxygen activation and oxygen mobility in Ce-doped strontium cobalt
ferrite perovskites.......................................................................................................... 55
Development of an organic-inorganic hybrid method: Toward improved NiMoO4 both
active and highly selective in the propane ODH .......................................................... 56
Hydropobic gold catalysts: Synthesis and application in oxidation catalysis............... 58
Selective side-chain oxidation of alkyl aromatic compounds on promoted vanadium
based materials .............................................................................................................. 59
Simple and scalable synthesis of highly active Lewis acidic Sn-β for Baeyer-Villiger
oxidation ....................................................................................................................... 60
Synthesis and characterization of layered precursors based in transition metal and its
catalytic tets in benzyl alcohol oxidation ...................................................................... 61
Controlable properties of Csx(NH4)3-xHPMo11VO40 mixed-salts catalysts Influence on the performances for the selective oxidation of isobutane into
methacrylic acid ............................................................................................................ 62
Alternative Catalyst for the selective oxidation in the SuperClaus Process ................. 63
The Palladium effective catalyst for “green” process. .................................................. 64
In situ carbon templating as a new route for anchoring Lithium in Magnesium Oxide
Lattice ........................................................................................................................... 66
B2. Greener Oxidants, Alternative Oxidants .................................................................... 67
Green oxidation of fine chemicals in the presence of bifunctional catalysts ................ 67
Influence of the chemical composition of the brucite-type layer of LDH-compounds
ZnxAl, MgxAl on their catalytic activity for the epoxidation of olefins using H2O2 as
greener oxidant.............................................................................................................. 68
Oxidative Carbonylation of Phenol to Diphenyl Carbonate using Pd Electrocatalyst . 69
Anthracycline mediated photocatalytic formation of hydrogen peroxide .................... 70
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Chemo- and Regioselective Hydroxylation of Aromatics to Phenols with Hydrogen
Peroxide Catalyzed by a Divanadium-Substituted Polyoxometalate............................ 71
Enzymatic oxidation of phenols by immobilized oxidoreductases............................... 72
Versatile eco-friendly Pickering emulsions for hydrogen peroxide-based catalytic
oxidations ...................................................................................................................... 73
The oxidation of 1,2-cyclohexanediol to adipic acid with oxygen: A study on
selectivity affecting parameters .................................................................................... 74
Gold-catalyzed aerobic epoxidation of stilbene in methylcyclohexane: Kinetic study of
the co-oxidation mechanism ......................................................................................... 75
Metal-Free Carbon Activation of Peroxymonosulfate for Catalytic Degradation of
Aqueous Contaminants ................................................................................................. 76
B3. New Ideas for Decoding Catalyst Complexity ........................................................... 77
Selective Oxidation using Ultra Low Loaded Au Catalysts ......................................... 77
A Novel Class of the Oscillating Reactions: Homogeneous Carbonylation of
Unsaturated Compounds in Pd Complexes Solutions .................................................. 78
Microwave conductivity measurements in a resonant cavity: A powerful in situ
technique for elucidating the relevance of interfacial charge transfer in selective
oxidation catalysis ......................................................................................................... 79
Minimalist Atomic Synthesis and TAP Kinetic Analysis: A New Approach to
Unraveling the Complexity of Mixed Metal Oxide Catalysts ...................................... 80
C1. Petrochemicals: Raw and Intermediates .................................................................... 81
Investigation of engineering aspects in ethane ODH over highly selective
Ni0.85Nb0.15Ox catalyst ................................................................................................... 81
Oxidative Dehydrogenation of Ethane to Ethylene ...................................................... 82
Alumina supported vanadium containing phosphotungstic acid as an effective catalyst
for oxidative dehydrogenation of ethane to ethylene .................................................... 83
Syngas generation over Ni-Pd/CeO2-ZrO2-Al2O3 catalysts: formation and evolution
of active sites for autothermal reforming of methane ................................................... 84
C2. Commodity and Fine Chemicals ................................................................................ 85
Whole-cell biocatalysis coupled to heterogeneous catalytic oxidation for
deracemization of chiral sulfoxides .............................................................................. 85
Concepts for the development of industrial phthalic anhydride catalysts - current
approaches and challenges ............................................................................................ 86
Heterogeneous Selective Oxidation of Fatty Alcohols: Oxidation of 1-Tetradecanol as
a Model Substrate ......................................................................................................... 87
Metal-Free Aerobic Alcohol Oxidation: Intensification under Three-Phase Flow
Conditions ..................................................................................................................... 88
Mixed nano-metal oxides: A novel approach for oxidation of styrene ........................ 89
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Supported Vanadium Antimony Oxides for the Oxidation of Methanol to
Formaldehyde ............................................................................................................... 90
The use of tri-metallic Au-Pd-Pt catalysts to enhance selectivity in alcohol oxidations
....................................................................................................................................... 91
Crude glycerol catalytic oxidation process in the liquid phase: Advantages and
disadvantages. ............................................................................................................... 92
1-Octanol Selective Oxidation over Supported Gold Catalysts: Influence of the Support
Nature, Metal Load and Reaction Conditions............................................................... 93
Acetoxylation of toluene: Marked effect of reaction pressure on the activity, selectivity
and long-term stability of Pd-containing catalysts........................................................ 94
The effect of ring size on product distribution during the oxidation of cyclic alkenes
using gold catalysts ....................................................................................................... 95
Oxidation of Benzyl Alcohol Benzaldehyde over Supported Gold Nanoparticles....... 96
Promotion of Sm/Gd-doped Cu-Zn Washcoat Catalyst for a Steam Reforming of
Methanol in a Microchannel Reactor ............................................................................ 97
C3.Renewable Chemistry ................................................................................................. 98
2,5-Furandicarboxylic acid synthesis in water as green alternative to terephtalic acid 98
Role of active phase and support in Au and Au-Cu catalysts used for selective
oxidation of HMF ......................................................................................................... 99
Highly efficient cerium and nickel based catalysts for hydrogen production from
ethanol at room temperature ....................................................................................... 100
Synergetic behavior of bimetallic Pd-Pt/TiO2 catalysts in the green synthesis of methyl
formate ........................................................................................................................ 101
The Low-temperature Catalytic Pyrolysis of Organic Waste ..................................... 102
C4.Oxidation Technology for CleanTech ....................................................................... 104
A chemical-loop approach for the generation of hydrogen by means of ethanol
reforming..................................................................................................................... 104
Synthesis of Hydrogen Oxidation Electrocatalyst from Metal Organic Frameworks 105
Effect of K on soot combustion by combined TPO and Raman spectroscopy ........... 106
Influence of methanol concentration on CO oxidation over CuOx/CeO2 catalysts ... 107
Title: H2 oxidation as criteria for PROX catalyst selection ....................................... 108
High reactive mixed LNT/CeZr catalytic systems for the simultaneous removal of NOx
and soot from Diesel exhausts .................................................................................... 109
Utilization of Carbon Dioxide by Catalyst-Assisted Chemical Looping.................... 110
Desulfurization of diesel oil with H2O2 catalyzed by lacunary Keggin 11tungstophosphates ....................................................................................................... 111
Alloyed Pd-Rh catalysts: balancing between deactivation and stable activity. .......... 112
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Titanium dioxide phases in mesostructured silica matrices: Synthesis, characterization
and oxidation activity.................................................................................................. 113
Partial Oxidation of H2S over NaxV2O5 Bronze....................................................... 114
Low temperature methane combustion over palladium supported on a mixture of TiO2
and ZSM-5 catalyst in the presence of water .............................................................. 115
Green Catalytic Oxidation Route of Cyclohexane to Adipic Acid Using Gold
Bimetallic Catalysts. ................................................................................................... 116
Index of Presenting Authors ........................................................................................... 117
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A1. Atomic Level Characterization
Abstract Number: 1122 Oral Presentation
Session: Atomic Level Characterization
Sunday, June 9, 1:00 pm, Brauer Hall, Room 12
Ammoxidation of glycerol to acrylonitrile via acrolein as intermediate
Sebastien Paul1, Carsten Liebig2, Wolfgang F. Hölderich2, Cyrille Guillon1, Benjamin
Katryniok1, Franck Dumeignil1
1
Unité de Catalyse et Chimie du solide, Ecole Centrale de Lille, Villeneuve d'Ascq, France
RWTH Aachen, Dept. of Chemical Technology and heterogeneous Catalysis, Aachen,
Germany
2
[email protected]
Acrylonitrile can be obtained by successive dehydration of glycerol to acrolein followed
by the ammoxidation of the latter. The corresponding reactions necessitate an acid
catalyst for the first step and an ammoxidation catalyst for the second one. Thus, a well
known solid acid (tungsten oxide on titania) catalyst was chosen and combined with an
antimony-iron mixed oxide using various Sb/Fe ratios. The corresponding reactions were
performed in a tandem reactor without any purification of the intermediately formed
acrolein, allowing thus an independent optimization of the reaction conditions for each
step.
The obtained catalytic performance reached up to 39% yield in acrylonitrile. From a
more detailed study using XPS, XRD and control experiments, we could show that the
presence of pure FeSbO4 mixed phase was responsible for high selectivity in
acrylonitrile in the second step and was furthermore formed in-situ under reaction
conditions. Finally the influence of the by-products from the dehydration step was
studied in detail.
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Abstract Number 1206 Oral Presentation
Session: Atomic Level Characterization
Sunday, June 9, 1:30p.m., Brauer Hall, Room 12
Role of the micropore of orthorhombic Mo3VOx catalyst for the selective
oxidation of ethane
Satoshi Ishikawsa1, Toru Murayama1,Wataru Ueda1,
1
Catalysis Research Center, Hokkaido University, Sapporo, Hokkaido, Japan
[email protected]
We have reported that orthorhombic Mo3VOx catalysts with a micropore based on 7membered rings showed outstanding catalytic activity for selective oxidation of light
alkane. Here, we report the role of the micropore for the selective oxidation of ethane,
propane, and isopropanol. Mo3VOx catalysts with different particle sizes were
synthesized by the addition of an anionic surfactant and by changing synthesis
temperature under hydrothermal conditions. Synthesized materials had the same
crystal structure, ethane adsorption capacity of micropore, and chemical composition,
except external surface area due to the different particle sizes. All the catalysts showed
almost the same catalytic activity for the selective oxidation of ethane, indicating that
the external surface area had almost no effect on the catalytic activity. In contrast,
selective oxidations of propane and isopropanol were affected by the external surface
area. It is concluded that ethane is activated in the micropore, which result in the
outstanding catalytic activity.
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Abstract Number 1227 Oral Presentation
Session: Atomic Level Characterization
Sunday, June 9, 2:00p.m., Brauer Hall, Room 12
Kinetic modeling the new reaction network of the partial oxidation of o-xylene
to phthalic anhydride
Gerhard Mestl1, Robert Marx1, Jörg Wölk2,Thomas Turek3
1
Clariant, Oxidation Catalysis, Bruckmühl, Germany
Sasol Germany GmbH, Hamburg, Germany
3
Clausthal University of Technology, Inst. Of Chemical Process Engineering,
Clausthal,Germany
2
[email protected]
The oxidation of o-xylene to phthalic anhydride is one of the important industrial
processes based on selective oxidation reactions. For the last 50 years vanadia - titania
catalysts have been used in this process. The reaction parameters like temperature
range of operation, reactor inlet pressure, contact time, etc. slightly changed during this
continuous process optimization. However, the fundamental understanding of the byproduct formation is still an open task. By using a sample port pilot plant, a detailed
investigation was conducted for the first time of the by-product formation at different
operation conditions. Several hitherto unknown intermediates could unambiguously be
identified. The combination of process conditions and by-product formation enables the
discussion of a new improved reaction scheme for the catalytic oxidation of o-xylene.
Most of the published results on reaction kinetics are based on tests using laboratory or
bench scale reactors. Therefore, only a limited view was possible on realistic conditions
during the o-xylene conversion mechanisms. This study utilizes for the first time a
commercial-scale pilot plant charged with a commercial multilayer catalyst and
equipped with axial sample ports for the on-line investigation of the oxidation process.
Thus, for the first time, a detailed reaction scheme could be developed under industrial
process conditions generating a deeper understanding of the by-product formation as
function of the reaction propagation as well as the process conditions.
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Abstract Number 1214 Oral Presentation
Session: Atomic Level Characterization
Sunday, June 9, 2:45, Brauer Hall, Room 12
Molecular design of metal oxide catalysts for carbon dioxide and methane
activation
Cynthia S. Lo1, Zhuo Cheng1, Eunmin Lee1, Milorad P. Dudukovic1 ,Christopher Singer1,
Vesna Havran1
1
Washington University in St. Louis, Department of Energy, Environmental Chemical
Engineering, Saint Louis, Missouri, U.S.A.
[email protected]
We have been developing structure-property relationships for carbon dioxide and
methane activation and conversion on metal oxide catalysts that lead us to believe that
charge carriers at the metal-support interface must influence the thermodynamics and
kinetics of these reactions. We use density functional theory calculations and quantum
dynamics simulations to study structure, properties, and reactivities of catalytic
systems. We will discuss carbon dioxide photodissociation in the gas phase and on
surfaces, and progress in achieving selective methane partial oxidation. We will also
highlight major findings from our recent publication (J. Chem. Phys., 138, 014702,
(2013)) on carbon dioxide activation and conversion on reduced ceria (110)
surfaces. Finally, we will discuss strategies for catalyst design at the atomic level based
on our electronic analyses.
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Abstract Number 1241 Oral Presentation
Session: Atomic Level Characterization
Sunday, June 9, 3:15, Brauer Hall, Room 12
Silica-Supported Transition Metal Oxide Catalysts: Structural Analysis by DFT and
X-ray Absorption.
Klaus Hermann1, Lili Sun1, Chunsheng Guo1,Kazuhiko Amakawa1,A. Trunschke1,R.
Schlögl1, Michael Hävecker2
1
Fritz-Haber-Institut der MPG, inorganic Chemistry, Berlin, Germany
Helmholtz Center, Solar Energy Research, Berlin, Germany
2
[email protected]
Density-functional theory (DFT) together with experimental results from X-ray
absorption (NEXAFS) can provide an understanding of electronic and structural
properties of metal oxides forming active centers in catalysts of industrial relevance.
DFT calculations, using the StoBe cluster code, are performed on oxygen core
excitations in different vanadia-, molybdena-, and titania-silica clusters. These results
are compared with O K-edge NEXAFS measurements of corresponding catalysts on SBA15 silica. Different oxygen, inside MeOx (Me = V, Mo, Ti) and SiO2, can be clearly
distinguished in the theoretical spectra. A comparison with experimental NEXAFS
spectra for different vanadia species provides clear evidence of polymeric VOx at the
catalyst surface. The studies for molybdena species indicate that tetrahedral dioxo
MoO4 units dominate the experimental spectra. The calculations suggest that
monomeric titania species at low coverage on SBA-15 will form tetrahedral complexes
where titanyl oxygen is saturated by hydrogen yielding OH groups at the Ti centers.
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Abstract Number: 1147 Oral Presentation
Session: Atomic Level Characterization
Sunday, June 9th, 3:45 pm, Brauer Hall, Room 12
In situ observation of Cl promoters modifying the active sites of Ag catalysts
under ethylene epoxidation
Tulio C R Rocha1, Axel Knop-Gericke1, Robert Schlögl1
1
Fritz Haber Institute of the Max Planck Society, Inorganic Chemistry, Berlin, Germany
[email protected]
Since the discovery of the first catalytic processes and their further development for
commercial use, it is known that the performance of heterogeneous catalysts can be
modified by the incorporation of additional elements at very small concentrations
known as promoters. However, general understanding of the mechanism of action of
promoters at atomic level is limited to a few systems. This lack of fundamental
knowledge can be related to the experimental challenge of elucidating the catalysts
modifications induced by promoters. Here, we report a direct observation of the action
of a promoter modifying the active sites of a heterogeneous catalyst under reaction
conditions by near ambient pressure X-ray photoelectron spectroscopy. For a silver
catalyst under ethylene epoxidation, the increase in selectivity obtained by chlorine
promotion is related to modifications in the balance between electrophilic and
nucleophilic oxygen species, which constitute the catalyst active sites for the selective
and unselective oxidation reactions.
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Abstract Number 1167 Oral Presentation
Session: Atomic Level Characterization
Sunday, June 9, 4:45 p.m., Brauer Hall, Room 12
Study of Reactive Intermediates in Methane to Methanol conversion over CuZSM-5
Julie Vancauwenbergh1, Pieter Vanelderen1, Ryan G. Hadt2, Edward I. Soloman2, Robert
Schoonheydt1, Bert Sels1
1
KULeuven, Centre for Surface Chemistry and Catalysis (COK), Vlaams-Brabant, Belgium
Stanford University, Department of Chemistry, Stanford, California
2
[email protected]
Methane will become an important alternative as energy source and feedstock for the
chemical industry. The usage of methane is however hampered by its high chemical
inertness. This research focuses on oxygen-activated Cu-ZSM-5 which selectively
oxidizes methane to methanol. Despite this unique observation, a continuous catalytic
cycle has not been demonstrated today for reasons of an unknown reaction mechanism.
More fundamental insight in the reaction mechanism is thus highly mandatory. The
active site in copper exchanged zeolites has unique spectroscopic features reflecting
novel geometric and electronic structures that are essential to the reactivity. The
presentation addresses new steps forward in the understanding of the reactive Cu core,
an important issue in the activation of inert methane.
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Abstract Number 1260 Oral Presentation
Session: Atomic Level Characterization
Monday, June 10, 1:00p.m., Green Hall, Rodin Auditorium
Catalytic cooperation between small and large noble supported nanoparticles
explaining the activity of nanocatalysts having heterogeneous particle size
distribution
Camila Fernandez1, Alejandro Karelovic1, Patricio Ruiz1
1
Université catholique de Louvain, Louvain-la-Neuve,Brabant wallon, Belgium
[email protected]
The use of metallic nanocatalysts is a key factor to develope processes under mild
reaction conditions. A new model is proposed to explain the catalytic performance of
noble supported nanoparticles. Two reactions were studied: i) NH3 synthesis
(Ru/alumina) and CO2 methanation (Rh/alumina) at low temperature (< 200°C) and
pressure (< 5 bar). The size of metallic nanoparticles (2-18 nm) is determinant for both
reactions. Larger particles are more active than small ones having a higher fraction of
metallic active sites. In NH3 synthesis, the reaction rate over small Ru nanoparticles is
limited by the adsorption of nitrogen. In CO2 methanation, the reaction rate over small
Rh nanoparticles is limited by the strongly adsorbed and hardly hydrogenated CO
species. A catalytic cooperation is put in evidence. Large metallic nanoparticles activate
hydrogen with higher efficacy, promoting the hydrogenation of the adsorbed species on
small particles. Model could be generalized to other catalytic systems.
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Abstract Number 1179 Oral Presentation
Session: Atomic Level Characterization
Monday, June 10, 1:30p.m., Green Hall, Rodin Auditorium
Oscillation regimes performed over the flexible surfaces of the metal Pd
nanoparticles: Monte-Carlo modeling
Vladimir Elokhin1, Konstantin Kalgin2, Vladimir Gorodetskii1, Evgenii Kovalyov1, Andrei
Matveev1
1
Boreskov Insitute of Catalysis, Novosibirsk, Russian Federation
2
Institute of Computational Mathematics and Mathematical Geophysics, Novosibirsk,
Russian Federation
[email protected]
We studied the model of the oscillatory dynamics of the CO oxidation reaction over the
supported Pd nanoparticles, thereto we combine the kinetic Monte-Carlo approach to
model the reaction and the stochastic model for the imitating the supported particle
with dynamically changing shape and surface morphology. Furthermore, it is necessary
to take into account the contribution of COads diffusion over the support onto the
active metal particle surface (collection zone). The influence of the reaction parameters
(rate coefficients and diffusion intensities) and particles characteristics (size, degree of
roughening, etc.) on the oscillation parameters and pattern formation has been studied.
The presence of COads spillover determines the character of concentration waves over
the surface of Pd nanoparticle: oxygen wave propagates from the central region of the
particle to the perimeter; COads wave moves in opposite direction. In the case when the
collection zones overlap (the density of the particles on the support is high) the
synchronization of oscillations between neighboring nanoparticles due to COads
diffusion over the support seems to be possible.
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Abstract Number 1177 Oral Presentation
Session: Atomic Level Characterization
Monday, June 10, 2:00p.m.,Green Hall, Rodin Auditorium
Influence of palladium impurities and size of gold nanoparticles on catalytic H2O2
formation and dissociation: DFT approach
Anna Beletskaya1, Daria Pichugina1, Nikolay Kuz’menko1
1
M.V. Lomonosov MSU,Chemistry, Moscow, Russian Federation
[email protected]
Supported gold nanoparticles are promising catalysts for new production of H2O2 from
O2 and H2. Efficiency of a catalyst can be improved by changing size of nanoparticles
and by adding palladium impurities. Investigation of H2O2 formation and dissociation
mechanism on gold and mixed gold-palladium nanoparticles of different size is very
important to create new type of efficient heterogeneous catalysts. For this purpose
DFT/PBE approach with relativistic all electron basis set is used.
Aun and Aun-1Pd (n=2, 8, 20) have been chosen as a models of a catalysts. H2O2
formation (H+OOH=H2O2) and its dissociation (H2O2=HO+HO) have been considered.
H2O2 synthesis on gold is hindered due to high Ea of H+OOH=H2O2, which increase with
increase of gold cluster size. Palladium impurities promote H2O2 synthesis lowering
corresponding Ea. Regardless to nanoperticle size H2O2 dissociation is more probable
on bimetallic systems. Thus bimetallic catalyst is more active and less selective
compared to gold catalyst.
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A2. Kinetic Characterization
Abstract Number: 1212 Oral Presentation
Session: Kinetic Characterization
Tuesday, June 11, 2:45 p.m., Whitaker Hall, Room 100
A new methodology to capture the complexity of catalytic materials systems:
combining precise manipulation of surface composition with intrinsic kinetic
characterization
Rebecca Fushimi1, John Gleaves2, Gregory Yablonsky1
1
Saint Louis University, Parks College of Engineering, Aviation and Technology
Saint Louis, Mo, USA
2
Washington University, Department of Energy, Enivironmental and Chemical
Engineering
[email protected]
A new methodology for correlating a complex material’s surface composition to its
kinetic performance will be discussed. Using complex materials (as opposed to model
catalysts) we can make precise, incremental changes in surface metals composition
using atomic beam deposition. The deposition is coupled with detailed kinetic
characterization using the TAP (Temporal Analysis of Products) pulse response
technique. The TAP technique can be used to develop microkinetic models of the gas
interacting with the surface; a great deal of information is offered about the chemical
processes that the material induces but there is limited information about the
composition of the material itself.
Our present work is focused on correlating kinetic performance to surface
composition of the material. The deposition experiment does more than just add active
sites to the surface, properties of the emergent chemical system will change as well.
The TAP technique offers primary data about reaction of the gas on the surface but
more importantly we can also describe secondary characteristics that represent the
materials system (e.g. surface/bulk diffusion of oxygen, surface diffusivity of reacting
species, etc.). By understanding the evolution of such secondary kinetic features with
surface composition we hope to gain insight in to the function of the system as a whole.
Proof-of-concept experiments using Pd deposition on coarse SiO2 particles are
discussed that demonstrate this methodology. The ability for these materials to store
oxygen and convert CO was measured using the TAP (Temporal Analysis of Products)
pulse response experiment. Temperature programmed reaction with CO revealed an
interesting kinetic behavior that suggests a process of reactive self-assembly. The
oscillatory kinetic behavior was attributed to changes in the amount of reactive oxygen
available and a change in the surface composition of Pd and PdO. A model for the
formation of a highly active Pd species is described.
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Abstract Number: 1264 Oral Presentation
Session: Kinetic Characterization
Tuesday, June 11, 3:15 p.m., Whitaker Hall, Room 100
Equilibrium relationships for non-equilibrium chemical dependenies
Gregory Yablonsky1
1
Saint Louis University, Parks College of Engineering, Aviation and Technology, Saint
Louis, Missouri, USA
[email protected]
In contrast to common opinion, it is shown that equilibrium constants determine the
time-dependent behavior of particular ratios of concentrations for any system of
reversible first-order reactions. Indeed, some special ratios actually coincide with the
equilibrium constant at any moment in time. This is established for batch reactors, and
similar relations hold for steady-state plug-ow reactors, replacing astronomic time by
residence time. Such relationships can be termed time invariants of chemical kinetics.
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Abstract Number: 1163 Oral Presentation
Session: Kinetic Characterization
Tuesday, June 11, 3:45 p.m., Whitaker Hall, Room 100
Mechanism of ethylene epoxidation by a-oxygen on the surface of FeZSM-5
zeolite
Evgeny Starokon1, Mikhail Parfenov1, Larisa Pirutko1, Gennady Panov1
1
Boreskov Institute of Catalysis, Novosibirsk, Russian Federation
[email protected]
Silver is a unique catalyst for ethylene epoxydation. In spite of great efforts the nature
of oxygen, which selectively adds to C=C bonds is not identified. In this connection of
great interest are anion-radical species of α-oxygen, (FeIII-O·-)α, that form at high
concentration (100 µmol/g) from N2O on FeZSM-5 zeolite. At room temperature (RT), αoxygen readily oxidizes methane, benzene and other hydrocarbons yielding
hydroxylated compounds extracted from the surface.
In this work, we report for the first time on ethylene epoxidation by α-oxygen,
C2H4+(O)α. Ethylene oxide (EO) is the primary product, which depending on conditions
undergoes secondary transformations on acidic centers. Acetaldehyde is mainly
extracted upon RT reaction. The reaction at -60°C, conducted on Na-modified FeZSM-5,
yields mainly EO, which fraction comprises 80 %.
In contrast to oxidation of methane, no hydrogen abstraction takes place in the case of
ethylene (FTIR in situ). The reaction mechanism is discussed.
Page | 20
Abstract Number: 1182 Oral Presentation
Session: Kinetic Characterization
Tuesday, June 11, 4:15 p.m., Whitaker Hall, Room 100
Water in C1-C2 hydrocarbon oxidation: Spectator or active participant?
Mikhail Sinev1, Vladimir Lomonosov2, Yuriy Gordienko2
1
Semenov Institute of Chemical Physics, Moscow, Russia
ZAO ‘Schag’ Company, Moscow, Russia
2
[email protected]
A unique effect of water onto the oxidation of C1-C2 hydrocarbon over NaWMn/SiO2
oxidative coupling of methane (OCM) catalyst is investigated. Both rate of reaction and
OCM selectivity are enhanced by water addition during methane oxidation. At
increasing water content in the feed its relative effect substantially decreases, so the
increasing concentration of water above 8 vol.% does not further enhance the rate of
methane oxidation. In the case of ethane oxidation, the rate of reaction is even more
strongly affected by water addition, whereas selectivity to ethylene does not change at
equal conversions. The observed effects are explained in terms of water participation in
the active site turnover, namely by shifting the prevailing re-oxidation route from filling
surface oxygen vacancies to oxidative dehydrogenation of surface hydroxy-groups.
Page | 21
Abstract Number 1160 Oral Presentation with Corresponding Poster
Session: Kinetic Characterization
Wednesday, June 12, 10:30 a.m., Brauer Hall, Room 12
Comparative study of the partial oxidation of methacrolein and acrolein on Mo/V/Woxides
Nadine Menning1, Nadine Dürr1, Wolfgang Rüttinger2, Alfons Drochner1, Herbert Vogel1
1
Technische Universität Darmstadt, Ernst-Berl-Institut, Technische Chemie I, Darmstadt,
Germany
2
BASF SE, Ludwigshafen, Germany
[email protected]
The partial oxidation of methacrolein (MAC) on heteropoly acids is an important
industrial synthesis for the production of methacrylic acid (MAA). Unfortunately, the
catalysts lifetime is limited to several months. In contrast to this, Mo/V/W-oxides used
for the oxidation of acrolein (ACR) to acrylic acid are far more stable. However, the
mixed oxides are significant less active towards oxidation of MAC and less selective to
MAA, although MAC differs from ACR only in one additional methyl group. The main
focus of this contribution will be on the differences between the partial oxidations of
MAC and ACR on mixed Mo/V/W oxides. In order to gain more insight into mechanistic
aspects, temperature-programmed reactions and isotopic exchange studies with 18O2
and H218O, have been completed. In this context, the preliminary formed
intermediates, the active role of water, the oxygen incorporation into the products and
the formation of coke layers will be discussed.
Page | 22
Abstract Number 1207 Oral Presentation
Session: Kinetic Characterization
Wednesday, June 12, 11:00 a.m., Brauer Hall, Room 12
Mechanistic studies of the selective oxidation of acrolein to acrylic acid on
Mo/V/W mixed oxides by isotopic transient kinetic analysis and DRIFTS
Tina Petzold1,Alfons Drochner1,Nadine Menning1,Herbert Vogel1, Nadine Dürr1
1
Technische Universität Darmstadt,Ernst-Berl-Institut,Darmstadt,Hessen, Germany
[email protected]
This contribution deals with the selective oxidation of acrolein (ACR) to acrylic acid (AA)
on Mo/V/W mixed oxide catalysts. Parts of the mechanism have been investigated by
introducing different transient response methods (CP reaction pulse-wise, TP reaction)
and DRIFT spectroscopy. For isotopic studies the so-called SSITKA (steady state isotopic
transient kinetic analysis) has been applied. Here, isotopic exchanges were performed
with different pairs of isotopes or isotopologues (16O2/18O2, H216O/H218O,
H2O/D2O). Based on the obtained results a reaction model will be given, which shows
the relevance of the cooperation of surface and bulk oxygen species as well as the active
role of water. Supported by variation of the temperature and feed concentrations
during the different applied SSITKA variants and by kinetic modelling of the transient
responses the significance of the different processes occurring on the catalyst (bulk
diffusion, acrolein adsorption via acetal, etc.) will be supplementary illustrated.
Page | 23
Abstract Number 1193 Oral Presentation
Session: Kinetic Characterization
Wedneday, June 12, 11:30 a.m., Brauer Hall, Room 12
The role of water in methacrolein oxidation on heteropoly acids
Nadine Dürr1, Wolfgang Rüttinger2, Nadine Menning1, Alfons Drochner1, Krasimir
Kantchev1, Herbert Vogel1
1
Technische Universität Darmstadt,
Darmstadt,Hessen, Germany
2
BASF SE, Ludwigshafen, Germany
Ernst-Berl-Institut,
Technische
Chemie
I,
[email protected]
Heteropoly acids (HPAs) are used as catalyst in the selective oxidation of methacrolein
(MAC) to methacrylic acid (MAA). Their performance, especially the stability and
activity, strongly depends on the presence of water in the feed. Results from
temperature-programmed reactions show that the activity increases with increasing
concentration of water while the selectivity to MAA shows a maximum. In this context
isotopic exchange experiments (18O2-SSITKA with and without water, H218O-SSITKA)
have been performed in order to gain more insight into the processes occurring on the
catalyst. Due to the observed oxygen exchange between H2O and MAC it can be
concluded that OH-groups are adsorption sites on the catalyst surface which forms
acetal-like species with MAC in a first step. However, also important seems to be the
competitive adsorption of water and intermediately formed MAA or MAA precursor.
Supported by different possible models the interactions within the HPA/MAC/H2O/O2
system will be discussed.
Page | 24
Abstract Number 1210 Oral Presentation
Session: Kinetic Characterization
Wedneday, June 12, 1:00 p.m., Brauer Hall, Room 12
On the mechanism of ethane ODH over highly selective Ni0.85Nb0.15Ox catalyst
Zinovia Skoufa1, Eleni Heracleous2, Angeliki A. Lemonidou1,2
1
Aristotle University of Thessaloniki, Department of Chemical Engineering, Thessaloniki,
Greece
2
Centre for Research and Technology Hellas, Chemical Process & Energy Resources
Institute, Thessaloniki, Greece
[email protected]
The advanced isotopic experiments performed in this work show that, much like a
typical Mars van Krevelen mechanism, the ODH reaction over NiO and Ni0.85Nb0.15
proceeds via activation of the ethane C-H bond (RDS) by lattice oxygen, as established
by the use of deuterated ethane and calculation of the Kinetic Isotope Effect (KIE) and
by introducing 18O2 in the feed, while gas phase oxygen reoxidizes the catalyst surface
via irreversible dissociative chemisorption. The similar KIE values recorded for host NiO
and Ni0.85Nb0.15 possibly point out to the existence of a single active site responsible
for the activation of ethane over the two catalysts. By combining our current results
with previous observations demonstrating that selectivity is inversely related to the
amount of non-stoichiometric oxygen on the catalyst, while activity seems to correlate
well with the amount of surface Ni sites, a possible mechanism for ethane ODH is
proposed.
Page | 25
Abstract Number 1180 Oral Presentation
Session: Kinetic Characterization
Wedneday, June 12, 1:30p.m., Brauer Hall, Room 12
The curious case of benzaldehyde oxidation: active radicals Vs. Au catalyst and
benzyl alcohol
Ewa Nowicka1, Sankar M. Sundaram2, David W. Knight1,Graham J. Hutchings1,Donald
Bethell3, Damien M. Murphy1
1
Cardiff University, Chemistry, Cardiff, Glamorgan, United Kingdom
Utrecht University, Inorganic Chemistry and Catalysis, Utrecht, The Netherlands
3
University of Liverpool, Chemistry, Liverpool, United Kingdom
2
[email protected]
In the oxidation of alcohols to aldehydes, Au-Pd supported catalysts were found to be
very active and selective. Important fact is that benzaldehyde can undergo oxidation to
benzoic acid even in ambient conditions in presence of air. However, in this reaction
selectivity to benzoic acid is negligible. The investigation of the role of Au-Pd supported
catalyst, TiO2, and addition of benzyl alcohol was conducted for the aerobic oxidation of
benzaldehyde to benzoic acid, which is based on radical mechanism. Gold catalyst was
found to act as radical scavenger decreasing, while TiO2 increasing reaction rate for
oxidation of benzaldehyde. Interestingly, addition of benzyl alcohol slows down the
reaction rate, which is believed to be related to the quenching of active radicals. This
phenomenon is investigated in details with the use of EPR technique. Radicals
responsible for reactions are identified and full scheme of the reaction is proposed.
Page | 26
Abstract Number: 1128 Oral Presentation
Session: Kinetic Characterization
Wednesday, June 12, 2:00p.m., Brauer Hall, Room 12
Insights in the Cobalt(II) Catalyzed Decomposition of Peroxide
Prof. Ive Hermans1
1
ETH Zurich, Zurich, Switzerland
[email protected]
The homolytic activation of alkyl hydroperoxides with transition metal ions like CoII/III
plays an important role in many industrial oxidation processes (for instance, the
oxidation of p-xylene to therephtalic acid). New computational predictions put forward
CoIII-OOR as the crucial intermediate. This species can either eliminate ROO● and
regenerate the active CoII species, or trigger catalyst deactivation. The computed barrier
for Co-OOR dissociation is in quantitative agreement with the measured activation
energy of the overall reaction, supporting the hypothesis that this is the ratedetermining step. Various approaches to the quantification of the reaction kinetics will
be discussed, ranging from titrations, to in situ UV-Vis spectroscopy. Furthermore,
experimental evidence, supported by quantum-chemical calculations, shows that
dimeric cobalt species are responsible for the appearance of a maximum in the ROOHdecomposition rate versus cobalt concentration. Site-isolated immobilization of the
cobalt to alumina support prevents dimerization and thereby catalyst deactivation.
Page | 27
A3. Nanostructured Catalysts
Abstract Number 1169 Oral Presentation
Session: Nanostructured Catalysts
Monday June 10, 12:30 p.m., Brauer Hall, Room 12
Preparation and Characterization of Metal-Loaded Titania Nanotubes for
Photocatalysis of Dyes and Environmental Hormones Contaminated Wastewaters
Kuen-Song Lin1, Khanh Toan, Dinh1, Chi-Yu Wang1, Ho-Yang Chan1, Jing-How Yang1
1
Yuan Ze University, Chemical Engineering & Materials Science, Tao-Yuan County,
Taiwan, R.O.C.
[email protected]
Preparation/characterization of titania nanotubes (TNs) and removal efficiency of
dye/environmental hormones pollutants in wastewaters were investigated. FESEM/TEM microphotos showed that the length and diameter of TNs were ranged of
400~1000 and 10~15 nm, respectively. The XRD patterns showed TNs were titanate
after heat treatment for 6 h at 150°C. The TNs were also washed in acid solution to
identify the transition of structure from titanate to anatase. ESCA/EDS data indicated
that TNs consist of Ti, O, and Na atoms and therefore it may produce NaCl in the
synthetic processes. EXAFS data showed that 5% V/TNs had a Ti -O bond with bond
distance of 2.29 Å and coordination number of 1.95. The photodegradative efficiency
orders of TNs were Basic Violet 3>Methylene Blue>Basic Green 5>Basic Violet 10>Acid
Blue 9>Acid Orange 7>Acid Red 1 and PCE>Chlorpyrifos>DBP, respectively. Moreover,
TNs loaded with Ag, Fe, W, and V can promote the photocatalytic efficiencies
significantly.
Page | 28
Abstract Number 1250 Oral Presentation
Session: Nanostructured Catalysts
Monday, June 10, 1:00 p.m., Brauer Hall, Room 12
Fundamental Studies of Reactions on Nanoporuos Gold Under Well Defined
Conditions: Catalyst Activation and Oxygen-assisted Coupling
Robert J. Madix1, Kara Stowers1, Cassandra Freyschlag-Siler1, Monica Biener2,Cynthia M.
Friend1
1
Harvard University, School of Engineering and Applied Science, Belmont, MA, United
States of America
2
Livermore National Laboratory, Livermore, CA, United States of America
[email protected]
Nanoporous gold has been shown to be active for oxygen-assisted vapor phase coupling
of primary alcohols to form esters. Typically these as produced materials are difficult to
activate and show irregular behavior. Using ozone exposures in ultrahigh vacuum, we
have found that extensive cleaning is necessary to remove bulk carbon. Once cleaned
the material efficiently activates dioxygen and readily couples methanol to methy
formate. Temperature programmed reaction spectroscopy reveals high selectivity for
ester formation when oxygen is the limiting reactant on the surface. Details of the
reaction on NG gold and comparisons to pure gold and silver will be discussed.
Page | 29
Abstract Number 1203 Oral Presentation
Session: Nanostructured Catalysts
Monday, June 10, 1:30 p.m., Brauer Hall, Room 12
Influence of Fe addition on activity of Ag-containing catalysts in selective
oxidation of alcohols
Olga V. Vodyankina1, A.S. Savelyeva1, V.I. Sobolev2, K.Yu. Koltunov2,4
1
Tomsk State University, Tomsk
Boreskov Institute of Catalysis SB RAS, Novosibirsk, Russia
3
Russian Academy of Sciences, D.Zelinsky Institute of Organic Chemistry, Moscow,
Russia
4
Novosibirsk State University, Novosibirsk, Russia
2
[email protected]
In this study the characterization and ethanol oxidation activity of Ag-based catalysts
deposited on Si3N4 and SiO2 and modified by iron oxide (0.01-10 wt %) have been
investigated. The first series of catalysts was prepared on the basis of Si3N4 and
denoted as Ag-Fe/Si3N4. Fe-containing modifier was incorporated during the Si3N4
synthesis with subsequent Ag deposition from precursor solution. The second series of
Ag-based catalysts was prepared by one-step wet impregnation of SiO2 by
corresponding precursors and denoted as Ag-Fe/SiO2. Fe content in Si3N4 does not
influence on the state of silver in Ag-Fe/Si3N4, but affects Ag particles state on SiO2
surface. The activity growth in reaction of hydrogen oxidation is observed for all samples
in comparison with Fe-containing system without Ag. Ag-Fe/SiO2 catalysts show high
activity in low-temperature oxidative dehydrogenation of ethanol (100% conversion and
selectivity towards acetaldehyde of 86-88 % at 250 °C) in comparison with Ag-Fe/Si3N4.
The growth of Fe content in Ag-Fe/SiO2 by 10 wt % increases COx formation.
Page | 30
Abstract Number 1157 Oral Presentation
Session: Nanostructured Catalysts
Monday, June 10, 2:00 p.m., Brauer Hall, Room 12
Design and Application of Single-site Ti-containing Macro- and Meso- Porous Silica for
Selective Oxidations
Hiromi Yamashita1, Takashi Kamegawa1, Takahiro Ando1, Norihiko Suzuki1,
1
Osaka University, Division of Materials and Manufacturing Science, Graduate School of
Engineering, Osaka, Japan
[email protected]
Preparation of single-site Ti-containing silica with three-dimensional (3D) hierarchical
porous structure, i.e., combined structure of mesoporous and macroporous materials,
was successfully achieved by using poly(methyl methacrylate) (PMMA) and organic
surfactant as templates. The comparative studies revealed that the prepared samples
with 3D hierarchical porous structure exhibited higher catalytic performances for
epoxidation of α-olefins, especially epoxidation of α-olefins with long alkyl chain as
compared to the conventional catalysts. As a result of the construction of 3D
hierarchical porous structure, the efficient catalytic performance is presumably
accomplished by decreasing diffusion limitations and facilitating the efficient
transportation of reactants to the catalytically active single-site Ti-moieties. The detailed
characterizations and the catalytic activities of single-site Ti-containing silica in the
selective oxidation reactions will be presented.
Page | 31
Abstract Number 1224 Oral Presentation
Session: Nanostructured Catalysts
Monday, June 10, 2:45 p.m., Brauer Hall, Room 12
Effect of cerium doping on the morphology and activity of cobalt on SBA-15
catalysts prepared by the two-solvent method
Alan Chaffee1, Jamileh Taghavimoghaddam1, Gregory P Knowles1
1
Monash University, School of Chemistry, Victoria, Australia
[email protected]
Cerium was added as a promoter to SBA-15 supported cobalt catalysts prepared via the
`two-solvent method'. Co(NO3) 2.6H2O and Ce(NO3)3.6H2O were used as the metal
precursors. The composite materials were characterized by N2 adsorption-desorption,
XRD, FTIR, ICP-MS, TEM, HRTEM, SEM, STEM and elemental mapping. The addition of Ce
was found to reduce the size of the crystalline Co3O4 patches and increase their
dispersion, with the occasional occurrence of individual Co3O4 nanorods. The catalytic
activity of the Ce-doped Co-composites was compared with that of Co-composites
prepared without Ce addition and also with analogous Ce-only composites. The Cedoped composites were found to exhibit improved catalytic activity towards the
oxidation of a series of small alcohols and olefins with tert-butylhydroperoxide. This is
attributed to the better dispersion of the active species and/or an improvement of the
Co3+/Co2+ redox properties due to the presence of Ce3+/Ce4+.
Page | 32
Abstract Number 1249 Oral Presentation
Session: Nanostructured Catalysts
Monday, June 10, 3:15 p.m., Brauer Hall, Room 12
Epoxidation of alkenes through oxygen activation over a bifunctional CuO/Al2O3
catalyst
Nicola Scotti1, Claudio Evangelisti1, Federica Zaccheria1, Rinaldo Psaro1, Nicoletta
Ravasio1
1
ISTM-CNR,Milano, Italy
[email protected]
Epoxides are versatile synthetic intermediates but actually their production routes
overlook energy, atom efficiency and environmental concerns, therefore more
affordable production pathways are constantly pursued[1].
Here we report our results on the one-pot epoxidation of alkenes over a bifunctional
alumina-supported copper catalyst (CuO/Al2O3), mediated by the in situ formation of
cumyl hydroperoxide, generated by reaction between cumene and O2[2]. The reaction
(T=100 °C, pO2=1 bar), performed without the addition of any radical initiators, leads to
high conversion and selectivity with different substrates: e.g. trans-β-methylstyrene
gave the corresponding epoxide in 95% yield (t=3h), while using cyclooctene the yield
was 72% (t=6h). Furthermore CuO/Al2O3 shows a good stability and reusability: it can
be used at least 3 times, affording only a slight decrease in its catalytic performances.
[1] F. Cavani, J.H. Teles, ChemSusChem, 2009, 2, 508.
[2] N. Scotti, N. Ravasio, F. Zaccheria, R. Psaro, C. Evangelisti, Chem. Commun., 2013, 49,
1957.
Page | 33
Abstract Number: 1124 Oral Presentation
Session: Nanostructured Catalysts
Monday, June 10, 3:45 p.m., Brauer Hall, Room 12
One-step hydrothermal synthesis of ZnO-reducted graphene oxide using Zn
powder for photocatalysis
Shaobin Wang1, Shizhen Liu1, Hongqi Sun1, Shaomin Liu1
1
Curtin University, Department of Chemical Engineering, Perth, Western Australia,
Austrlia
[email protected]
Graphene as a novel carbonaceous nanomaterial has a single or muliple carbon atom
layer with two dimensional aromatic structure. Graphene modified TiO2 or ZnO can
improve the photocatalytic behaviour for UV-vis light response. Here, Zn powder was
utilized as a reducing agent and ZnO precursor for one-step synthesis of reduced
graphene oxide (rGO) -ZnO photocatalysts. The composites were synthesised in a
hydrothermal method with or without a surfactant. The structural, morphological, and
physicochemical properties of the samples were thoroughly investigated by means of Xray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), field emission
scanning electron microscopy (FE-SEM), UV-vis diffuse reflectance (UV-vis DRS), thermogravimetric-differential thermal analysis (TG-DTA), and Raman spectroscopy. Zn powder
could effectively reduce GO to graphene and form ZnO-graphene composites. G-ZnO
photocatalysts can successfully decompose MB under UV-vis illumination. The catalytic
activity is much higher than ZnO. In addition, the synthesis method also influences ZnOgraphene properties and catalytic activity. under reaction conditions. Finally the
influence of the by-products from the dehydration step was studied in detail.
Page | 34
Abstract Number: 1145 Oral Presentation
Session: Nanostructured Catalysts
Tuesday, June 11, 2:45 p.m., Brauer Hall, Room 12
New multicomponent catalysts for the selective aerobic oxidative condensation
of benzylamines to N-benzylidenbenzilimine
Vasile I. Parvulescu1, Alaina Moragues2, Jamal El Haskouri2, Daniel Beltrán2, Pedro
Amorós2, Cristina Opris1
1
University of Bucharest, Organic Chemistry, Biochemistry and Catalysis, Bucharest,
Romania 2Institut de Ciencia dels Material, Universitat de Valencia, Valencia, Spain
[email protected]
The aim of this work is to present results on the selective aerobic oxidative
condensation of benzylamine to N-benzylidenbenzylamine on Au, Sn, Ce and Ni mixed
oxide catalysts encapsulated in a UVM-7 texture using a green route. This is an
important reaction since the product of reaction is a valuable intermediate in organic
synthesis. Traditionally, it is performed using stoichiometric amounts of oxidants. The
catalysts were prepared via encapsulation of those elements in the mesoporous UVM-7
structure and characterized ex-situ and in-situ using specific techniques. Aerobic
oxidative condensation of benzylamine on these catalysts occurred selectively only with
the formation of N-benzylidenbenzylamine. While the selectivity was total, the
conversion varied in a large range as a function of the catalysts composition. The best
results were obtained on the mesoporous Au-Ce-Ni-UVM-7 catalysts. The comparison
with the individual or bicomponent catalysts led to the conclusion of a synergetic effect
between the components.
Page | 35
Abstract Number 1252 Oral Presentation
Session: Nanostructured Catalysts
Tuesday, June 11, 3:15p.m., Brauer Hall, Room 12
Aerogel-prepared nanocrystalline CoOx/MgO and VOx/MgO systems for
oxidative catalysis
Mishakov IIya1, IIyina Ekaterina1, Vedyagin Aleksey1, Bedilo Alexander1
1
Boreskov Institute of Catalysis, Novosibirsk, Novosibirsk region, Russia
[email protected]
For oxidative catalysis it is well known that the size effects are the most expressed. From
other hand, nanocrystalline oxide systems have attracted much attention due to their
unique physicochemical characteristics, morphology and enhanced catalytic properties
in various processes. We proposed an aerogel method based on sol-gel technique which
allows one to synthesize binary CoOx/MgO and VOx/MgO systems with controllable
particle size and uniform distribution of the active component. A series of synthesized
aerogel oxide samples obtained by the following temperature-programmed
decomposition of the corresponding hydroxides have been characterized by a number
of physicochemical methods (XRD, TGA, BET and HRTEM with EDX). Aerogel VOx/MgO
catalysts were found to possess superior activity in the oxidative dehydrogenation of
propane as compared to samples prepared by conventional impregnation. At the same
time, nanocrystalline CoOx/MgO catalyst has demonstrated unique catalytic ability
towards CO oxidation as well as very high thermal stability.
Page | 36
Abstract Number 1239 Oral Presentation
Session: Nanostructured Catalysts
Tuesday, June 11, 3:45 p.m., Brauer Hall, Room 12
Precise control of the microstructure and the catalytic properties of
Sb2O4/VSbO4 catalsyts prepared by electron lithography.
Takahiro Wada 1, Hua Huang2, Satoru Takakusagi2, Yui Haraguchi2, Kiyotaka Asakura2,
Hiroko Ariga2
1
Tokyo Medical and Dental University, Graduate School of Medical and Dental Sciences,
Bunkyo, Tokyo, Japan
2
Hokkaido University, Catalysis Research Center, Sapporo, Japan
[email protected]
α-Sb2O4/VSbO4 shows good performance in selective oxidation of hydrocarbons. They
have two phases; an oxygen donor phase composed of α-Sb2O4 and an active phase
composed of VSbO4 that activate the hydrocarbons using the oxygen supplied by the αSb2O4 phase. Such synergism certifies the high activity and selectivity of the catalyst.
We have precisely control the microstructure of catalysts with definite width and
separations prepared by the electron lithography. The microstrutured αSb2O4/VSbO4/Si samples showed strong dependence of the acrolein generation rate on
the separation which showed a maximum on the 1 μm α-Sb2O4 lines in width with the 4
μm VSbO4 separating two adjacent α-Sb2O4 lines. The maximum of the acrolein
generation rate is 1.16*10-13 Torr/min. We will discuss the reaction mechanism in the
presentation
Page | 37
Abstract Number 1225 Oral Presentation
Session: Nanostructured Catalysts
Tuesday, June 11, 4:15 p.m. Brauer Hall, Room 12
The impact of microstructure geometry on the mass transport in artificial pores a numerical approach
Prof. Cornelia Breitkopf1, Matthias Galinsky1, Ulf Sénéchal1
1
Technische Universität Dresden, Chair of Technical Thermodynamics, Dresden,
Germany
[email protected]
The microstructure of porous materials used in heterogeneous catalysis determines the
mass transport inside the network, which may vary over many length scales due to new
preparation techniques. Characterizations of such pore networks are based on methods
as Temporal Analysis of Products (TAP) reactors or Frequency Response (FR). The
classical evaluation of experimental outcomes follows the solution of Fick´s second law
where an integral and effective diffusion coefficient is recognized.However, recent
approaches aim at a detailed local understanding of diffusion and sorption processes. As
there is a lack of proved models, existing classical concepts need to be evaluated with
respect to their ability to reflect local geometries on the nanometer level.In this study,
DSMC (Direct Simulation Monte Carlo) models were used to investigate the impact of
microstructures on the diffusion behavior and to simulate gas pulses inside artificial
microstructures. The resulting diffusion coefficients were compared to those from
investigations with TAP or FR methods.
Page | 38
Abstract Number 1149 Oral Presentation
Session: Nanostructured Catalysts
Wednesday, June 12, 1:00 p.m., Whitaker Hall, Room 100
Adsorption phenomena in oxidation catalysis studied by microcalorimetry
Dr. Sabine Wrabetz1, Dr. Rosa Arrigo1, Dr. Benjamin Frank1, Dr. Detre Teschner1, Dr.
Annette Trunschke1, Prof Robert Schlögl1
1
Fritz-Haber-Institute der Max-Planck-Gesellshaft, Inorganic Chemistry, Berlin, Germany
[email protected]
Adsorption phenomena have been seldom studied, but play an important role in
oxidation catalysis. The knowledge about heat of adsorption of reactant on the surface
of a catalyst can contribute to a better understanding of the complex microkinetics.
Moreover, the quantitative data provide a basis for theoretical modeling. Since perhaps
only a minor fraction of all surface atoms form active centers, the determination of their
number and strength requires a sensitive analytical method. Here, we focus on
adsorption microcalorimetry [1]. To facilitate the correlation of microcalorimetric results
with the catalytic performance, a molecule similar to the reactant, or the reactant itself,
was used. Tads. was chosen lower than Treaction to separate the adsorption process
from the catalytic reactions.
In this work, we will demonstrate how structure-activity correlations can be established
by combining microcalorimetry with electron microscopy and spectroscopic techniques,
like IR and XPS. The power of these complementary methods will be illustrated by
choosing the following examples: (i) carbon-based catalysts (oCNT) for ODH of propane
or ethylbenzene [2], (ii) supported metals (Pd/N-CNT) for liquid phase oxidation of
benzyl alcohol [3], (iii) supported oxides (CeO2/support) for HCl oxidation [4], and (iv)
mixed metal oxides (MoVTeNb oxide) for selective oxidation of propane to acrylic acid
[5].
[1] S. Wrabetz, R. Schlögl, F. Jentoft et.al., J. Catal. 269 (2010) 351-358.
[2] B. Frank, S. Wrabetz, A. Trunschke, R. Schlögl, et.al., ChemPhysChem 12 (2011) 27092713.
[3] R. Arrigio, S. Wrabetz et.al., PCCP 14 (2012) 10523-10532.
[4] R. Farra, S. Wrabetz, D. Teschner et.al., accepted, PCCP, Dec. 2012
[5] M. Hävecker, S. Wrabetz, A. Trunschke et.al., J.of Catalysis. 285 (2012) 48-60.
Page | 39
Abstract Number 1218 Oral Presentation
Session: Nanostructured Catalysts
Wednesday, June 12, 1:30 p.m., Whitaker Hall, Room 100
Tuning Catalytic Performances by Restructuring Transition Metal Oxides under
Reaction Conditions
Franklin (Feng) Tao1, Shiran Zhang1
1
University of Notre Dame, Notre Dame, Indiana
[email protected]
Removal of poisonous gases, including nitric oxide and carbon monoxide, released from
vehicle engines and other sources is critical toward environmental remediation. The
search for cost-effective catalysts without any nonprecious metals highly selective and
active in reduction of nitric oxide to nitrogen (N2) has remained a significant challenge.
Here we report on that a new catalyst, non-stoichiometric cobalt monoxide formed
through restructuring of Co3O4 nanorods under reaction conditions and identified with
in-situ analytical technique, which is highly active for reduction of nitric oxide with
carbon monoxide with a 100% selectivity to production of N2. This catalytic
performance remains unchanged at 420oC through 36 hours. In-situ studies revealed
that the active phase is nonstoichiometric CoO. This study demonstrated the
significance of in-situ and operando studies in search of new catalysts and
understanding of catalytic mechanisms.
Page | 40
Abstract Number 1161 Oral Presentation
Session: Nanostructured Catalysts
Wednesday, June 12, 2:00 p.m., Whitaker Hall, Room 100
Metal-organic frameworks Cr- and Fe-MIL-101 as heterogeneous catalysts for
liquid-phase selective oxidations
Oxana Kholdeeva1, Nataliya Maksimchuk1, Igor Skobelev1, Konstantin Kovalenko2,
Vladimir Fedin2, Irina Ivanchikova1
1
Boreskov Institute of Catalysis, Novosibirsk, Russia
Nikolaev Insstitute of Inorganic Chemistry, Novosibirsk, Russia
2
[email protected]
Metal-organic frameworks (MOFs) have attracted considerable attention as prospective
materials for heterogeneous catalysis due to a unique ensemble of properties, such as
high surface areas, crystalline open structures, tunable pore size and functionality, and
high contents of uniformly distributed accessible metal sites. The chromium
terephthalate Cr-MIL-101 [1] possesses high stability to air, solvents and thermal
treatment (up to 300 °C). Here we report on the potential of Cr- and Fe-MIL-101 as
heterogeneous catalysts for liquid-phase selective oxidation of hydrocarbons (alkanes,
alkenes, aromatics) with environmentally benign oxidants [2,3]. Catalyst reusability and
nature of catalysis were thoroughly investigated. Suggestions on the reaction
mechanisms have been made to explain the differences in the product selectivities
achieved over Cr- and Fe-MIL-101.
[1] G. Férey, C. Mellot-Draznieks, C. Serre, F. Millange, J. Dutour, S. Surblé, I. Margiolaki,
Science 309 (2005) 2040.
[2] N.V. Maksimchuk, K.A. Kovalenko, V.P. Fedin, O.A. Kholdeeva, Chem. Commun. 48
(2012) 6812.
Page | 41
Abstract Number 1236 Oral Presentation
Session: Nanostructured Catalysts
Wednedsay, June 12, 2:45 p.m., Whitaker Hall, Room 100
Preparation of CuCr2O4 Spinel Nanoparticles Catalyst for Selective Oxidation of
Benzene to Phenol with Molecular Oxygen
Shankha Shubhra Acharyya1, Rajib Kumar Singha1, Dr. Ankur Bordoloi1,Dr. Rajaram Bal1
1
CSIR-Indian Institute of Petroleum, Nano Catalysis Area, Catalytic Conversion Processes
Division, Dehradun, India
[email protected]
We have succeeded in preparing the CuCr2O4 spinel nanoparticles with size of ~ 30 nm
by hydrothermal synthesis method. The catalyst was characterized by XRD, ICP-AES,
XPS, TPR, BET- surface area, SEM, and HR-TEM. This CuCr2O4 spinel nanoparticles
catalyst is very active for selective oxidation of benzene to phenol. A benzene
conversion of about ~ 29% with ~96% phenol selectivity was achieved at vapour phase
using air as oxidant. The main advantages of our catalyst CuCr2O4 are that, the catalyst
shows no deactivation till 30 h on time on stream without changing the spinel phase
Page | 42
Abstract Number 1235 Oral Presentation
Session: Nanostructured Catalysts
Wednesday, June 12, 3:15 p.m., Whitaker Hall, Room 100
Selective oxidation of glycerol to acrylic acid over Cu-nanoclusters supported on
nanocrystalline MnO2
Bipul Sarkar1, Reena Goyal1, Ankur Bordoloi1, Rajaram Bal1
1
CSIR-Indian Institute of Petroleum, Dehradun, India
[email protected]
Cu-nanoclusters supported on nanocrystalline-MnO2 were prepared by the
hydrothermal method in presence of surfactant, and it was found the catalyst is highly
active for the selective oxidation of glycerol to acrylic acid. The catalyst was
characterized by XRD, N2-sorption, ICP-AES, TPD, TPR, XPS, SEM, TEM and EXAFS. XRD
reveals the formation of α-MnO2 phase in the catalyst. Absence of any crystalline Cu
phases was detected by XRD indicating the presence of very small size of the Cu species.
Moreover, the Cu particles could not be imaged by TEM but the EXAFS study confirms
the presence of very small Cu-nanoclusters on the α-MnO2 support. The influence of
various reaction parameters like reaction time, substrate: H2O2 mole ratio,
temperature, solvent and the reusability of the catalyst were studied in detail. A glycerol
conversion of 77.1 % with 74.7% selectivity of acrylic acid was achieved after 30 h of
reaction.
Page | 43
Abstract Number 1221 Oral Presentation
Session: Nanostructured Catalysts
Wednesday, June 12, 3:45 p.m., Whitaker Hall, Room 100
Oxidative activation of methane over Mn-Na-W/SiO2 catalysts: Products yield
control through the catalyst nanostructure design
Ilyas Ismagilov1, Ekaterina Matus1, Vadim Kuznetsov1, Zinfer Ismagilov1, Noelia Mota2,
Rufino Navarro2, Jose Luis Fierro2, Mikhail Kerzhentsev1, Gijsbert Gerriten3, Erik
Abbenhuis3
1
Boreskov Institute of Catalysis, Novosibirsk, Russia
Instituto de Catalisis y Petroleoquimica, Madrid, Spain
3
Eindhoven Univeristy of Technology, Eindhoven, The Netherlands
2
[email protected]
The oxidative coupling of methane (OCM) has been comparatively studied over Mn-NaW/SiO2 catalysts prepared by the incipient wetness impregnation method, mixture
slurry method and metal POSS nanotechnology. The effects of metals content, support
type and preparation method on the electronic, redox, structural and catalytic
properties in OCM of Mn-Na-W/SiO2 samples were studied using XPS, HRTEM-EDX, TPR,
XRD, and BET methods. It was shown that the synthesis method and type of SiO2 have
significant effect on the texture, while the Na/W ratio determines phase composition of
the catalysts. Using mass-spectrometric measurements, it was established that ethane
and ethylene yields were strongly affected by the catalyst surface composition, and
these yields have increased with surface Mn concentration. The precise regulation of
product yields was achieved by appropriate variation of catalyst preparation conditions.
Under optimal reaction conditions at 850oC, the 2%Mn1.6%Na3.1%W/SiO2 catalyst
provides C2 hydrocarbons yield of 23.5% at 41% methane conversion.
Page | 44
Abstract Number 1266 Oral Presentation
Session: Nanostructured Catalysts
Wednesday, June 12, 4:15p.m., Whitaker Hall, Room 100
Oxidation of ethylene glycol to glyoxal: from polycrystalline silver to nanostrucrured
Ag/P2O5/SiO2 catalyst.
Olga V. Vodyankina1, G.V. Mamontov1, A.A. Kreiker1,O.V. Magaev1,A.S. Knyazev1,M.A.
Salaev1
1
Tomsk State University, Laboratory of Catalytic Researches, Romak, Russia
[email protected]
Selective oxidation of alcohols to aldehydes is very important process for industrial
production of carbonyl compounds. However, polycrystalline silver and copper catalysts
used in this process are not enough active and stable.In the present work a new
conception allowing to create highly effective nanostructured Ag/P2O5/SiO2 catalyst for
selective oxidation of alcohols is presented. Using of phosphate component providing
stabilization of silver and active species formation on the catalyst surface is a main point
of this approach. For the first time it was shown that phosphate component participated
in alcohol adsorption that led to changing of mechanism of ethylene glycol oxidation on
the base of in situ IR-spectroscopy data and kinetics. Also it was shown that reversible
oxidation/reduction of silver with participation of phosphate component took place.
That provided a high stationary concentration of active sites selective in the glyoxal
formation on silver nanoparticles in wide range of reaction conditions.+.
Page | 45
B1.Materials Synthesis
Abstract Number 1200 Oral Presentation
Session: Materials Synthesis
Sunday, June 9, 1:00 p.m., Laboratory Sciences Building, Room 300
Modification of vanadium
sesquihydrate route
phosphorus
oxide
catalyst
synthesised
via
Kang Jo Yee1, Dr. Leong Loong Kong1
1
Universiti Tunku Abdul Rahman, Mechanical and Material Engineering, Setapak, Kuala
Lumpur, Malaysia
[email protected]
Bulk vanadyl pyrophosphate catalysts prepared via sesquihydrate route drying using
microwave irradiation exhibited a well-crystallized (VO)2P2O7 phase. Catalysts heated
by microwave irradiation in Stage 1 promoted the formation of V5+ phases, which led to
an increased in the specific surface area and average oxidation state of vanadium.
Microwave heated VPOs catalysts show higher total amount of oxygen desorbed in TPD
profiles compare to conventionally heating. The total amount lattice oxygen removed
from microwave drying catalysts in TPR profiles suggested that microwave process is
capable of producing highly reactive V5+ species for H2 consumption
Page | 46
Abstract Number 1198 Oral Presentation with Corresponding Poster
Session: Materials Synthesis
Sunday, June 9, 1:30, Laboratory Sciences Building, Room 300
Modification of vanadium based oxide catalysts using low Ga/V molar ratio
Dr. Leong Loong Kong1, Ling Kuan Hoe1
1
Universiti Tunku Abdul Rahman, Chemical Engineering, Setapak, Kuala Lumpur,
Malaysia
[email protected]
The present work addresses the effect of low level doped by gallium to the vanadyl
pyrophosphate catalysts formulation via sesquihydrate route (VPOs-method) in order to
obtain information of catalytic behaviour with their physicochemical properties. A series
of 0.1%, 0.3% and 0.5% Ga-doped vanadyl pyrophosphate catalysts were synthesised
and denoted as VPOS-0.1%Ga, VPOS-0.3%Ga and VPOS-0.5%Ga. XRD revealed that Gapromoted vanadyl pyrophosphate catalysts prepared via sesquihydrate route exhibited
a well-crystallized (VO)2P2O7 phase and the formation of β-VOPO4 phase which led to
an increase in the specific surface area and average oxidation state of vanadium. Gapromoted VPO catalysts showed at least two times higher total amount of oxygen
evolved than bulk VPO catalyst in TPD profile. Moreover, the addition of Ga promoter
significantly increased both activity and selectivity to maleic anhydride as compared to
undoped VPO catalyst in the oxidation of n-butane.
Page | 47
Abstract Number 1220 Oral Presentation
Session: Materials Synthesis
Sunday, June 9, 2:00p.m., Laboratory Sciences Building, Room 300
Shaping of oxidation catalysts: a systematic molecular-level investigation of its
role. The case of vanadium-aluminium (hydr)oxides and bismuth molybdate
Victor Gabriel Baldovino Medrano1, Eric M Gaigneaux1, Benjamin Farin1, Minh T. Le2, E.
Bruneel3, Isabel Van Driessche3
1
Institute of Condensed Matter and Nanosciences (IMCN), Division “Molecules, Solids
and reactivity” (MOST), Université catholique de Louvain, Belgium
2
Department of Petrochemistry, Hanoi University of Technology, Hanoi, Vietnam
3
Department of Inorganic and Physical Chemistry, Gent University, Krijgslaan, Gent,
Belgium
[email protected]
Shaping is a critical step in the preparation of industrial catalysts. Nevertheless, its
impact on the properties of catalytic materials remains behind the veil of industrial
secrecy. Herein, a systematic study on the effect of shaping over the properties and
functionalities of three catalytic materials is presented: namely, vanadium aluminium
mixed (hydr)oxides, bismuth molybdate, and manganese oxide. These catalysts were
tested in three model reactions: propane oxidative dehydrogenation, propylene partial
oxidation to acrolein, and benzene total oxidation, respectively. Shaping was performed
by tableting and extrusion. Graphite was used as binding agent for tableting and the
changes brought over the catalysts' physicochemical and catalytic properties were
evaluated as a function of graphite loading. In the case of extrusion, a thorough analysis
of the preparation of the extrudates and the effect of using colloidal silica as binding
agent was performed. The ensemble of results showed how crucial shaping is in
oxidation catalysis.
Page | 48
Abstract Number 1215 Oral Presentation
Session: Materials Synthesis
Sunday, June 9, 2:45 p.m., Laboratory Sciences Building, Room 300
Importance of the aviation treatment on K free and K- containing MoVSbO
catalysts for propane selective oxidation.
Francisco Ivars Barcelo1, Jean-Marc M. Millet2, Teresa Blasco Lanzuela1, Patricia
Concepción Heydorn1, Jaime S. Valente1, Jose M. López Nieto1
1
Instituto de Tecnologia Quimica (UPV-CSIC), Valencia, Spain
Institut de Recherches sur la Catalyse et l’Environnement de Lyon, IRCELYON, Lyon,
France
2
[email protected]
The use of Sb-containing Mo-V-O bronzes instead of Mo-V-Te-O (nowadays more
effective but apparently less thermally stable), has been always proposed almost in
parallel to be employed for the one-step propane selective oxidation process to obtain
acrylic acid as a more sustainable and cheaper alternative to substitute the current
industrial two-steps process from propylene.A proper activation treatment at high
temperature and the use of promoters have been widely reported as key to get
effective Sb-MoVO catalysts for propane selective oxidation. However, activation
treatments found in literature significantly differ from each other, being the main
difference the use or not of a thermal treatment in air previous to the high temperature
treatment in nitrogen. Thus, in the present work we present a comparative study about
the influence of different activating heat-treatments on the evolution of the physicchemical and catalytic properties of hydrothermally prepared K-free and K-containing
Sb-MoVO bronzes.
Page | 49
Abstract Number 1201 Oral Presentation
Session: Materials Synthesis
Sunday, June 9, 3:15, Laboratory Sciences Building, Room 300
Hydrothermal Synthesis and Characterization of Bismuth Molybdate Catalysts for
the Selective Oxidation of Propene to Acrolein
Kirsten Schuh1,Wolfgang Kleist1, Jan-Dierk Grunwaldt1, Martin Høj2, Anker Degn
Jensen2, Greta R. Patzke3
1
Karlsruhe Institute of Technology, Institute for Chemical Technology and Polymer
Chemistry, Karlsruhe, Baden-Wuerttemberg, Germany
2
Technical University of Denmark, Department of Chemical Engineering, Kgs. Lyngby,
Denmark
3
University of Zurich, Institute of Inorganic Chemistry, Zurich, Switzerland
[email protected]
This work presents a systematic study on the influence of the preparation method for
bismuth molybdate catalysts on the activity and selectivity in the oxidation of propylene
to acrolein. Different bismuth molybdate phases with well-defined morphology were
synthesized via hydrothermal methods by variation of the Bi/Mo ratio and the initial pH
value. Synthesis of the corresponding materials by flame spray pyrolysis led to
nanocrystalline oxides with relatively high surface area. The catalytic performance of
these novel materials was compared with catalysts prepared by co-precipitation.
The selectivity for acrolein remained high with increasing propylene conversion up to
45% at 400 °C using 500 mg of catalyst, a gas composition of C3H6/O2/N2 = 5/25/70 and
a flow of 50 to 120 Nml/min. Calcination of the hydrothermally synthesized samples at
550 °C strongly decreased their catalytic oxidation activity. Hence, present studies focus
on possible changes in surface area, phase and morphology during calcination and/or
catalytic tests.
Page | 50
Abstract Number 1189 Oral Presentation
Session: Materials Synthesis
Sunday, June 9, 3:45 p.m., Laboratory Sciences Building, Room 300
Synthesis of Orthorhombic Mo-W-V-Ox and its Catalytic Application in Selective
Oxidation of Acrolein to Acrylic Acid
Chen Chen1, Nakatani Kosuke1, Satoshi Ishikawa1, Zhenxin Zhang1, Wataru Ueda1, Toru
Murayama1
1
Hokkaido University, Catalysis Research Center, Sapporo, Hokkaido, Japan
[email protected]
Acrylic acid is an important bulk chemical with a broad application in polymer industry,
which is usually obtained from the catalytic oxidation of acrolein. Various pure phasic
Mo3VOx including orthorhombic, trigonal, and tetragonal system associated with the
amorphous one were successfully synthesized and utilized for catalytic oxidation of
acrolein, respectively. Crystalline structure showed obvious effect on catalytic
performance, and the orthorhombic and trigonal system were found to be much more
efficient. Furthermore, tungsten ions were incorporated in the framework of OrthMo3VOx while remaining the orthorhombic phase structure. This novel Orth-Mo-W-VOx material presents as uniform nanorod, and owns a high external surface area.
Introduction of tungsten ions showed promotion effect on the conversion of acrolein.
And what is more attractive is that, for Orth-Mo-W-V-Ox the activity remained almost
the same after water decreased by half in feed gas, while for Orth-Mo3VOx obvious
decrease of acrolein conversion happened.
Page | 51
Abstract Number 1226 Oral Presentation
Session: Materials Synthesis
Sunday, June 9, 4:15 p.m., Laboratory Sciences Building, Room 300
Combinatorial design and preparation of transition metal doped MoVTe catalysts
for oxidation of propane to acrylic acid
Andras Tompos1, Gerhard Mestl2, József L. Margitfalvi3, Lajos Végvári3
1
Institute of Materials and Environmental Chemistry, Research Centre for Natural
Sciences HAS, Renewable and Clean Energy, Budapest, Hungary
2
Clariant Produkte (Deutschland) GmbH, Department Oxidation Catalysis, Bruckmühl,
Germany
3
Combitech-Nanotech Kft., Budapest, Hungary
[email protected]
Currently, Acrylic acid (AA) is produced in a two-step process using propene as a raw
material. Nevertheless, development of a novel process based on direct selective
oxidation of propane to acrylic acid is driven by the expected price increase and
shortage of propene in the future and the increased availability of propane from shale
gas exploitation.
Mo-V-Nb-Te-O type catalysts have been developed by means of combinatorial
approaches and high-throughput experimental techniques. Beside the main
components the experimental space consisted of 7 transition metal promoters and it
was further extended by introducing two components affecting the redox behavior of
the synthesis mixture and fine distribution of the constituents in the resulted material
matrix. Microwave assisted hydrothermal synthesis led to M1 phase crystalline
materials with unexpectedly large surface area (20-40 cm2/g). In five generations
promoted catalysts providing as high as 55 % AA yield and 80 % selectivity has been
obtained.
Page | 52
Abstract Number 1253 Oral Presentation
Session: Materials Synthesis
Monday, June 10, 1:00p.m., Laboratory Sciences Building, Room 300
New look at the problem of three-way catalysts
Vedyagin Aleksey1, Mishakov IIya1, Shubin Yury2,
1
Boreskov Institute of Catalysis, Novosibirsk, Novosibirsk region, Russia
Nikolaev Institute of Inorganic Chemistry, Novosibirsk, Novosibirsk region, Russia
2
[email protected]
Three-way catalysts have been used in automotive exhaust systems since the late
1970s. The precious metals usually used in these systems are platinum, palladium and
rhodium. During the last few years a lot of studies were devoted to the development of
Pd-only catalysts. High prices on platinum and rhodium as well as instability of multicomponent catalysts were the main grounds for searching the cheap and sustainable
catalytic systems. In our work we have scientifically substantiated that the three-way
catalysts containing palladium clusters with addition of small amounts of Pt or Rh show
the superior activity. Such parameters as metal precursor, preparation procedure, and
metals ratio play the determinative role for these systems. As an example, two samples
of the same chemical composition could behave the opposite properties. New
approaches to the synthesis of bimetallic Pd-Pt and Pd-Rh catalysts with improved
activity and stability will be presented.
Page | 53
Abstract Number 1142 Oral Presentation
Session: Materials Synthesis
Monday, June 10, 1:30 p.m., Laboratory Sciences Building, Room 300
Particle size effects in selective oxidation of lactose with Pd/h-BN catalysts
Nathalie Meyer1, Michel Devillers1, Sophie Hermans1
1
Université catholique de Louvain, Institut de la Matière Condensée et des
Nanosciences, Louvain-la-Neuve, Brabant Wallon, Belgium
[email protected]
Lactose, a renewable resource, can be oxidized in lactobionic acid which has high
potential as bioactive molecule[1]. We have shown that boron nitride is a suitable
alternative as support for Pd in this reaction carried out in water[2].
various reducers, wet-impregnation (WI) in different solvents with several Pd precursors
and aqueous-impregnation (AI), were characterized by XRD, TEM, CO-chemisorption and
in situ Raman spectroscopy.
BN demonstrated its superiority: the absence of hydroxyl groups limits side reactions
and guarantees 100% selectivity. Moreover, BN stabilizes the metal in its reduced form
which is the active phase. The best catalysts were obtained by AI, followed by
WI>DP>DI. This could be related to a dispersion effect but only to some extent as
particles below 3nm are detrimental for the activity. The most active catalysts presented
Pd particle sizes between 3 and 15nm and a dispersion of ~8%.
[1] L-F. Gutiérrez, S. Hamoudi, K. Belkacemi, Intern. Dairy Journal, 26 (2012) 103-111.
[2] N. Meyer, K. Bekaert, D. Pirson, M. Devillers, S. Hermans, Catal. Comm., 29 (2012)
170-174
Page | 54
Abstract Number 1208 Oral Presentation
Session: Materials Synthesis
Monday, June 10, 2:00p.m., Laboratory Sciences Building, Room 300
Physical Grinding of Metal Acetates to form Alloyed Bimetallic Catalysts
Greg Shaw1, Simon Kondrat1, Stuart Taylor1, Peter Miedziak1, Christopher Keily2, Jennifer
Edwards1,Graham Hutchings1
1
Cardiff Catalysis Institute, Cardiff, Wales, United Kingdom
Lehigh University, Center for advanced materials and nanotechnology
2
[email protected]
Alloyed Au-Pd nanoparticles are highly effective as catalysts for the oxidation of alcohols
and the direct synthesis of hydrogen peroxide. Preparation techniques have been used
to give Au-Pd supported nanoparticles, including wet impregnation, deposition
precipitation and sol-immobilisation, use HAuCl4, making it difficult to completely
remove chloride from the catalyst. Studies have shown that Cl will interact with Au and
this interaction suppresses the catalyst activity. Metal acetate are halide free and can be
utilised as a route to provide halide free Au and AuPd catalysts. Here we report the
preparation of supported Au, Pd and Au-Pd nanoparticles by a simple preparation
technique of physically mixing the acetate salts with the support and heat treating
under helium. The catalysts prepared by this technique display exceptionally high
activity for oxidation reactions and the simplicity of preparation and absence of solvent
facilitate the scale up of the preparation without significant difficulty.
Page | 55
Abstract Number 1240 Oral Presentation
Session: Materials Synthesis
Monday, June 10, 2:45 p.m., Laboratory Sciences Building, Room 300
Controlling oxygen activation and oxygen mobility in Ce-doped strontium cobalt
ferrite perovskites
Umit S. Ozkan1, Hyunkyu Choi1,Anshuman Fuller1
1
The Ohio State University, Chemical and Biomolecular Engineering, Columbus, Ohio,
United States Of America
[email protected]
Solid oxide fuel cells (SOFCs) offer many advantages for power generation applications
due to their high efficiency and fuel flexibility. Perovskite-type materials with a general
formula of ABO3 have shown promise as both cathode and anode electro-catalysts.
Doping of the A- and/or B-sites of the perovskite material can change many properties,
including oxygen activation on the cathode and sulfur and coking resistance on the
anode. The present work is aimed at examining the effect of doping the A site with Ce
on the structure, oxygen mobility, and electro-catalytic activity of the SrFeCoO3
catalysts. Results from in-situ and ex-situ characterization studies using X-ray
photoelectron spectroscopy (XPS), X-ray absorption fine structure spectroscopy (XAFS),
X-ray diffraction (XRD), temperature programmed desorption and reduction (TPD and
TPR), Thermogravimetric analysis (TGA) as well as button-cell performance tests will be
presented. Studies examining the activity of these materials for oxidation reactions and
oxygen exchange characteristics will also be included.
.
Page | 56
Abstract Number 1190 Oral Presentation
Session: Materials Synthesis
Monday, June 10, 3:15 p.m.,Laboratory Sciences Building, Room 300
Development of an organic-inorganic hybrid method: Toward improved NiMoO4
both active and highly selective in the propane ODH
Benjamin Farin1, Eric Gaigneaux1, Colas Swalus1, Michel Devillers1
1
Université catholique de Louvain (UCL), Institute of Condensed Matter and
Nanosciences (IMCN), Louvain-la-Neuve, Belgium
[email protected]
NiMoO4 are active in the propane ODH, but do not often exhibit the required
combination of high conversion and of high propene selectivity. Herein, we report a
novel preparation route that leads to the high propene selective β-NiMoO4 (> 70%)
without sacrificing its texture, and thus maintaining its activity level high as well (> 10%).
This method is based on the controlled thermal degradation of a unique hybrid
precursor made from a copolymer displaying a supramolecular organization. The rapid
and exothermic burning of such precursors favours the stabilization of the highly
propene selective β-NiMoO4 phase. Being metastable, preparing this phase normally
requires high calcination temperatures (>650°C) which usually causes sintering, with a
resulting activity decrease. The use of copolymers to form supramolecularly organized
precursors, and the possibility it offers to form oxides under “soft conditions”, leads to
β-NiMoO4, presenting some significant porosity with correspondingly higher specific
areas.
Page | 57
Abstract Number 1197 Oral Presentation
Session: Materials Synthesis
Monday, June 10, 3;45 p.m., Laboratory Sciences Building, Room 300
Hybrid organic-inorganic catalysts efficient for advanced selectivity control in liquid
phase olefin epoxidation reaction
Colas Swalus1, Benjamin Farin1, Michel Devillers1, Eric M. Gaigneaux1
1
Institute of Condensed Matter and Nanosciences – IMCN, Division « Molecules, Solids
and reactivity – MOST, Louvain-la-Neuve, Belgium
[email protected]
Hybridization with advanced polymeric matrixes is here demonstrated to improve
considerably the selective behavior of inorganic clusters in liquid phase olefin
epoxidation reaction. Such a benefit of hybrids results from the possibility to adequately
adjust the catalyst supramolecular organization and its surface polarity. Therefore,
various nanostructured hybrids were synthesized by the insertion of polyoxometalates
in supramolecular self-assembled polymeric matrixes. The hydrophobicity of the
catalysts was tuned via the polarity of the polymer substituents. Results show (1) the
successful heterogenization of polyoxometalates, (2) exhibiting a high activity, (3) easy
recovery, (4) remarkable reusability and (5) no deactivation. Moreover (6) activity and
selectivity to epoxide considerably increase with the hydrophobicity of the polymer.
Finally (7) a further selectivity enhancement is obtained when a polar solvent is used.
Better activity and selectivity are explained by a better olefin adsorption and a faster
epoxide desorption and retrodiffusion due to the hydrophobic catalyst surface.
Page | 58
Abstract Number 1196 Oral Presentation
Session: Materials Synthesis
Monday, June 10, 4:15 p.m., Laboratory Sciences Building, Room 300
Hydropobic gold catalysts: Synthesis and application in oxidation catalysis
Valérie Caps1, Fabrice Vigneron1, Cuong Pham-Huu1,Alexandre Piquet1, Véronique
Pitchon1,Walid Baaziz1, Corinne Petit1
1
CNRS/University of Strasbourg, ICPEES - Institut de Chimie et Procédés pour l'Energie,
l'Environnement et la Santé, Strasbourg, France
[email protected]
Gold nanoparticles have proven highly effective in catalyzing oxidations at low
temperature. Under these conditions, dissociative adsorption of oxygen on gold is
energetically disfavored and oxygen activation relies on the presence of a reducible
oxide support interacting with the particles. However, when a sacrificial reductant is cofed with the substrate (e.g. in the PROX reaction), other modes of oxygen activation are
triggered on the gold surface.1 Hence, alternative supports can be associated with gold.
Passivated silicas2 for example have shown particularly suitable for ensuring optimal
dispersion of the catalyst within the apolar liquid media of gold-catalyzed aerobic cooxidations of higher alkanes and alkenes,3 which has prompted us to design new
methods for the formation of gold nanoparticles over hydrophobic silicas.4 The new
strategies currently developed at ICPEES (ex-LMSPC) for preparing gold nanoparticles
directly at the surface of other hydrophobic supports, such as unfunctionalized pristine
few layers graphene, will be presented.
Page | 59
Abstract Number 1199 Oral Presentation
Session: Materials Synthesis
Tuesday, June 11, 1:00p.m., Brauer Hall, Room 12
Selective side-chain oxidation of alkyl aromatic compounds on promoted
vanadium based materials
Florea Mihaela1, Florentina Neatu1, Roxana S. Marin1, Codruta G. Rotaru1, Vasile I.
Parvulescu1
1
University of Bucharest, Department of Organic Chemistry, Biochemistry and Catalysis,
Bucharest, Romania
[email protected]
Vanadium-aluminum oxides doped with gallium or iron were successfully synthesized
through co-precipitation and tested in p-xylene and toluene selective oxidation. The
effects of pH, vanadium concentration, V/Al and Fe(Ga)/Al molar ratio were investigated
by using different techniques. Catalytic tests were carried out in aerobic conditions,
with/without solvent. The results of this study showed that the texture, chemical
composition, reducibility and nature of the vanadium oxide species were strongly
influenced by the vanadium concentration, co-precipitation pH and metal promotion.
Two promotion effects were identified: increase in surface area observed for the Ga/Fepromoted catalysts and the change in the reduction temperature, indicated that the
promotor is either acting as an electronic modifier affecting the oxidation state of the
catalyst or is introducing defects, due to the substitution of VO2+ by Ga3+. Higher
conversions of p-xylene and toluene for promoted samples were attributed to higher
mobility of the lattice oxygen to the surface.
Page | 60
Abstract Number 1127 Oral Presentation
Session: Materials Synthesis
Tuesday, June 11, 1:30 p.m., Laboratory Sciences Building, Room 300
Simple and scalable synthesis of highly active Lewis acidic Sn-β for Baeyer-Villiger
oxidation
Prof. Ive Hermans1
1
ETH Zurich, Zurich, Switzerland
[email protected]
Sn-β is a Lewis acidic zeolite with high potential in the area of sustainable oxidation
chemistry. Nevertheless, the lengthy and complicated synthesis and the low amount of
active metal incorporated per kilogram of catalyst, as well as the large crystallite sizes
curtail industrial implementation.Recently, we reported a novel route for the
preparation of Sn-β, via a two-step procedure. A commercial β-zeolite, possessing small
crystallite size and a high SiO2/Al2O3 ratio, was dealuminated by an acidic treatment in
concentrated HNO3. Subsequently, the dealuminated zeolite was mechanically mixed
with tin(II)acetate, followed by a high temperature treatment in air (550 ºC). A
multitude of spectroscopic techniques verified that the catalyst contained isolated,
tetrahedral SnIV sites, and the catalytic performance was evaluated for Baeyer-Villiger
oxidations. Given its high active metal content and favourable physical properties, the
observed space-time-yield was one order-of-magnitude higher than previously reported
for these reactions.
ACIE 2012, 51, 11736 (+cover)
Page | 61
Abstract Number 1257 Oral Presentation
Session: Materials Synthesis
Tuesday, June 11, 2:00p.m., Brauer Hall, Room 12
Synthesis and characterization of layered precursors based in transition metal
and its catalytic tets in benzyl alcohol oxidation
Adriana Echavarría Isaza 1, Alfonso Enrique Ramirez Sanabria2, Cristian David Miranda
Muñoz2, Johana Arboleda Echavarría1, John Mario Franco Ramírez1
1
Universidad de Antioquia, Instituto de Química - Grupo Catalizadores y Adsorbentes,
Medellín, Antioquia, Colombia
2
Universidad del Cauca, Departamento de Química - Grupo de Catálisis, Popayán, Cauca,
Colombia
[email protected]
Two bi-metal and tri-metal compounds (NiV and CuNiV) were synthesized by
hydrothermal method in order to obtain precursors for catalyst useful in benzyl alcohol
oxidation reaction. X-ray diffraction (XRD) analysis showed that precursors exhibited Фz
lamellar phase (PDF 01-087-0417), however, the diffractions patterns showed small
differences, attributed to different chemical composition. Using thermogravimetric
analysis (TGA), calcination temperature was established to 400°C. At this temperature,
materials have reached thermal stability and complete formation of mixed oxides.
Others characterization technics were used. Catalytic tests were conducted in a threenecked flask coupled to a condenser, with an oxygen flow for 6 hours. Catalytic results
showed a selectivity to benzaldehyde of 100%, with conversion of benzyl alcohol of 56%,
using NiV, and 47% using CuNiV.
Page | 62
Abstract Number 1134 Oral Presentation
Session: Materials Synthesis
Wednesday, June 12, 2:45 p.m., Brauer Hall, Room 12
Controlable properties of Csx(NH4)3-xHPMo11VO40 mixed-salts catalysts Influence on the performances for the selective oxidation of isobutane into
methacrylic acid
Sébastien Paul1 , Benjamin Katryniok1, Elisabeth Bordes-Richard1, Fangli Jing2, Franck
Dumeigmil2
1
Ecole Centrale de Lille, Unité de Catalyse et de Chimie du Solide (UCCS, UMR CNRS
8181), Villeneuve d'Ascq, Nord, Franc
2
Lille 1 University, Unité de Catalyse et de Chimie du Solide (UCCS, UMR CNRS 8181),
Villeneuve d'Ascq, Nord, France
[email protected]
The selective oxidation of isobutane represents a simple, economical and
environmentally-friendly route to produce valuable chemical intermediates such as
methacrolein and methacrylic acid. The Keggin-type heteropolycompounds are effective
catalysts for this reaction, as they possesses tunable redox and acidic properties. In this
work, we introduced various amount of Cs+ cations into (NH4)3HPMo11VO40 to modify
the textural properties and the stability of the catalyst. It showed that the textural
properties strongly depend on the Cs amount. Actually a progressive transition from
non-porous to mesoporous properties, and a linear increase of the surface area was
observed as the Cs content increased. On the contrary, the acidity showed an inverselinear relationship with the increase of Cs amount. The best catalytic results were
observed for medium surface area and acidity corresponding to a Cs number between
1.7 and 2.5 per Keggin unit. This optimum can be related to a high acid site surface
density.
Page | 63
Abstract Number 1265 Oral Presentation
Session: Materials Synthesis
Wedneday, June 12, 3:15 p.m., Brauer Hall, Room 12
Alternative Catalyst for the selective oxidation in the SuperClaus Process
Roberto Garcia de Leon1, Brent Handy2, Miriam Jazmin Cueto Bernal1, Joanan Lopez
Morales1
1
Instituto Mexicano del Petroleo, Dirección de Investigación y Posgrado, Distrito Federal,
Mexico
2
Universidad Autónoma de San Luis Potosí, Facultad de Ciencias Químicas, San Luis
Potosí, Mexico
[email protected]
Alternative catalytic systems for the selective oxidation (SUPERCLAUS® process) were
synthesized, such as TiO2-SiO2, Active carbon, Fe2O3/MCM and Al2O3 based nanotubes
modified with Ce, La and V.
The catalysts were characterized and evaluated, in a first stage using a feed stream
consisting of H2S, O2 and N2. In a second stage, in closer Industrial scenery, 10 and 20 %
mole water in the feed stream was fed. From the experimental results, in the absence of
water, most of the catalysts exhibited high activity in the oxidation of H2S and selectivity
to So. In presence of water some catalysts activities decreased however others
maintained high activity, stability and selectivity, with conversions between 98 and 99
%wt of H2S, reaching the level of the reference catalyst with high selectivity towards
So> 95%. The preparation technique and hereby the active phase dispersion on the
support for the catalytic performance are absolutely critical.
Page | 64
Abstract Number 1256 Oral Presentation
Session: Materials Synthesis
Wednesday, June 12, 3:45, Brauer Hall, Room 12
The Palladium effective catalyst for “green” process.
V.G. Matveeva1, E.M. Sulman1, V.Yu. Doluda1, M.G. Sulman1, B.D. Stein2, L.M.
Bronstein2,3,4,
1
Tver State Technical University, Department of Chemistry,Tver, Russia
Indiana University, Department of Biology, Bloomington, United States of America
3
A.N. Nesmeyanov Institute of Organoelement Compounds, Moscow, Russia
4
King Abdulaziz University, Faculty of Science, Department of Physics
Jeddah, Saudi Arabia
2
[email protected]
In recent years, sustainable “green” process received considerable attention because
the use of environmentally friendly solvents and decreased energy consumption
became requirements for chemical industry in many countries [1, 2]. It is already well
established that catalytic nanoparticles (NPs) posses unique catalytic properties due to
large surface areas and a considerable number of surface atoms leading to an increased
amount of active sites [3-5].
In this abstract we suggest formation of Pd-containing nanoparticulate catalysts based
on hypercrosslinked polystyrene (HPS) as a support and palladium acetate as a Pd
precursor in direct catalytic oxidation of D-glucose to D-gluconic acid. This reaction is of
both fundamental and technological importance [6, 7]. D-gluconic acid and its Ca salt
are used in industry for pharmaceuticals and food supplement production. D-glucose
oxidation is carried out in water which makes it especially appealing for environmentally
friendly catalysis.
The catalysts developed were characterized using transmission electron microscopy
(TEM), X-ray photoelectron spectroscopy (XPS), nitrogen physisorption and were studied
in D-glucose oxidation by oxygen. These catalysts demonstrated high selectivity and
stability along with reasonable activity, making them promising for industrial
applications in sustainable processes.
We suppose that formation of well-defined Pd-containing NPs can be controlled in the
pores of HPS. This nanocomposite can be used directly in the D-glucose catalytic
oxidation and then catalytic species from in situ. Alternatively, the catalytic NPs can be
formed by hydrogen reduction of Pd acetate in the HPS pores. In the former case, direct
D-glucose oxidation shows an induction period when catalytically active sites are formed
while in the latter case, no induction period is observed. This prefabricated catalyst
shows significantly higher catalytic activity although selectivity drops. On other hand,
the decrease of the Pd precursor loading allows higher activity and selectivity of the
Page | 65
prefabricated NPs than in the case of a higher loading. We believe that this is due to
smaller Pd/PdO NPs with lower activation energy of the catalytic reaction which display
higher catalytic activity at selectivity making it a promising candidate for industrial
applications in sustainable processes.
Authors sencerely thanks Rassuin Minestery of Education, Russian fond of basic
research and Seventh Framework Programme of the European Community (CP-IP
246095-2 POLYCAT) for finansial support.
Page | 66
Abstract Number 1131 Oral Presentation
Session: Materials Synthesis
Wednesday, June 12, 4:15 p.m. ,Brauer Hall, Room 12
In situ carbon templating as a new route for anchoring Lithium in Magnesium
Oxide Lattice
G. Raman 1, K.Seshan1, L. Lefferts1
1
University of Twente, Catalytic Processes and Materials
(CPM), Enschede, Overijssel, The Netherlands
[email protected]
Oxycracking of hydrocarbons converts alkanes to alkenes which are used to synthesize
variety of polymers. This reaction is considered as an alternate to steam cracking.
Typical oxidation catalysts that possess redox properties, V2O5, MoO3 show selectivity
towards combustion reactions. Non redox catalysts such as Li/MgO improve olefin
yields, during oxy-cracking of hydrocarbons. But lithium doping in MgO is difficult and
results in low surface area and low catalytic activity. This contribution describes a novel
method of doping lithium in magnesium oxide is by in-situ carbon templating. This
method gives high surface area Magnesium oxide in which considerable amount of
lithium is incorporated. Lithium is well dispersed in MgO up to 10 wt% loading in
contrast to conventional impregnation and sol-gel method. Lithuim doped magnesium
oxide prepared by in-situ carbon templating shows two-three times higher conversion
than Li/MgO prepared without carbon in propane and hexane oxycracking. The detailed
characterization and catalytic activity will be presented.
Page | 67
B2. Greener Oxidants, Alternative Oxidants
Abstract Number 1165 Oral Presentation
Session: Greener Oxidants, Alternative Oxidants
Tuesday, June 11, 1:00p.m., Green Hall, Rodin Auditorium
Green oxidation of fine chemicals in the presence of bifunctional catalysts
Tatiana B. Khlebnikova1, Zinaida P. Pai1, Dmitry Yu. Yushchenko1, Yulia V. Mattsat1,
Natalia V. Selivanova1
1
Boreskov Institute of Catalysis, Department of Catalytic Processes of Fine Chemicals
Synthesis, Novosibirsk, Russia
[email protected]
Selective oxidation of various classes of organic substrates (olefins, alcohols, amines)
with hydrogen peroxide was performed in the presence of catalysts combining the
properties of metal complex and phase-transfer catalysts. The catalytic oxidation
proceeds without the use of organic solvents and explosive oxidants, at atmospheric
pressure and temperatures below 1000C, using catalyst concentrations of 0.1-1 mol. %
against substrate. Two-phase reaction media (organic phase - water phase) facilitates
the separation of catalyst and products remaining in different phases. The structure of
the catalysts composed of peroxopolyoxometalates and quaternary ammonium cations
and its influence on the catalytic properties were studied using EXAFS, IR, and Raman
spectroscopy. The efficient methods of oxidation of aromatic and aliphatic alcohols,
linear and cyclic olefins, unsaturated fatty acids, amines and amino acids yielding
epoxides, carbonic acids, and N-oxides have been developed. The valuable products
have been obtained with high conversions (90-100%) and selectivities (85-95%).
Page | 68
Abstract Number 1150 Oral Presentation
Session: Greener Oxidants, Alternative Oxidants
Tuesday, June 11, 1:30 p.m., Green Hall, Rodin Auditorium
Influence of the chemical composition of the brucite-type layer of LDHcompounds ZnxAl, MgxAl on their catalytic activity for the epoxidation of olefins
using H2O2 as greener oxidant
Rodica Zavoianu1, Octavian Dumitru Pavel1, Corina Bradu1, Emilian Angelescu1, Anca
Cruceanu1, Ruxandra Birijega2
1
University of Bucharest, Faculty of Chemistry, Organic Chemistry, Biochemistry and
Catalysis, Bucharest, Romania
2
National Institute for Physics of Lasers, Plasma and Radiation, Bucharest, Romania
[email protected]
This contribution concerns the effect of chemical composition of the brucite-type layer
of LDHs materials ZnxAl and MgxAl (x = 2 - 5) on their catalytic activity for olefin
epoxidation with H2O2 in the presence of acetonitrile. LDH materials were prepared by
the standard method of coprecipitation at constant pH 10, using an aqueous solution of
the corresponding metal nitrates and a base solution containing NaOH and Na2CO3. The
fresh LDHs were calcined to yield the corresponding mixed oxides and then the
reconstruction of the LDHs structure by hydration of the mixed oxides was
performed. The resulted samples were characterized by XRD, DRIFT, SEM-EDX and
determination of base sites. The results of the catalytic tests for olefin epoxidation were
well correlated with the basicity of the samples which was at its turn related to the ratio
x (M2+/Al) and the electronegativity of the bivalent metal in the brucite type layer.
Page | 69
Abstract Number 1251 Oral Presentation
Session: Greener Oxidants, Alternative Oxidants
Tuesday, June 11, 2:00p.m., Green Hall, Rodin Auditorium
Oxidative Carbonylation of Phenol to Diphenyl Carbonate using Pd Electrocatalyst
Ichiro Yamanaka1, Ryoichi Kanega1,
1
Tokyo Institute of Technology, Department of Chemistry and Materials Science,
Neguro-ku, Tokyo, Japan
[email protected]
Diphenyl carbonate (DPC) is received much attention as alternative of phosgene. The
industrial DPC production is operated by using phosgene or dimethyl carbonate for
transesterifications. Recently our research group have found and reported that
oxidative carbonylation of phenol to DPC by a heterogeneous Pd electrocatalyst under
mild conditions. To increase the formation rate and selectivity of DPC, a new
homogeneous Pd electrocatalyst was screened and developed. Oxidative
electrochemical carbonylation of phenol with CO to DPC using Pd electrocatalyst was
studied at P(CO) = 1 atm and room temperature. Oxidative electrochemical
carbonylation was conducted by galvanostatic electrolysis at 1 mA in an electrolyte
containing phenol, sodium phenoxide, and CH3CN. It was found that electrochemical
carbonylation by Pd was promoted by using N-heterocyclic carbene (NHC) ligands. The
current efficiency of DPC increased and the maximum current efficiency was 80% by
using .
Page | 70
Abstract Number 1242 Oral Presentation
Session: Greener Oxidants, Alternative Oxidants
Tuesday, June 11th, 2:45, p.m., Green Hall, Rodin Auditorium
Anthracycline mediated photocatalytic formation of hydrogen peroxide
Nawara Krzysztof 1, Pawel Krysiński1, Gary J. Blanchard2
1
University of Warsaw, Chemistry, Warszawa, Poland
Michigan State University, Chemistry, East Lansing, Michigan, United States of America
2
[email protected]
Anthracyclines are water soluble derivatives of 1,4-dihydroxyanthraquinones. These
bacterium derived compounds are commonly used in medicine to treat wide variety of
cancers. One process that is involved in anthracycline's biological activity is called redox
cycling. It occurs at 1,4-dihydroxyanthraquinone part of the molecule. In this process the
molecule undergoes enzymatic reduction to the corresponding 1,4dihydroxyhydroquinone. Subsequently, in the presence of oxygen and water, the
dihydroquinone is reoxidized to the anthracycline with the formation of hydrogen
peroxide. We have shown that the same chemical process can proceed without enzyme.
Anthracycline solutions exposed to UV radiation undergo reduction. The product in
contact with dissolved oxygen spontaneously oxidizes back to anthracycline and
hydrogen peroxide is produced. In this process anthracycline function as the catalyst for
hydrogen peroxide formation. It offers some advantages over Riedl-Pfleiderer synthesis
of hydrogen peroxide.
Page | 71
Abstract Number 1140 Oral Presentation
Session: Greener Oxidants, Alternative Oxidants
Tuesday, June 11, 3:15p.m., Green Hall, Rodin Auditorium
Chemo- and Regioselective Hydroxylation of Aromatics to Phenols with Hydrogen
Peroxide Catalyzed by a Divanadium-Substituted Polyoxometalate
Noritaka Mizuno1, Keigo Kamata1
1
The University of Tokyo, Department of Applied Chemistry, Tokyo, Japan
[email protected]
Phenols with one or more functional groups are valuable organic intermediates related
to resins, plastics, pharmaceuticals, and agrochemicals in chemical industries. Herein,
we report direct hydroxylation of various kinds of structurally-diverse aromatics to
phenols catalyzed by a divanadium-substituted polyoxometalate, [g-PW10O38V2(mOH)2]3− with aqueous hydrogen peroxide.[1] The present system showed specific
regioselectivities to para-phenols for mono-substituted benzenes. The orthohydroxylation would be suppressed by the steric crowding between the
polyoxometalate framework and substituents, resulting in the high regioselectivities to
para-phenols (74-95%). In addition, alkylaromatics with reactive primary, secondary,
and tertiary aromatic side-chain sp3 C-H bonds could chemoselectively be hydroxylated
without significant formation of the side-chain oxygenated products. Notably, xanthene
with the very weak aromatic side chain sp3 C-H bonds (BDE: 326 kJ mol-1) was
selectively hydroxylated to xanthen-2-ol.
[1] K. Kamata, T. Yamaura, N. Mizuno, Angew. Chem. Int. Ed. 2012, 51, 7275-7279.
Page | 72
Abstract Number 1261 Oral Presentation
Session: Greener Oxidants, Alternative Oxidants
Tuesday, June 11, 3:45 p.m. Green Hall, Rodin Auditorium
Enzymatic oxidation of phenols by immobilized oxidoreductases
E. Sulman1, V. Matveeva1, B. Tikhonov1, O. Matveeva1, N. Lakina1,A. Sidorov1
1
Tver Technical University, Department of Biotechnology and Chemistry, Tver, Russia
[email protected]
The use of oxidoreductases in the industrial catalysis has considerably increased
recently. In this work catalytic efficiency of peroxidase and tyrosinase from various
sources were investigated. 7 various cation-exchange resins on the basis of
styrenedivynilbenzene with SO3H or COOH active groups were used as the carriers. Ion
exchangers were treated with sodium alginat, chitosan, glutaric dialdehyde and
carbodiimide hydrochloride. Oxidation in the presence of tyrosinase was performed by
atmospheric oxygen. The activity of biocatalysts was defined in reactions of oxidation of
phenol and catechol to melanin-type polymers. Experiments showed that the most
efficient carriers are Ku 2-8 and Amberlite 200, which functional groups (SO3H) ave high
reactivity. Besides, they can be applied for biocatalysis by surface characteristics. For the
investigated biocatalysts the optimal conditions of phenols oxidation process with the
achievement of high degree of conversion (more than 95 %) were found: temperature 25 °C, intensity of mixing - 300 min-1, pH 6.5 and 7 - for peroxidase and tyrosinase,
respectively. The optimal ratio of the components of the catalytic systems was
determined, and physicochemical investigations (FTIR spectroscopy, XPS, nitrogen
physicosorption) of optimal biocatalytic systems were carried out. During the
measurements it was determined that consecutive deposition of chitosan and glutaric
aldehyde on cation-exchanger provides the strongest and more stable bounding of
enzyme with the carrier. Kinetic and physicochemical investigations showed that
biopolymer (chitosan) is distributed on the surface of the carrier as separate molecules
or bidimentional clasters without formation of 3D structures. Such distribution
promotes minimization of intradiffusive limitation during the oxidation. The decrease
ofimmobilized peroxidase and tyrosinase activities are the consequence of
heterogenization of enzymes and the influence of intradiffusive factors. However,
biocatalysts are stable in more than 10 cycles, and heterogenization makes the system
more technological. One more advantage of the developed biocatalytic systems is an
essential depreciation of catalyst due to the obtaining of enzymes from vegetative raw
material without expensive purification.
Page | 73
Abstract Number 1223 Oral Presentation
Session: Greener Oxidants, Alternative Oxidants
Tuesday, June 11, 4:15 p.m., Green Hall, Rodin Auditorium
Versatile eco-friendly Pickering emulsions for hydrogen peroxide-based catalytic
oxidations
Véronique Nardello-Rataj1, Adrien Mouret1, Roberto Company1, Loïc Leclercq1,JeanMarie Aubry1
1
University Lille 1, Chemistry, Villeneuve d'Ascq, France
[email protected]
Pickering emulsions are emulsions stabilized by colloidal particles. Up to now, despite
their numerous advantages, they have been very little applied to catalysis. First, we will
show that the combination of an alkyl quaternary ammonium with a polyoxometalate
(POM) provides spherical catalytic nanoparticles which are able to stabilize W/O
emulsions. The aqueous droplets (≈ 50 µm) are stabilized by [CnH2n+1]3[POM] (n = 10
or 12) solid particles (≈ 30 nm estimated from TEM and DLS) adsorbed at the
water/solvent interface. Then, solvent-less Pickering emulsions stabilized by inclusion
complexes between cyclodextrins and substrates will also be presented. For both of
these non conventional reaction media, the catalytic performances will be illustrated
with the oxidation of various substrates (olefins, organosulfurs, alcohols) and the
physicochemical parameters controlling their formation will be discussed. These ecofriendly microstructured systems show high efficiency, afford an easy work-up as they
are destabilized on demand and they are recycled without loss of activity.
Page | 74
Abstract Number 1126 Oral Presentation
Session: Greener Oxidants, Alternative Oxidants
Wednesday, June 12, 10:30 a.m., Green Hall, Rodin Auditorium
The oxidation of 1,2-cyclohexanediol to adipic acid with oxygen: A study on
selectivity affecting parameters
Elena Rozhko1, Fabrizio Cavani1,
Accorinti2, Pierpaolo Babini2
Katerina Raabova1, Stefano Alini2,
Pasquale
1
University of Bologna, Dipartimento di Chimica Industriale "Toso Montanari", Bologna,
Italy
2
Radici Chimica SpA, Novara, Italy
[email protected]
The aerobic oxidation of trans-1,2-cyclohexanediol, aimed at the synthesis of adipic acid
(AA), has been investigated using either supported Ru(OH)3 catalysts, under basic
conditions, or Keggin-type P/Mo/V polyoxometalates, under acid conditions. The Rucontaining catalyst was very efficient in the double oxidehydrogenation of the two C-OH
groups to yield the 1,2-cyclohexanedione; the latter compound underwent several
undesired side reactions which were responsible in the end for the low yield to AA. The
formation of AA occurred via the intermediate formation of 6-hydroxycaprolactone, the
latter being formed by intramolecular Cannizzaro-type disproportionation of 1,2cyclohexanedione. Polyoxometalates were extremely selective to AA (especially the
compound with composition H4PMo11VO40), but under acid conditions, AA reacted
with 1,2-cyclohexanediol to yield the corresponding ester. Overall, the possibility to
selectively transform 1,2-cyclohexanediol into AA is limited either by the characteristics
of the key reaction intermediate which forms under basic conditions, 1,2cyclohexanedione, or by the nature of the reactant itself.
Page | 75
Abstract Number 1195 Oral Presentation
Session: Greener Oxidants, Alternative Oxidants
Tuesday, June 11, 11:00 a.m., Green Hall, Rodin Auditorium
Gold-catalyzed aerobic epoxidation of stilbene in methylcyclohexane: Kinetic
study of the co-oxidation mechanism
Valérie Caps1,2, Kevin Guillois2,Alain Tuel2,
1
CNRS/University of Strasbourg, ICPEES - Institut de Chimie et Procédés pour l'Energie,
l'Environnement et la Santé, Strasbourg,France
2
CNRS/University of Lyon, IRCELYON - Institut de recherches sur la catalyse et
l'environnement de Lyon (UMR5256), Villeurbanne, France
[email protected]
Gold nanoparticles have turned out to be efficient oxidation catalysts at low
temperature. They catalyze the aerobic epoxidation of stilbene (tS) in
methylcyclohexane (MCH) highly selectively, whether unsupported [1] or dispersed over
hydrophobic supports [2]. The identification (GC-MS) and quantification
(triphenylphosphine titration followed by 31P NMR) of methylcyclohexyl hydroperoxide
(MCOOH) has recently suggested that the radical mechanism involved interconnected
methylcyclohexane autoxidation and stilbene epoxidation pathways, both leading to the
production of methylcyclohexan-1-ol (MCOH) [3].
In this communication, we will present the kinetics of this alkane/alkene co-oxidation
over a reference hydrophobic gold catalyst developed previously [4], including the effect
of the MCH/tS/Au ratios on MCOH, MCOOH and epoxide apparent production rates,
which shows that:
- gold is involved in both hydroperoxide degradation and radical recombination
(termination)
- each reactant can act as a promoter for the selective oxidation of the other by
enhancing propagation (MCH) or inhibiting termination (tS).
1. M. Boualleg, K. Guillois, B. Istria, L. Burel, L. Veyre, J.-M. Basset, C. Thieuleux, V. Caps,
Chem. Commun. 46 (2010) 5361.
2. D. Gajan, K. Guillois, P. Delichère, J.-M. Basset, J.-P. Candy, V. Caps, C. Copéret, A.
Lesage, L. Emsley, J. Am. Chem. Soc. 131 (2009) 14667.
3. K. Guillois, A. Tuel, V. Caps, Catal. Today (2013) in press.
4. K. Guillois, L. Burel, A. Tuel, V. Caps, Appl. Catal. A 415-416 (2012) 1.
Page | 76
Abstract Number 1123 Oral Presentation
Session: Greener Oxidants, Alternative Oxidants
Wednesday, June 12, 11:30 a.m., Green Hall, Rodin Auditorium
Metal-Free Carbon Activation of Peroxymonosulfate for Catalytic Degradation of
Aqueous Contaminants
Shaobin Wang1, Edy Saputra1, Syaifullah Muhammad1, Hongqi Sun1, Ha-Ming Ang1,
Moses O. Tadé1
1
Curtin University, Department of Chemical Engineering, Perth, Western Australia,
Austrlia
[email protected]
Activated carbons (AC) have been widely used in heterogeneous catalysis either as
supports or catalysts. Some recent results have shown that activated carbons are active
in degradation of aqueous organic pollutants in the presence of H2O2, due to the
formation of hydroxyl radicals. However, AC exhibits much low activity in such a
reaction. Recently, sulphate radicals have been proposed as an alternative to hydroxyl
radicals for organic degradation. Up to now, activation of persulphate (PS) or
peroxymonosulfate (PMS) was only achieved by metal ions, heat and light, which either
requires high energy input or produces metal toxicity. No investigation has been
reported using carbonaceous materials for production of sulphate radicals. In this work,
we demonstrate for the first time that AC can be a green catalyst in effective activation
of peroxymonosulphate for degradation of phenol in high efficiency. The complete
phenol removal could be achieved at 0.2 g AC in 15 min. It was also found that phenol
degradation is significantly influenced by amount of PMS loading and particle size of AC.
Page | 77
B3. New Ideas for Decoding Catalyst Complexity
Abstract Number 1154 Oral Presentation
Session: New Ideas for Decoding Catalyst Complexity
Sunday, June 9, 2:45, Green Hall, Rodin Auditorium
Selective Oxidation using Ultra Low Loaded Au Catalysts
Jennifer Edwards1, Adrian Thomas1, Qian He2
1
Cardiff Catalysis Institute, Chemistry, Cardiff, United Kingdom
Lehigh University, Department of Materials Science and Engineering, PA, U.S.A.
2
[email protected]
Cyanide leaching was used to obtain Au/SiO2 catalysts with very low gold loadings.
Catalysts with nominal 5 wt% loading were prepared using impregnation and deposition
precipitation techniques and were found to be active catalysts for the solvent-free
aerobic oxidation of benzyl alcohol. Exposure of these catalysts to a basic solution of
NaCN for 600s leached gold from the materials to give catalysts which were found to
contain just 0.06 wt% Au. The concentration of Au removed from the catalyst was
constant regardless of the length of NaCN exposure. When the cyanide leached
materials were employed for alcohol oxidation the conversions were identical to the
parent catalysts. When the activity was normalised to Au content the TOFs were much
higher for the NaCN treated catalysts (>400,000 h-1). These results demonstrate that
NaCN leaching is an effective route to the development of catalysts containing very low
gold content, whilst maintaining high activity
Page | 78
Abstract Number 1141 Oral Presentation
Session: New Ideas for Decoding Catalyst Complexity
Sunday, June 9, 3:15 p.m., Green Hall, Rodin Auditorium
A Novel Class of the Oscillating Reactions: Homogeneous Carbonylation of
Unsaturated Compounds in Pd Complexes Solutions
Sergey Gorodsky1
1
Moscow State University of Fine Chemical Technologies, Basic organic synthesis,
Moscow, Russia
[email protected]
The most part of oscillatory homogeneous reactions investigated in chemistry are
processes of organic substrate oxidation by strong oxidants. The investigations of
oscillating modes of the oxidative carbonylation reactions in homogeneous catalysis by
metal complex in alcohol solutions of palladium complexes with various organic
substrates were conducted in our university for several years.
We have showed that the phenomenon of oscillations can be observed for reactions
with participation of different alkynes, and also in different catalytic systems, for
example, in system PdBr2 - LiBr, in which the occurrence of chaotic oscillations was
demonstrated. The modes of developed oscillations in reactions involving phenyl- and
methyl acetylene, 2-methyl-3-butin-2-ol, 2-propin-1-ol in the systems PdI2-KI-CO-O2CH3OH; PdBr2-LiBr-CO-O2-CH3OH; PdBr2-LiBr-CO-O2-(CH3)2CO-H2O have been found.
Recently very interesting modes of oscillations in carbonylation reactions of 1-nonin, 1decin and 1-dodecin in the system PdI2-KI-CO-O2-CH3OH were found.
Page | 79
Abstract Number 1213 Oral Presentation
Session: New Ideas for Decoding Catalyst Complexity
Sunday, June 9, 3:45, Green Hall, Rodin Auditorium
Microwave conductivity measurements in a resonant cavity: A powerful in situ
technique for elucidating the relevance of interfacial charge transfer in selective
oxidation catalysis
Maik Eichelbaum1, Christian Heine1, Frank Rosowski2, Annette Trunschke1, Robert
Schlögl1
1
Fritz-Haber-Institut der Max-Planck-Gesellschaft,BasCat UniCat-BASF Joint
Lab,Berlin,Germany
2
BASF SE, BasCat UniCat-BASF Joint Lab, Berlin, Germany
[email protected]
Based on our newly developed contact-free microwave cavity perturbation technique
[1,2] the electrical conductivity (i.e. catalyst-substrate charge transfer) of vanadium(III),
(IV) and (V) oxide and phosphate catalysts is studied under reaction conditions for the
selective oxidation of ethane, propane and n-butane with unprecedented sensitivity.
The conductivity response on temperature, gas phase, gas flow and time (kinetics) is
directly compared to complementary in situ measurements performed under similar
reaction conditions (XPS, NEXAFS: surface, sub-surface; XRD: bulk crystal phase; Raman:
bulk, sub-surface; UV-Vis: bulk, point defects; FTIR: surface, adsorbates). By correlating
these results with the catalytic performance of active and inactive as well as selective
and unselective samples, bulk and (sub-)surface charge transfer processes are
discriminated and the relevance of each on the respective catalytic properties is
elucidated.
[1] M. Eichelbaum et al., Phys. Chem. Chem. Phys. 14, 1302 (2012).
[2] M. Eichelbaum et al., Angew. Chem. Int. Ed. 51, 6246 (2012).
Page | 80
Abstract Number: 1263 Oral Presentation
Session: New Ideas for Decoding Catalyst Complexity
Sunday, June 9, 4:15p.m., Green Hall, Rodin Auditorium
Minimalist Atomic Synthesis and TAP Kinetic Analysis: A New Approach to
Unraveling the Complexity of Mixed Metal Oxide Catalysts
John Gleaves1
1
Washington University, Department of Energy, Enivironmental and Chemical
Engineering, Saint Louis, Missouri, USA
[email protected]
This presentation will discuss a new advanced Temporal Analysis of Products (TAP)
Reactor System, which allows one to perform incremental surface modification and
precise kinetic characterization. Using this system mixed metal and metal-metal oxide
films can be deposited on a variety of different substrates including single crystals,
micron sized catalyst and support particles, and sapphire or quartz spheres. A
continuous range of metal dispersions from discreet atoms to nanoparticles, to
multilayer metal films and deposits composed of several different metals can be
produced. Exposing a substrate to a beam of metal atoms and low background pressure
of oxygen mixed metal-metal oxide deposits can be created. Altering the metal atom
deposition rate, the oxygen feed (using continuous or intermittent input), or other
reaction factors can control the metal-oxygen ratio and the nature and amount of the
deposit. Deposits ranging from nonstoichiometric metal oxide islands to full metal oxide
films can be produced in this fashion. As an example, we discuss the reaction of C3
hydrocarbons with mixed metal oxides exposed to a stepwise addition of submonolayer
quantities of Pt atoms. The example illustrates how a minimalist atomic synthesis
approach allows one to detect the onset of catalytic properties, and characterize the
evolution of catalytic properties on a complex surface.
Page | 81
C1. Petrochemicals: Raw and Intermediates
Abstract Number 1209 Oral Presentation
Session: Pertrochemicals: Raw and Intermediates
Wedneday, June 12, 3:15 p.m., Lopata Hall, Room 101
Investigation of engineering aspects in ethane ODH over highly selective
Ni0.85Nb0.15Ox catalyst
Zinovia Skoufa1, Eleni Heracleous1, Angeliki A. Lemonidou1
1
Atistotle University of Thessaloniki, Thessaloniki, Greece
[email protected]
The objective of the present study is the investigation of engineering aspects affecting
ethylene production in ethane ODH over Ni0.85Nb0.15Ox catalyst. Ethylene selectivity is
enhanced by the use of C2H6/O2 ratios higher than 1 and introducing a denser reactant
mixture in the catalytic reactor leads to increased ethylene productivity. Experimental
and modeling results showed that enhanced ethylene selectivity with high conversion
can be achieved with staged oxidant admission. On the other hand, a minimum oxygen
concentration in the reactant mixture is always required in order to maintain the
catalyst in oxidized state, thus excluding operation in a redox/ decoupling mode.
Considering reactor type, preliminary testing of the NiNbO catalyst under fluid bed
conditions proves quite promising. Finally, Ni0.85Nb0.15Ox mixed oxide presented
satisfactory stability, as proven both by 100h on stream stability test and by subjection
to a steaming procedure after which the catalytic performance was not deteriorated.
Page | 82
Abstract Number 1136 Oral Presentation
Session: Pertrochemicals: Raw and Intermediates
Wedneday, June 12, 3:15 p.m., Lopata Hall, Room 101
Oxidative Dehydrogenation of Ethane to Ethylene
1
Anne M. Gaffney
1
The Langmuir Research Institute, Saint Louis, Missouri
[email protected]
This seminar will discuss a newly patented catalytic process and catalyst for the
selective, oxidative dehydrogenation (ODH) of ethane to ethylene. Recent advances in
shale gas technology, especially as practiced in the United States, has significantly
improved the economics around producing ethylene and has revolutionized
manufacturing approaches to basic chemicals, polymers and materials. Ethane is
second to methane as a major hydrocarbon component of shale gas, serving as the
precursor to ethylene. Ethylene is used to produce a wide variety of consumer goods,
including packaging, building & automotive materials, fibers, tires and bottles. In 2012,
a number of U.S. chemical companies announced plans to invest in new plant capacity,
expand existing facilities, or re-open plants near shale gas supplies, primarily based on
the assumption that the U.S. is entering a period of sustained low natural gas prices and
growing supply.
This selective ODH process provides an alternative to ethylene production via naphtha
or ethane cracking. In addition to replacing these crackers and recycle crackers, the
ethylene product effluent from the ODH process may be used to feed ethyl
benzene/styrene monomer and ethylene oxide plants. The synthesis, characterization
and catalytic applications of the new, M1 structured, mixed metal oxide catalyst will be
reviewed.
Page | 83
Abstract Number 1137 Oral Presentation
Session: Pertrochemicals: Raw and Intermediates
Wednesday, June 12, 3:45p.m., Lopata Hall, Room 101
Alumina supported vanadium containing phosphotungstic acid as an effective
catalyst for oxidative dehydrogenation of ethane to ethylene
1
1
2
2
1
2
P.S. Sai Prasad , Sri Hari Kumar , V.N. Kalevaru , A. Qiao , N.Lingaiah , A. Martin , A.
3
Alshammari , Ch. Sailu4
1
Inorganic & Physical Chemistry Division, Indian Institute of Chemical Technology,
Hyderabad-500 007, India
2
Leibniz-Institut für Katalyse e.V. an der Universität Rostock, 18059 Rostock, Germany
3
National Nanotechnology Research Center, King Abdulaziz City for Science and
Technology, Riyadh 11442, Saudi Arabia
4
Univ. College of Technology, Osmania University, Hyderabad-500 013, India
[email protected]
Oxidative dehydrogenation of ethane (ODHE) has the potential to replace the
conventional cracking processes that suffer from heavy coking, side products (COx) and
high energy requirement. In this study, we describe the potential of alumina supported
vanadium containing phosphotungstic acid (TPAV) catalysts with varying loadings (030wt%) for ODHE. The catalysts were characterized by BET-SA, XRD, FT-IR, TPR etc. and
tested their performance in fixed bed reactor. XRD revealed that no distinct Wcontaining phases could be seen; however the crystalline reflections correspond to alumina was found. Calcination of the catalysts at 600°C/6h/air caused destruction of
Keggin structure, which is confirmed by FTIR. Despite such destruction, the decomposed
TPAV/-Al2O3 catalysts displayed considerably good activity in ODHE. X-C2H6 and S-C2H4
are varied in the range from 2-60% and 44-90% with varying temperature (450 to
600°C). Among all, 25wt% TPAV/Al2O3 catalyst exhibited ethane conversion of 52% with
ethylene selectivity of >70% along with good long-term stability (48h).
Page | 84
Abstract Number 1254 Oral Presentation
Session: Pertrochemicals: Raw and Intermediates
Wedneday, June 12, 4:15p.m., Lopata Hall, Room 101
Syngas generation over Ni-Pd/CeO2-ZrO2-Al2O3 catalysts: formation and
evolution of active sites for autothermal reforming of methane
Zinfer Ismagilov1, Ekaterina Matus1, Vadim Kuznetsov1, Mikhail Kerzhentsev1, Noelia
Mota2, Rufino Navarro2, José Luis Fierro2, IIyas Ismagilov1, Svetlana Yashnik1, Igor
Prosvirin1
1
Boreskov Institute of Catalysis, Laboratory of Environmental Catalysis, Novosibirsk,
West Siberia, Russia
2
Instituto de Catálisis y Petroleoquímica, Grupo de Energía y Química Sostenibles,
Madrid, Spain
[email protected]
Nickel-ceria-zirconia based catalysts, both bulk and supported on spherical alumina,
were developed and studied for autothermal reforming (ATR) of methane, with
perspective of their application in membrane reactors for syngas generation. The
electronic, structural and redox properties of as-prepared and used catalysts were
comparatively evaluated using the techniques of XPS, HRTEM-EDX, TPR, XRD, and BET.
The results show that genesis of the active phase is affected by the preparation method
and support composition of the catalysts. Using mass-spectrometric measurements in
the flow laboratory setup, the catalytic activity was correlated with the increase of
reducibility of Ni species as a result of weakening of the Ni-support interaction, and the
role of Pd modifier for the removal of carbon deposits was emphasized. The catalysts
exhibited high performance (yields of H2 ~ 50% and CO ~ 70%, respectively, at CH4
conversion ~ 100%) and stability during the long-run operation in ATR of CH4.
Page | 85
C2. Commodity and Fine Chemicals
Abstract Number 1146 Oral Presentation
Session: Commodity and Fine Chemicals
Sunday, June 9, 1:00p.m., Lopata Hall, Room 101
Whole-cell biocatalysis coupled to heterogeneous catalytic oxidation for
deracemization of chiral sulfoxides
Vasile Parvulescu1, Madalina Tudorache1, Simona Nica1, Emerich Bartha1
1
University of Bucharest, Bucharest, Romania
[email protected]
A new concept for deracemization of racemic (rac) sulfoxides using a two-stage protocol
had been developed. Enantio-pure sulfoxide was obtained using Escherichia coli cells.
They catalyzed the reduction of (R)-sulfoxide to the corresponding thioether. The
limitation of E. coli resolution (chemical conversion of 49.3% for rac-MPSO) was
overcome by combining E. coli resolution with achiral oxidation of thioether product
back to the rac-sulfoxide. A heterogeneous Ta2O5-SiO2 catalyst was used for this
purpose. Deracemization process was cyclically applied for rac-MTSO leading to a 97.5%
ee of (S)-sulfoxide and a 56% yield in (S)-sulfoxide after three cycles.
Page | 86
Abstract Number 1238 Oral Presentation
Session: Commodity and Fine Chemicals
Sunday, June 9, 1:30p.m., Lopata Hall, Room 101
Concepts for the development of industrial phthalic anhydride catalysts - current
approaches and challenges
Michael Kraemer 1, Nico Fischer1, Stefan Altwasser2, Christian Walsdorff1, Hans-Martin
Allmann2, Juergen Zuehlke2
1
BASF SE Heterogeneous Catalysis-Oxidation Catalysts, Ludwigshafen, Rheinland Pfalz,
Germany
2
BASF SE, Mannheim, Baden Württemberg, Germany
[email protected]
From the first mercury sulphate catalyzed liquid phase process to the current multimillion ton selective gas-phase oxidation of o-xylene or naphthalene on V/Ti based
catalysts BASF has been at the forefront of the catalyst development for the production
of phthalic anhydride.
To maintain and to extend this globally leading position huge efforts are put into the
constant improvement of the current catalyst system to increase the yield of PA at high
reactant loadings and full conversion. New and complex catalyst compositions
consisting of known promoters in various concentrations and different catalyst layers
with varying catalytic properties in one reaction tube as well as new crystalline phases,
still allow for significant improvements in the catalyst performance.
Despite extensive research in the past, many key questions reagrding reaction
mechanism, active species and the role of promoters remain unanswered and require a
deeper understanding.
Page | 87
Abstract Number 1258 Oral Presentation
Session: Commodity and Fine Chemicals
Sunday, June 9, 2:00p.m., Lopata Hall, Room 101
Heterogeneous Selective Oxidation of Fatty Alcohols: Oxidation of 1-Tetradecanol
as a Model Substrate
Vicente Cortés Corberán1, Susana Martínez-González1, Almudena Gómez-Avilés1, Maria
I. Dominguez2, Svetlana Ivanova2, M. Elena González-Pérez1
1
Institute of Catalysis and Petroleumchemistry (ICP), CSIC (Spanish Council for Scientific
Research), Madrid, Spain
2
Institute of Material Science of Seville (ICMS), CSIC-Univ. Seville, Seville, Spain
[email protected]
The search for new raw materials is driving new processes using biomass for fine
chemicals production. Fatty (i.e., long-chain (usually C16+) aliphatic) alcohols present in
forest wastes could be used to obtain their corresponding aldehydes and acids, widely
used for pharma and cosmetics applications, and as emulsifiers. However, to date their
heterogeneous (non-enzymatic) oxidation has been scarcely investigated. We report
here for the first time the liquid phase heterogeneous oxidation of 1-tetradecanol, used
as a model for fatty alcohols, using a Au/CeO2-Al2O3 catalyst and O2 as oxidant.
Conversion reached 19% after 6h at 80 ºC with ROH/Au=100, and selectivity to
tetradecanal was 100% in all tests. The effect of the chain length of the alcohol was
studied by comparison with similar tests with 1-octanol. The longer chain decreases the
alcohol conversion but inhibits the formation of acid (and hence, to ester) probably due
to a greater steric effect.
Page | 88
Abstract Number: 1129 Oral Presentation
Session: Commodity and Fine Chemicals
Sunday, June 9, 2:45p.m., Lopata Hall, Room 101
Metal-Free Aerobic Alcohol Oxidation: Intensification under Three-Phase Flow
Conditions
Prof. Ive Hermans1
1
ETH Zurich, Chemistry and Applied BioSciences, Zurich, Switzerland
[email protected]
Recently, we reported on the metal-free aerobic oxidation of benzyl alcohol using substoichiometric amounts of HNO3 in combination with the ion exchange resin Amberlyst15 in protonic form, leading to an (H)NOx-propagated oxidation with O2 as terminal
oxidant. A continuous flow reactor on a millimeter scale using a gas-liquid Taylor flow
was used to increase the space-time-yield, compared to a conventional batch reactor. In
view of the increased H(NO)x chain length, the initial amount of HNO3 could be further
decreased while maintaining full conversion and high selectivity. Additionally, the
formation rate of N2O could be decreased, promising from both an ecological and
economical point of view. Different primary and secondary alcohols were evaluated, all
showing high reaction rates, conversions and selectivities towards the corresponding
aldehyde and ketone products.
ACIE 2011, 50, 12355
ChemCatChem 2012, 4, 525
ChemSusChem 2012, 9, 1732
Page | 89
Abstract Number 1230 Oral Presentations
Session: Commodity and Fine Chemicals
Sunday, June 9, 3:15p.m., Lopata Hall, Room 101
Mixed nano-metal oxides: A novel approach for oxidation of styrene
Hitesh Parekh1, Jignesh Valand1, Holger Friedrich1
1
University of KwaZulu-Natal, School of Chemistry and Physics, Durban, KwaZulu-Natal,
South Africa
[email protected]
Progress in catalysis is strongly dependent on the development of new catalytic
materials. One field in which catalyst development is particularly vital is chemical
manufacturing via oxidation of alkenes. The oxidation of olefins is a significant
transformation in the manufacture of a large number of fine and pharmaceutical grade
chemicals. Metal-catalyzed oxidation of olefins can give rise to a whole variety of
organic products, for examples aldehydes, ketones, alcohols, epoxides and acids.
Besides, olefins can also be converted into aldehydes by the cleavage of C=C double
bond using a catalyst.
In the present study, the ultrasonic cavitation-impregnation method was used for the
preparation of supported mixed nano-metal oxide catalysts containing Ni, Cu and Co. All
the prepared catalysts were analyzed by SEM-EDX, XRD, BET, ICP, TEM to identify their
physical and chemical properties. The heterogeneous catalytic oxidation of styrene was
investigated with different metal loadings, oxidizing agents and reaction conditions.
Page | 90
Abstract Number 1166 Oral Presentation
Session: Commodity and Fine Chemicals
Sunday, June 9, 3:45p.m. Lopata Hall, Room 101
Supported Vanadium Antimony Oxides for the Oxidation of Methanol to
Formaldehyde
Melanie Schumann1, Jan Henning Curtze1, Alfons Drochner1, Herbert Vogel1
1
Technische Universität Darmstadt,
I,Darmstadt,Hessen,Germany
Ernst-Berl-Institut,
Technische
Chemie
[email protected]
Formaldehyde is produced by methanol oxidation, using two different types of catalysts
based on silver or Mo-Fe-Oxides. Unfortunately, the activity of Mo-Fe-Oxide decreases
due to the loss of molybdenum oxide. Therefore, new catalysts without molybdenum
oxide are necessary and concerning this silica supported V-Sb-Oxides are a promising
new catalytic system for this reaction.
The reaction of methanol to formaldehyde was studied by cyclic performed
temperature-programmed-reactions. Comparative measurements show that vanadium
oxide is the major active component and antimony oxide is less active. Antimony spezies
isolates the active vanadia spezies and leads to higher selectivity to formaldehyde. IRmeasurements (DRIFTS) demonstrate that vanadium and antimony oxides species react
with isolated terminal silanol sites for all catalysts. In this context differences between
silica supports will be shown. To compare this new promising system with molybdenum
iron oxides both were tested with transient methods. Both show similarly performances
concerning the activity and selectivity.
Page | 91
Abstract Number 1153 Oral Presentation
Session: Commodity and Fine Chemicals
Monday, June 10, 1:00p.m., Lopata Hall, Room 101
The use of tri-metallic Au-Pd-Pt catalysts to enhance selectivity in alcohol
oxidations
Peter J. Miedziak1, Nikolaos Dimitratos1, Jennifer K. Edwards1, Stuart H. Taylor1, David
W. Knight1, Qian He2, Graham J. Hutchings1, Christopher J. Kiely2
1
Cardiff Catalysis Institute, Chemistry, Cardiff, United Kingdom
Lehigh University, Department of Materials Science and Engineering, PA, U.S.A.
2
[email protected]
The oxidation of primary alcohols to aldehydes is an industrially important process,
conventionally this reaction is carried out using expensive and toxic oxidants such as
chromate or permanganate, causing serious environmental and economic concerns.
Hence, catalytic oxidation of primary alcohols to aldehydes using molecular oxygen/air
becomes an attractive alternative. In order to achieve high selectivity towards aldehyde,
a low reaction temperature approach is often chosen resulting in a low turnover
frequency or low conversion.
Herein, using benzyl alcohol oxidation as an example, we demonstrate that when a
small amount of Pt metal is alloyed into the Au-Pd sols, a high selectivity towards
benzaldehyde can be achieved with solvent-conditions, while still preserving high
conversion levels. STEM characterization reveals that the nanoparticles were tightly
controlled in size, with mean diameters around 2-3 nm, and they were all random
ternary alloys. However, a systematic size-dependant composition variation with
respect to Pd was observed.
Page | 92
Abstract Number 1229 Oral Presentation
Session: Commodity and Fine Chemicals
Monday, June 10, 1:30p.m., Lopata Hall, Room 101
Crude glycerol catalytic oxidation process in the liquid phase: Advantages and
disadvantages.
Skrzyńska Elżbieta1,2,4, Capron Mickaël1,4,Duneignil Franck1,3,4
1
UCCS - Unité de Catalyse et de Chimie du Solide - UMR CNRS 8181 Université des
Sciences et Technologies de Lille, Villeneuve d’Ascq,Nord-Pas-de-Calais,France
2
Cracow University of Technology, Cracow, Poland
3
Institut Universitaire de France, Paris, France
4
Univ.Lille Nord de France, Lille, France
[email protected]
Glycerol oxidation in liquid phase allows obtaining valuable oxygenates. In typical
process, at high pH with commercial platinum catalyst, it is possible to obtain glyceric
and tartronic acids with very high selectivities (after 3h at 60ºC 62.8% and 18.3%
respectively). Smaller molecules, like oxalic and formic acids, are the minor products,
while dihydroxyacetone, glyoxylic and hydroxypyruvinic acids, appear only in the
absence of base. All of them have a market value 20 to 4000 times higher than the value
of pure, anhydrous glycerol. Thus, using a crude fraction from biodiesel production,
make such process even more profitable. Nevertheless, an impurities present in such
raw material (methanol, salts, soaps, …) can strongly influence the glycerol conversion
and the selectivity. Thus, the results of our investigation using various glycerol fractions
(crude, technical and partially purified glycerol), will be discussed in order to identify the
effect of these impurities on the oxidation performances.
Page | 93
Abstract Number 1255 Oral Presentation
Session: Commodity and Fine Chemicals
Monday, June 10, 2:00p.m., Lopata Hall, Room 101
1-Octanol Selective Oxidation over Supported Gold Catalysts: Influence of the
Support Nature, Metal Load and Reaction Conditions
Vicente Cortés Corberán1, Almudena Gómez-Avilés1, Susana MartínezGonzález1,Svetlana Ivanova2, Maria I. Dominguez2, Roberto Fernandez-Lafuente1,
1
Institute of Catalysis and Petroleumchemistry (ICP), CSIC, Madrid, Spain
Institute of Material Science of Seville (ICMS), CSIC-Univ. Seville, Seville, Spain
2
[email protected]
Selective oxidation of long-chain aliphatic alcohols has received much less attention
than that of other more reactive (short chain aliphatic or benzylic) alcohols. The liquidphase direct oxidation of 1-octanol over gold supported catalysts has been investigated
in a semicontinuous reactor at 40-80 ºC, using O2 as oxidant and base-free n-heptane as
solvent. The nature of the supports explored (CeO2-Al2O3, TiO2, Fe2O3 and CeO2)
influenced both activity and product distribution. The most active catalysts were those
supported on CeO2-Al2O3, which showed remarkably high octanal selectivity (Sald). The
best performance was found with 0.7 wt.% Au: higher metal loads decreased activity.
With this catalyst the influence of reaction conditions (temperature, substrate/catalyst
ratio R, oxygen flow, reaction time) was studied. The highest conversion after 6h (62%,
Sald=50-60 %.) was obtained at 80ºC with R=100. Tests with bare support added to
catalyst in reactor evidenced the role of the support surface in product distribution.
Page | 94
Abstract Number: 1132 Oral Presentation
Session: Commodity and Fine Chemicals
Monday, June 10, 2:45p.m., Lopata Hall, Room 101
Acetoxylation of toluene: Marked effect of reaction pressure on the activity,
selectivity and long-term stability of Pd-containing catalysts
V.N. Kalevaru1, N. Madaan1, S. Gatla1, J. Radnik1 , B. Lücke1, A. Brueckner1, A. Martin1
1
Leibniz Institute for Catalysis at University of Rostock, Rostock, MecklenburgVorpommer , Germany
[email protected]
Vapour phase acetoxylation of toluene to benzyl acetate has been carried out in a fixed
bed reactor using Pd-containing catalysts (e.g. Pd-Sb/TiO2) at 210°C under varying
reaction pressures (1 to 10 bar). Attempts were made to derive correlations between
reaction pressure and structure-activity relationships with a special emphasis on
evaluating the effect of pressure on the activity, selectivity, long-term stability,
formation period, Pd particle size and coke deposition. Results revealed that the
conversion of toluene has been increased from 34 to 75% with increase in pressure from
1 to 6 bar and then remained more or less constant. The selectivity of benzyl acetate
also enhanced (S~100%) up to 6 bar and then decreased slightly. Increase in pressure
also caused a faster growth of Pd particles. Furthermore, reaction pressure showed
considerable influence on the reducibility of Pd species and surface composition, which
in turn displayed significant impact on the catalytic performance.
Page | 95
Abstract Number: 1152 Oral Presentation
Session: Commodity and Fine Chemicals
Monday, June 10, 3:15p.m., Lopata Hall, Room 101
The effect of ring size on product distribution during the oxidation of cyclic
alkenes using gold catalysts
Peter J. Miedziak1, Hamed Alshammari1, David J. Willock1, David W. Knight1, Graham J.
Hutchings1
1
Cardiff Catalysis Institute, Chemistry, Cardiff, United Kingdom
[email protected]
Oxidations often use non-green stoichiometric oxygen donors, such as chromate or
permanganate, there is a desire to replace these with greener alternatives. Gold
catalysts show promising activity in the partial oxidation of cycloalkenes to the epoxide
with dioxygen as the oxidant gas and a radical initiator, such as tert-butyl hydroperoxide
present.We have previously reported the oxidation of cyclooctene, however the
selectivity was found to be strongly dependent on the choice of solvent. In this
contribution we have oxidised various sized cycloalkenes (5-12 carbons) under green
conditions, solvent-free and using oxygen from air as the oxidant gas. The product
distribution varies with the ring size, these practical trends will be discussed in terms of
DFT calculations of the key intermediates and transition states. In the context of these
calculations the reaction pathway and product selectivity will be discussed in relation to
the ring size of the substrate.
Page | 96
Abstract Number 1176 Oral Presentation
Session: Commodity and Fine Chemicals
Monday, June 10, 3:45p.m., Lopata Hall, Room 101
Oxidation of Benzyl Alcohol Benzaldehyde over Supported Gold Nanoparticles
Dr. Ahmad Alshammari1, Dr. Abdulaziz Bagabas1, Dr. Angela Koeckrtiz 2 , Dr. Andreas
Martin2, V. Narayana Kalevaru2
1
King Abdulaziz City for Science and Technology, National Nanotechnology Research
center, Riyadh, Saudi Arabia
2
Leibniz Institute for catalysis, Heterogeneous Catalytic Process, Rostock, Germany
[email protected]
The oxidation of benzyl alcohol (BA) to benzaldehyde (BAL) is essential and demanding
target in green chemistry. BAL is widely used in the production of perfumery,
pharmaceutical and agro-chemicals. In this study, supported gold nanoparticles (AuNPs)
on different metal oxides were tested toward BA oxidation. Catalysts were prepared in
two steps, characterized by BET, thermal analysis, XRD and TEM. The catalytic activity
was carried out using an autoclave reactor. The conversion of BA in blank test was
~10%. However, in the presence of catalysts, the catalytic activity significantly depended
on the nature of support used. BAL was the major product along with other side
products such as benzoic acid, benzyl benzoate and acetal. Among all investigated
catalysts, AuNPs supported by TiO2 gave the better activity (X-BA = 81%) and selectivity
(S-BAL = 95%). AuNPs over MgO showed the lowest catalytic performance.
Page | 97
Abstract Number 1178 Oral Presentation
Session: Commodity and Fine Chemicals
Monday, June 10th 4:15 p.m., Lopata Hall, Room 101
Promotion of Sm/Gd-doped Cu-Zn Washcoat Catalyst for a Steam Reforming of
Methanol in a Microchannel Reactor
Kuen-Song Lin1, Wan-Ting Hong1, Ho-Yang Chan1, Chi-Yu Wang1,Chieh-Hung Wang1
1
Yuan Ze University, Chemical Engineering & Materials Science, Tao-Yuan County,
Taiwan, R.O.C.
[email protected]
Demand of hydrogen generation by steam reforming of methanol for fuel cell
application can be met by microstructured compact reformer. Therefore, a steam
reforming of methanol was carried out over Cu-Zn catalysts prepared via coprecipitation method. Experimentally, addition of Sm and Gd species in the catalyst
composition affected the catalytic performance were also developed. These metal
oxides improved the activities of Cu -Zn catalysts, increase the selectivity of hydrogen
and decrease the concentration of CO. The advantages of Sm and Gd promotion of Cu Zn catalysts have been characterized using TPR, XRD, FE-SEM/TEM, ASAP-BET, and
EXAFS/XANES. In addition, the XRD patterns of Gd/Sm-doped catalysts showing that
addition of dopants leads to increase of CuO dispersion. The reduction temperature of
Cu -Zn catalysts decreased from 230 to 190 oC due to Sm/Gd promotion. The
performance of Cu -Zn catalysts was estimated from temperatures required for 95%
methanol conversion (T95) in a SRM reaction. Consequently, T95 was significantly
decreased to 240 oC.
Page | 98
C3.Renewable Chemistry
Abstract Number 1222 Oral Presentation
Session: Renewable Chemistry
Wednesday, June 12, 11:00 a.m., Lopata Hall, Room 101
2,5-Furandicarboxylic acid synthesis in water as green alternative to terephtalic
acid
Vasile I Parvulescu1, Florentina Neatu1, Roxana S. Marin1, Nicoleta Petrea2, Vasile
Somoghi3, Mihaela Florea1, Octavian D. Pavel1
1
University Bucharest, Faculty of Chemistry, Organic Chemistry, Biochemistry and
Catalysis, Bucharest, Romania
2
Centrul de Cercetare Stiintifica pentru Aparare CBRN si Ecologie, Bucharest, Romania
3
SC Stimpex SA, Bucharest, Romania
[email protected]
2,5-Furandicarboxylic acid (FDCA) was identified as one of the top added chemicals from
biomass and, as a promising new building block for variuos industrial applications. FDCA
may replace terephthalic acid in the production of polyethylene terephthalate.
Following the classical chemical routes, the synthesis of FDCA is an expensive and
polluting process, which requires high pressures and temperatures, metal salts and
organic solvents. Therfore, a new greener synthetic route is a prerequisite.
Heterogeneous catalysis may represent a solution in this sense, and herein we report
the FDCA synthesis in water using hydrotalcite-supported copper and manganese
heterogeneous catalysts. The catalysts were fully characterized using different
techniques: textural characterization, XRD, DRIFT, Raman and XPS measurements.
Following the oxidation of 5-hydroxymethyl-2-furfural with molecular oxygen in water,
under heterogeneous base-free condition, FDCA resulted in a majority of 75 %. The
catalyst was reusable at least three times without any significant loss of activity and
selectivity.
Page | 99
Abstract Number 1148 Oral Presentation
Session: Renewable Chemistry
Wednesday, June 12, 11:30 a.m., Lopata Hall, Room 101
Role of active phase and support in Au and Au-Cu catalysts used for selective
oxidation of HMF
Alice Lolli1, Stefania Albonetti1, Thomas Pasini1, Fabrizio Cavani1, Vittorio Morandi2
1
Alma Mater Studiorum – Bologna University, Industrial Chemistry “Toso Montanari”,
Bologna, Italy
2
CNR-IMM Section of Bologna, Bologna, Italy
[email protected]
In the field of the transformation of carbohydrates into chemicals, an important role is
played by the derivatives of furfural like 5-hydroxymethyl-2-furfural (HMF), which is a
key precursor for the synthesis of 2,5-furandicarboxylic acid (FDCA). This monomer
could replace terephthalic acid for the preparation of a new class of polymers, that are
more easily degradable and do not present problems of bioaccumulation.
The oxidation of HMF to FDCA was studied using TiO2 and CeO2 supported Au and AuCu nanoparticles with various Au:Cu ratio. We also tried to figure out the reaction
mechanism.A strong synergistic effect was found out with the addition of Cu to Au,
especially in terms of sample stability and resistance to poisoning. We also observed an
increase in the FDCA yield due to the calcination temperature. Furthermore, we
obtained different results for TiO2 and CeO2 supported catalysts, suggesting that CeO2
acts actively in the reaction mechanism
Page | 100
Abstract Number 1158 Oral Presentation
Session: Renewable Chemistry
Wednesday, June 12, 1:00p.m., Lopata Hall, Room 101
Highly efficient cerium and nickel based catalysts for hydrogen production from
ethanol at room temperature
Louise Jalowiecki-Duhamel1, Wenhao Fang1, Cyril Pirez1, Mickaël Capron1, Sébastien
Paul1, Hervé Jobic2, Franck Dumeignil1
1
UCCS CNRS, UMR 8181, Unité de Catalyse et Chimie du Solide, Villeneuve d’Ascq,
France
2
IRCELyon, Institut de Recherche sur la Catalyse et l’Environnement de Lyon,
Villeurbanne, France
[email protected]
At the international level hydrogen has been proposed as a future clean energy and bioethanol obtained through biomass is a promising renewable source of
hydrogen. Providing low cost catalysts able to efficiently transform the alcohol is an
international major challenge. We have successfully developed cerium and nickel based
catalysts for hydrogen production from ethanol at almost room temperature. The
influence of different parameters was analysed, such as the reaction temperature, Ni
content, water-oxygen-ethanol feed compositions, and in-situ pre-treatment in H2. The
activity is very stable even after 70 h even if some carbon is formed. Different
physicochemical techniques were used to characterize the catalysts. It appears that the
active nickel species are in strong interaction with Ce species, allowing a redox process.
An active site based on the formation of anionic vacancies and a mechanism involving a
heterolytic abstraction of a hydride species from ethanol are proposed.
Page | 101
Abstract Number 1185 Oral Presentation
Session: Renewable Chemistry
Wednesday, June 12, 1:30p.m., Lopata Hall, Room 101
Synergetic behavior of bimetallic Pd-Pt/TiO2 catalysts in the green synthesis of
methyl formate
Victor G Baldovino Medrano1
1
Université catholique de Louvain, IMCN-MOST, Ottignies-Louvain-la-Neuve, Brabant
Wallon, Belgium
[email protected]
Reduced bimetallic Pd-Pt/TiO2 catalysts displayed a synergy behavior in the oxidative
conversion of methanol (MeOH) to methyl formate (MF) at T = 323 K and ambient
pressure. Synergetic effects as a function of the Pd/(Pd+Pt) molar ratio of the catalysts
were remarkable for the selectivity to MF at 80% conversion. At iso-conversion, MF yield
increased from 23% to 67%. Catalysts were synthesized by two preparation methods:
namely, conventional incipient wetness (co)impregnation (Pd-Pt-IWI) and water in oil
microemulsion (Pd-Pt-WIO). The preparation method had a deep impact on the catalytic
performance. Indeed, the Pd-Pt-WIO series of catalysts showed a higher MeOH
conversion and, at the same time, a higher selectivity to MF than the Pd-Pt-IWI one.
XRD, XPS, and HRTEM measurements showed that these differences arise because of
two factors: (i) the chemical interaction between Pd and Pt, and (ii) the structural
conformation of the mono- and bimetallic Pd and Pt nanoparticles.
Page | 102
Abstract Number 1262 Oral Presentation
Session: Renewable Chemistry
Wednesday, June 12, 2:00p.m., Lopata Hall, Room 101
The Low-temperature Catalytic Pyrolysis of Organic Waste
E. Sulman1, Y.U. Kosivtsov1, K. Chalov1, M.Sulman1, Yu. Lugovoy1
1
Tver State Technical University, Department of Chemistry, Tver, Russia
[email protected]
From the point of view of the simplicity of the process; level of pollutants control and
high yield of the final products, pyrolysis is considered to be an efficient way of
converting organic waste into combustible gases, oil-like liquid products and solid
carbon-containing residues [1].
In spite of their variety, modern technologies of waste pyrolysis are far from perfect as a
series of problems hasn't been solved (e.g. low yield of pyrolysis oil, blocking of pipelines with coal, quick deactivation of the catalyst). Zeolites exhibit good activity and
selectivity in the catalytic cracking of heavy oil feedstock to produce gasoline and gasoil. Their success is based on the ability to prepare zeolite materials with strong
Brønsted acidity that can be controlled within a certain range, and which resist high
reaction temperatures and catalyst regeneration conditions [2].
Various waste are available for pyrolysis: from clean biomass to fuel and polymeric
waste containing different amounts of ash, alkaline and emission precursors like N, Cl
and S. Biomass may vary significantly in its physical and chemical properties due to its
diverse origins and types. Compared to the other fossil fuels, peat is characterized by
the lowest content of fixed carbon along with the highest content of volatile substances.
The increase of cars production brings to the accumulation of used automobile tires,
which is a serious ecological problem. During the automobile tires processing by
mechanic crushing a large amount of polymeric cord is accumulated. The mixture of
polymeric cord and resin crumb do not decompose for a long time in nature. The
storage of cord results in the environment pollution with the products of polymers
decomposition. However, the mixture of polymeric cord and resin crumb is a valuable
source of organic material, which can be used for the production of liquid and gaseous
fuels.Oil-containing wastes are very complex systems, which consist of oil products,
water and mineral part (sands, clays, silts and others). The formation and accumulation
of oil-slime result in the pollution of the environment and causes the violation of the
ecological situation. Taking into account the limited stock of oil resources, the research
on effective processing of oil-slime with the production of gas and liquid fuel is very
topical. On the other hand a number of countries have a large stock of peat, which
energy is valuable renewable raw materials and can be used to increase the efficiency of
oil-containing waste processing.In this work the influence of natural and synthetic
Page | 103
aluminosilicates, metal chlorides of iron subgroup on the peat low-temperature
pyrolysis and co-pyrolysis of peat with oil-slime and polymeric waste was studied in
variety of conditions (t = 350-650ºC, catalyst loading: from 1 up to 30 % (wt.)). The use
of bentonite clay (30 % (wt.)) at 460 ºC as a catalyst in peat pyrolysis resulted in increase
of weight of gaseous and liquid products from 23 up to 30 % (wt.) and from 32 up to 45
% (wt.), respectively. Co-pyrolysis of peat and oil-slime in the presence of bentonite clay
resulted in increase of gaseous product weight from 18 up to 26 % (wt.) and liquid
fraction yield – from 45 up to 55 % (wt.) in comparison with precalculated value. The use
of metal chlorides of iron subgroup (2 % (wt.) concentration) at 500 ºС in the copyrolysis of peat and polymeric waste led to optimal conversion of substrate in desired
products, 15 % increase of total weight of gaseous and liquid products formed during
the pyrolysis process and simultaneous decrease of char formation. The increase in the
amount of methane and ethylene evolved during the pyrolysis of 2.8 and 5.2 times
respectively compared with the non-catalytic process was observed for nickel chloride.
Page | 104
C4.Oxidation Technology for CleanTech
Abstract Number 1143 Oral Presentation
Session: Oxidation Technology for CleanTech
Tuesday, June 11th 1:00 p.m., Laboratory Sciences Building, Room 300
A chemical-loop approach for the generation of hydrogen by means of ethanol
reforming
Cristian Trevisanut1, Jean-Marc M. Millet2, Fabrizio Cavani1, Massimiliano Mari1, Juliana
Velasquez Ochoa1
1
University of Bologna, Dipartimento di Chimica Industriale "Toso Montanari", Bologna,
Italy
2
IRCELYON, Villeurbanne, Rhone-Alpes, France
[email protected]
In order to produce hydrogen with inherent C-containing products separation, a
thermochemical cycle using ethanol as reducing fuel and ferrites as looping material has
been developed. In this cycle the materials were first reduced by a stream of ethanol at
450°C, and then reoxidized with water, to produce hydrogen and restore the original
oxidation state and O2- content of the ferrites. The ferrites investigated were Fe3O4,
CoFe2O4, NiFe2O4 and CuFe2O4, prepared by co-precipitation method, while new
supported and doped ferrites are being tested presently. Characterization using BET,
TPR, XRD, Mössbauer, XPS and TEM has been performed, in order to investigate on the
modification of the oxides occurring during the redox cycles. Tests have been performed
on a laboratory-scale plant and results analyzed on-line by chromatography. An
“operando” DRIFT-MS study was also performed for each material, in order to identify
the reaction pathway involved and the formation of by-products.
Page | 105
Abstract Number 1174 Oral Presentation
Session: Oxidation Technology for CleanTech
Tuesday, June 11, 1:30p.m., Laboratory Sciences Building, Room 300
Synthesis of Hydrogen Oxidation Electrocatalyst from Metal Organic Frameworks
Foroughhazam Afsahi1, Vinh Hoang Thang1, Serguei Mikhailenko1, Serge Kaliaguine1
1
Laval University, Chemical Engineering, Québec, Cananda
[email protected]
Pt nanoparticles as the common electrocatalyst for proton exchange membrane fuel
cells (PEMFCs) were prepared for the first time from metal organic frameworks (MOFs).
MOFs are highly crystalline structures comprised of metal ions or clusters linked
together by bifunctional organic ligands. MOF materials possess high specific surface
area and various pore sizes and geometry.
Pt containing MOF was synthesized and subsequently subjected to pyrolytic
carbonization under non-reactive gas condition. Upon pyrolysis, Pt nanoparticles
embedded in electronically conductive carbon media were produced. The prepared
electrocatalysts were characterized by XRD, N2 physisorption, TEM and XPS. The Pt
dispersion of the electrocatalysts was determined by hydrogen chemisorption. The
membrane electrode assemblies (MEAs) made of such electrocatalysts were tested as
anode in a H2/air single cell fuel cell. The most promising electrocatalyst (C3)
demonstrated an open circuit voltage of 970 mV and power density of 0.58 W
comparable to the commercial electrode
Page | 106
Abstract Number 1194 Oral Presentation
Session: Oxidation Technology for CleanTech
Tuesday, June 11, 2:45p.m., Laboratory Sciences Building, Room 300
Effect of K on soot combustion by combined TPO and Raman spectroscopy
Lidia Castoldi1, Roberto Matarrese1, Luca Lietti1, Luigi Brambilla2, Matteo Tommasini2
1
2
Politecnico di Milano, Dipartimento di Energia, Milano, Italy
Politecnico di Milano, Dipartimento CMIC, Milano, Italy
[email protected]
The effect of potassium in the oxidation of a Printex U model soot is investigated,
preparing samples in which potassium has been directly deposited on the soot (full
contact conditions). Raman spectroscopy and temperature-programmed oxidation were
combined to investigate changes in structure and reactivity of soot during oxidation by
oxygen at increasing temperatures. It is found that the combustion of soot is greatly
enhanced by the presence of K, decreasing the onset temperature from 480°C to 260°C.
The Raman spectra of soot during the oxidation show an increase of the “graphite” peak
(G peak, 1580 cm-1) relative to the “defect” peak (D peak, 1350 cm-1) indicating that
the degree of order in the graphitic structure increases. Conversely, over K-soot the D
peak increases suggesting that the presence of K prevents the formation of ordered
graphite domains and favors the preservation of a more disordered and hence slightly
more reactive structure.
Page | 107
Abstract Number 1173 Oral Presentation
Session: Oxidation Technology for CleanTech
Tuesday, June 11, 3:15p.m., Laboratory Sciences Building, Room 300
Influence of methanol concentration on CO oxidation over CuOx/CeO2 catalysts
Sandra Palma del Valle1, Alejando Pérez Flores1, Francisca Romero-Sarria1, Miguel Ángel
Centeno Gallego2, Óscar H. Laguna Espitia1, Jose Antonio Odriozola Gordon1
1
University of Seville, Inorganic Chemistry, Seville, Spain
CSIC, Seville, Spain
2
National Taiwan University, Chemical Engineering, Taipei City, Taiwan, R.O.C
3
Chung Yuan Christian University, Bioenvironmental Engineering, Chung-Li City, Taiwan,
R.O.C.
2
[email protected]
Hydrogen fuel for PEMFCs can be obtained by reforming of liquid hydrocarbons, like
methanol. Further steps of CO removing (WGS and PROX) are necessary in order to
obtain H2-rich fuel gases. Methanol reforming is appropriated for portable devices,
because the WGS step may be omitted and only the reformer and the CO-PROX reactor
are required. The integration of methanol reforming and PROX reaction involves the
presence of non-converted methanol and water in the inlet stream of the PROX feed.
Therefore, the effect of these products on the performance of the catalyst is essential
for the integration of both processes. In this context, the catalytic behavior of CuO-CeO2
model catalyst in the presence of methanol and water has been studied and correlated
to in situ DRIFTS results. The identification of the reaction intermediate allows to modify
the catalyst formulation, in order to achieve more robust catalysts in this process.
Page | 108
Abstract Number 1175 Oral Presentation
Session: Oxidation Technology for CleanTech
Tuesday, June 11, 3:45p.m., Laboratory Sciences Building, Room 300
Title: H2 oxidation as criteria for PROX catalyst selection
Tomás Ramírez Reina1, Alejandro Pérez Flórez1, Miguel Ángel Centeno1, José Antonio
Odriozola1, Svetlana Ivanova1
1
University of Sevilla-CSIC, Inorganic Chemistry-Material Science Institute, Sevilla, Spain
[email protected]
For a deep understanding of the activity evolution in the PROX reaction over Au-based
catalyst, the oxidation of hydrogen under realistic PROX conditions is considered in this
work. The competition between H2 and CO oxidation has been studied over a series of
Au/CeO2/Al2O3 and Au/CeO2-CoOx/Al2O3 catalysts. Following PROX reaction by
hydrogen oxidation simplifies the proper catalyst selection in terms of selectivity which
is the most demanding parameter for industrial applications. Our catalytic data together
with TPR and in situ DRIFT studies suggest the competitive adsorption of CO and H2 on
the metal crystallites as responsible for the differences in selectivity for these catalysts.
Cobalt addition to Ceria improves its redox properties while gold addition decreases the
H2 oxidation rate at low temperatures. These two factors allow explaining the selectivity
differences.
Page | 109
Abstract Number 1204 Oral Presentation
Session: Oxidation Technology for CleanTech
Tuesday, June 11, 4:15p.m., Laboratory Sciences Building, Room 300
High reactive mixed LNT/CeZr catalytic systems for the simultaneous removal of
NOx and soot from Diesel exhausts
Matarrese Roberto1, Ballarin Julian1, Gallucci Katia2, Villa Pierluigi2,
1
Politecnico di Milano, Energia, Milano, Italy
2
Università degli Studi di L'Aquila, Ing. Industriale e dell'informazione e di economia,
L’aquila, AQ, Italy
[email protected]
The environmental problems associated to Diesel engines has lead in recent years to
focus on new integrated De-NOx and De-soot after-treatment technologies. The
potentiality of combined Pt-K/Al2O3 LNT/CeZr novel catalytic systems in the
simultaneous removal of soot and NOx is investigated in this work. The behaviour of the
catalyst in soot combustion and NOx removal has been analyzed by means of
temperature programmed oxidation (TPO) experiments, isothermal combustions and
transient response method (TRM), respectively. A synergistic effect has been found on
the Pt-K/Al2O3 LNT/CeZr physical mixture if compared to the pure Pt-K/Al2O3 and CeZr
catalytic systems. The presence of Ce-Zr sample promotes the NOx storage capacity and
in particular the soot oxidation activity at low temperatures. In addition high NOx
removal efficiency and N2 selectivity have been also observed. Accordingly mixed PtK/Al2O3 LNT /CeZr catalytic systems result as good candidates for innovative DPNR
(Diesel Particulate NOx Reduction) systems.
Page | 110
Abstract Number 1125 Oral Presentation
Session: Oxidation Technology for CleanTech
Wednesday, June 12, 10:30 a.m., Laboratory Sciences Building, Room 300
Utilization of Carbon Dioxide by Catalyst-Assisted Chemical Looping
Vladimir Galvita1, Hilde Poelman1, Guy B. Marin1
1
Ghent University, Laboratory for Chemical Technology, Ghent, Belgium
[email protected]
Mixed CeO2-Fe2O3 was prepared for CO2 transformation to CO by means of chemical
looping. The process was combing with catalytic dry reforming of methane. The
generation of CO from CO2 through CH4-CO2 /CO2 redox cycles was investigated to
evaluate the effect of CeO2 upon Fe2O3.Space time yield of CO up to 30 mmol kg-1 s-1
were obtained.
A mixture of a Ni-base catalyst and CeO2-Fe2O3 as oxygen storage material is used to
intensify the chemical looping. During the reduction step, CH4/CO2 is converted over a
Ni base catalyst into syngas, which then reduces iron oxide, giving CO2 and H2O. During
re-oxidation of the oxygen storage material by CO2, CO is produced. This process utilizes
more carbon dioxide than it produces.
The proposed materials were characterized by means of HRTEM, EDX, SAED, in situ XRD,
and tested during 20 cycles for activity and stability.
Page | 111
Abstract Number 1186 Oral Presentation
Session: Oxidation Technology for CleanTech
Wednesday, June 12, 11:00 a.m., Laboratory Sciences Building, Room 300
Desulfurization of diesel oil with H2O2 catalyzed by lacunary Keggin 11tungstophosphates
Rui Wang1
1
Shandong University, School of Environmental Science and Engineering,Jinan,
Shandong, China
[email protected]
The lacunary Keggin 11-tungstophosphates were evaluated as catalysts for the oxidation
of dibenzothiophene with hydrogen peroxide as oxidant in normal octane/acetonitrile
biphasic system. The Na5[PW11O39Ni] exhibited good catalytic activity with the
desulfurization efficiency above 99.5%. The key factors affecting the reaction, including
amount of catalyst, O/S molar ratio, catalyst dosage and initial sulfur content, were
investigated, whereby the favorable conditions were determined. The presence and the
oxidative effect of the peroxo-heteropoly species in the oxidative reaction were
determined in the contrast experiments. Moreover, the Na5[PW11O39Ni] catalyst was
confirmed to have a high potential for deep desulfurization of diesel oil.
Page | 112
Abstract Number 1187 Oral Presentation
Session: Oxidation Technology for CleanTech
Wednesday, June 12, 11:30 a.m. Laboratory Sciences Building, Room 300
Alloyed Pd-Rh catalysts: balancing between deactivation and stable activity.
Mikhail Garilov1, Aleksey Vedyagin1, Alexander Volodin1, Elena Slavinskaya1, Ilya
Mishakov1, Vladimir Stoyanovskii1, Yuriy Shubin2
1
Boreskov Institute of Catalysis SB RAS, Novosibirsk, Novosibirsk Oblast, Russian
Federation
2
Nikolaev Institute of Inorganic Chemistry SB RAS, Novosibirsk, Novosibirsk Oblast,
Russian Federation
[email protected]
Three-way catalytic converter conventionally contains Pt and/or Pd and Rh. The
formation of alloys at high temperatures along with the sintering of Pd particles and Rh
bulk diffusion leads to the irreversible deactivation. Nevertheless, in our work it was
shown that the synthesis of alloyed Pd-Rh catalysts with predefined metal ratio
permitted increase durability and activity of samples. The atomic Pd/Rh ratio 4:1 was
chosen to correspond with the thermodynamically metastable area of Pd-Rh phase
diagram. The catalyst containing 0,2% of metals performed medium activity as
compared with monometallic Pd and Rh samples in CO oxidation and NOx reduction,
but much better stability. The formation of Pd agglomerates was prevented due to
formation of bimetallic particles. Laser-induced luminescence indicates that the
concentration of Rh in corundum phase for alloyed sample is less to an order of
magnitude than for the mechanical mixture with corresponding composition.
Page | 113
Abstract Number 1144 Oral Presentation
Session: Oxidation Technology for CleanTech
Wednesday, June 12, 2:45 p.m., Laboratory Sciences Building, Room 300
Titanium dioxide phases in mesostructured silica matrices: Synthesis,
characterization and oxidation activity
Vasile I. Parvulescu1, Divakara Soorly Gopala2, Rama Ranjan Bhattacharjee2,3, Robert
Haerr2, Bener Yeginoglu2, Octavian Dumitru Pavel1, Bogdan Cojocaru1, Vasile I.
Parvulescu1, Ryan M. Richards2
1
University of Bucharest, Organic Chemistry, Biochemistry and Catalysis, Bucharest,
Romania
2
Colorado School of Mines, Department of Chemistry and Geochemistry, Colorado,
U.S.A.
3
Sikkim Manipal Institute of Technology, Department of Chemistry, Majhitar, East
Sikkim, India
[email protected]
Nanostructured TiO2 particles were immobilized on the high surface area hexagonal
phase of mesoporous silica by means of a templated sol–gel method with ionic liquids as
templates. The TiO2 NPs were thermally stable and resistant to anatase-to-rutile phase
transformation during calcination. A preliminary evaluation of the catalyst activity was
performed by means of photooxidation and oxidation of cyclohexene, styrene, and
toluene. The catalysis results strongly indicate that the properties of this material are
controlled by the dispersed TiO2 nanoparticles. The solvent (dioxane, acetonitrile)
influences de conversion and selectivity, depending on the substrate. The role of the
solvent is not simple, but the most important factor is the hydrophilicity/hydrophobicity
ratio of the solid surface. The comparison between photocatalytic and liquid phase
oxidation of the same substrates showed that under UV irradiation the reaction occurs
to a much larger extent than in the liquid phase and also with a good selectivity.
Page | 114
Abstract Number 1130 Oral Presentation
Session: Oxidation Technology for CleanTech
Wednesday, June 12, 3:15 p.m., Laboratory Sciences Building, Room 300
Partial Oxidation of H2S over NaxV2O5 Bronze
Jose M. Lopez Nieto1, M.D. Soriano1, E. Rodriguez-Castellon2, Ester Garcia-Gonzalez3
1
UPV-CSIC, Valencia, Spain
Universidad de Málaga, Málaga, Spain,
3
Universidad Complutense, Madrid, Spain
2
[email protected]
Na-containing vanadium oxides (with Na/V ratios from 0 to 0.5) have been prepared
hydrothermally, heat-treated in N2 at 500ºC, and tested in the partial oxidation of
hydrogen sulfide to sulfur. The higher activity and selectivity during the partial oxidation
of H2S at 200ºC was achieved on catalysts with Na/V ratios between 0.1-0.2. The
catalysts have been characterized by using several techniques (XRD, FTIR, XPS, SEMTEM) before and after catalytic tests. In fresh catalysts, V2O5 and NaxV2O5 crystalline
phases have been detected at Na/V ratio from 0 to 0.2 (the last increasing with the Na/V
ratio), whereas NaxV2O5 and Na8V24O63 crystalline phases were observed at Na/V
ratios higher than 0.3. On the other hand, no changes on the nature of crystalline
phases were detected after catalytic tests except in those presenting V2O5, in which
V4O9 was also observed. Accordingly, NaxV2O5 can be proposed as active, selective and
stable crystalline phase.
Page | 115
Abstract Number 1228 Oral Presentation
Session: Oxidation Technology for CleanTech
Wednesday, June 12th, 3:45 p.m., Laboratory Sciences Building, Room 300
Low temperature methane combustion over palladium supported on a mixture of
TiO2 and ZSM-5 catalyst in the presence of water
Adi Setiawan1, Michael Stockenhuber1, Eric M. Kennedy1, Bogdan Z. Dlugogorski1
1
Priority Research Centre for Energy (PRICE), Chemical Engineering, The University of
Newcastle, New South Wales, Australia
[email protected]
Palladium supported on ZSM-5 modified with titanium was prepared for catalytic use in
a combustion system for ventilation air methane (VAM). The stability of Pd-based
catalyst against water is carried-out by modifying the support without increasing the
temperature necessary for the catalytic combustion. To help our understanding of the
water effect during the combustion process, temperature temperature-programmed
desorption (TPD) analysis on the fresh and deactivated catalyst was performed. Timeon-stream experiment in a tubular stainless steel micro-reactor at 400 ºC results in no
catalyst deactivation within 20 h indicating water produced from reaction does not
significantly inhibit the activity of this catalyst. A significant improvement was observed
compared to Pd/Al2O3 and Pd/ZSM-5 catalysts. TPD result shows variation of the
amount and interaction strength of water on titanium containing catalysts compared to
standard Pd/Al2O3 and Pd/ZSM-5. It also suggests reduced formation of palladium
hydroxide when TiO2 is added as support and acting as H2O scavenger.
Page | 116
Abstract Number 1135 Oral Presentation
Session: Oxidation Technology for CleanTech
Wednesday, June 12, 4:15p.m., Laboratory Sciences Building, Room 300
Green Catalytic Oxidation Route of Cyclohexane to Adipic Acid Using Gold
Bimetallic Catalysts.
Dr. Ahmad Alshammari1, Dr. Abdulaziz Bagabas1, Dr. Andreas Martin2, Dr. Venkata
Narayana Kalevaru2, Dr. Angela Koeckritz2
1
King Abdulaziz City for Science and Technology, National Nanotechnology Research
Center, Riyadh, Saudi Arabi
2
Leibniz Institute for Catalysis, Heterogeneous Catalytic Processes, Rostock, German
[email protected]
Adipic acid (AA) is an industrially important reaction for manufacturing polyamides (e.g.
nylon 6,6), polyurethanes, polyesters etc. AA is commercially obtained using
environmentally unfriendly route. Therefore, this study aims to explore a green
chemistry route for the direct oxidation of cyclohexane (CH) to AA using different goldcontaining bimetallic catalysts. For this purpose, several catalysts were prepared,
characterized and tested in Parr autoclave, and the products were analyzed by GC. Pure
TiO2 support, monometallic systems (e.g. 1% Au/TiO2 and 1% Pd/TiO2) and bimetallic
system (1% Au-1% Pd/TiO2) were tested. TiO2 displayed the poorest performance, while
the Au/TiO2 displayed improved catalytic activity (i.e. X-CH = ca. 25%, and S-AA = 26%).
The monometallic Pd catalyst (i.e. Pd/TiO2) exhibit somewhat inferior performance (XCH = 16%, S-AA = 18%) compared to Au/TiO2 solid. The combination of Au and Pd (PdAu/TiO2) markedly improved the selectivity of AA from 26 to ca. 34 %
Page | 117
Index of Presenting Authors
Hermans, 26, 60, 88
A
Acharyya, 41
Afsahi, 105
Aleksey, 52
Alshammari, 96, 116
B
Barcelo, 48
Beletskaya, 16
Breitkopf, 37
C
Caps, 58, 75
Castoldi, 106
Chaffee, 31
Chen, 50
Corberán, 87, 93
D
Duhamel, 100
Dürr, 23
E
Edwards, 77
Eichelbaum, 79
Elokhin, 15
Elżbieta, 92
F
Farin, 56
Fernandez, 14, 15
Fushimi, 17
G
Gaffney, 82
Galvita, 110
Garcia de Leon, 63
Garilov, 112
Gleaves, 80
Gorodsky, 78
H
Hermann, 11
I
Ichiro Yamanaka, 69
IIya, 35
Isaza, 61
Ishikawsa, 8
Ismagilov, 84
K
Kalevaru, 94
Khlebnikova, 67
Kholdeeva, 39, 40
Kondrat, 54
Kong, 46
Kraemer, 86
Krzysztof, 70
L
Lo, 10
Lolli, 99
Lopez Nieto, 114
M
Madix, 28
Matveeva, 64
Medrano, 47, 101
Menning, 21
Mestl, 9
Meyer, 53
Miedziak, 91, 95
Mihaela, 59
Mizuno, 71
N
Nowicka, 25
O
Ozkan, 55
P
Palma del Valle, 107
Parekh, 89
Parvulescu, 34, 98, 113
Paul, 7, 62
Page | 118
Petzold, 22
Prasad, 83
R
Raman, 66
Ramírez Reina, 108
Rataj, 73
Roberto, 109
Rocha, 12
Rozhko, 74
S
Schuh, 49
Schumann, 90
Scotti, 32
Setiawan, 115
Skoufa, 24
Song Lin, 27, 97
Sulman, 72, 102
Swalus, 57
T
Tompos, 51
Trevisanut, 104
V
Vancauwenbergh, 13
Vodyankina, 29, 42, 43, 44
W
Wada, 36
Wang, 33, 76, 111
Wrabetz, 38
Y
Yablonsky, 18, 19, 20
Yamashita, 30
Yee, 45
Z
Zavoianu, 68