Center for Direct Catalytic Conversion of Biomass to Biofuels (C3Bio)
C3Bio develops transformational knowledge and technologies for the direct conversion of plant lignocellulosic biomass to advanced (drop‐in) biofuels and other biobased products, currently derived from oil, by the use of new chemical catalysts and thermal treatments. RESEARCH PLAN AND DIRECTIONS
We will maximize the energy and carbon efficiencies of advanced biofuels production by the design of both thermal and chemical conversion processes and the biomass itself. Impacts are to more than double the carbon captured into fuel molecules and expand
the product range to alkanes and other energy‐rich fuels.
Sample Preparation for Biomass Biomaterials Microscopy
Scientific Achievement
Optimized and standardized a set of hybrid biological and materials‐science sample preparation techniques to enable consistently high quality multi‐
scale microscopy analysis of biomass.
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Significance and Impact
• Provides a single “go‐to” reference for the field that shares details and tips that are not possible to fully convey in the typical manuscript methods section. • Facilitates direct, quantitative comparison between samples prepared and imaged by these methods.
Research Details
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NREL’s Biomass Surface Characterization Laboratory (BSCL) is a leader in multi‐scale microscopic structural analysis of biomass conversion processes.
C3Bio enabled a critical transition in the BSCL workflow to include quantitative image analysis as the final goal of all imaging efforts.
The impact quantitative image analysis has had on informing sample prep and image acquisition is reflected in this chapter.
Donohoe, B. S.; Ciesielski, P. N.; and Vinzant, T. B. PRESERVATION AND PREPARATION OF LIGNOCELLULOSIC
BIOMASS SAMPLES FOR MULTI‐SCALE MICROSCOPY
ANALYSIS, In: Michael E. Himmel (ed.), Biomass Conversion: Methods and Protocols, Methods in Molecular Biology, 908, 31‐47 (2012). [10.1007/978‐1‐61779‐956‐3_4]
Work was performed at NREL
Tandem Mass Spectrometric Analysis of Degraded Cellulose 377
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Relative Abundance
Scientific Achievement
Demonstrated that chloride anion attachment/atmospheric pressure ionization generates only one ion for each carbohydrate in a mixture and that multistage tandem mass spectrometry can be used to determine the ions’ structures.
Significance and Impact
Allows more detailed characterization of mixtures of pyrolyzed and other‐
wise degraded cellulose than before. 60
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Research Details
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Used linear quadrupole ion trap and a variety of ionization methods to ionize pure carbohydrates After identification of the best ionization method, examined known mixtures of carbohydrates Measured tandem mass spectra up to MS4 to gather useful structural information from the fragmentation patterns of the carbohydrates
Vinueza, N.R., Gallardo, V.A., Klimek, J.F., Carpita, N., and Kenttämaa, H.I. ANALYSIS OF CARBOHYDRATES BY ATMOSPHERIC PRESSURE CHLORIDE ANION
ATTACHMENT TANDEM MASS SPECTROMETRY, Fuel, 105, 235‐246 (2013).
Work was performed at Purdue University
Scientific Achievement
A porphyrin‐based porous organic polymer (POP) loaded with Fe3+ catalyst is a thermally stable and recyclable catalyst for oxidation of hydroxymethylfurfural (HMF) to 2,5‐furandicarboxylic acid (FDCA) in water using molecular oxygen. Significance and Impact
• In C3Bio, we have shown that maleic acid catalysis converts glucose in non‐crystalline polymers in biomass to HMF.
• Saha et al achieved quantitative conversion of HMF with >85% selectivity in water under mild reaction conditions.
• The catalyst retained Fe(III) oxidation state after catalysis and metal does not leach into solution.
• FDCA is a promising replacement for petroleum‐
derived terephthalic acid for polyester production.
HMF conversion and product distribution, %
FeIII(POP) Catalyst for HMF Oxidation to FDCA
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Research Details
• Characterization of the catalyst showed uniform nanospheres of dimension 50‐100 nm which self‐assemble to larger sizes. • Hydroxymethyl group (‐CH2OH) of HMF oxidized first followed by oxidation of –CHO group.
• The data support a hypothesis that the reaction progresses via a free radical chain mechanism with the formation of peroxyl radical in the catalytic cycle.
12
After catalysis
Saha, B.; Gupta, D.; Abu‐Omar, M. M.; Modak, A.; and Bhaumik, A. PORPHYRIN
BASED POROUS ORGANIC POLYMER SUPPORTED
IRON(III) CATALYST FOR EFFICIENT AEROBIC
OXIDATION OF 5‐HYDROXYMETHYLFURFURAL
INTO 2,5‐FURANDICARBOXYLIC ACID. Journal of Catalysis, 299, 316‐320 (2013). [10.1016/j.jcat.2012.12.024] Work was performed at Purdue University and University of Delhi. Catalyst was prepared by collaborator at Indian Association for the Cultivation of Science.
3D Electron Tomography of Pretreated Biomass Informs
Atomic Modeling of Cellulose Microfibrils
Averagae radius of curvature (nm)
Scientific Achievement
• Using 3D electron tomography and novel computational analysis tools, we modeled and quantified the macromolecular architecture of thermochemically treated biomass.
Significance and Impact
• This study produced the first measurements of cellulose microfibril curvature. We investigated the significance of this parameter by construction and evaluation of atomic models that exhibited the geometry obtained from the microscopy data.
Tomographic subvolumes showing space curves fit to cellulose microfibrils (scale bars 10 nm)
The radius of curvature of the microfibrils was measured from the fitted curves. Atomistic models were constructed using the extracted geometric parameters. Kink defects were predicted in the atomic models when the fibril was bent about certain Original atomic
Energy‐minimized crystallographic directions. coordinates
atomic coordinates
Ciesielski, P. N.; Matthews, J. F.; Tucker, M. P.; Beckham, G. T.; Crowley, M. F.; Himmel, M. E.; Donohoe, B. S. 3D ELECTRON TOMOGRAPHY OF PRETREATED
BIOMASS INFORMS ATOMIC MODELING OF CELLULOSE MICROFIBRILS. ACS Nano, 7, 8011‐8019. 2013. DOI: 10.1021/nn4031542.
Work performed at the National Renewable Energy Laboratory
• Our results and analyses have elucidated new relationships between the nanostructure and energetics of plant cellulose that may be exploited in catalytic conversion processes.
Catalytic cleavage and hydrodeoxygenation of lignin models
Scientific Achievement
A combined Zn/Pd/C catalyst effectively cleaved the lignin β‐O‐4 linkage and subsequently hydrodeoxygenated the aromatic fragments without loss of aromatic functional groups. The catalyst is robust and fully recyclable without the need for additional zinc.
Significance and Impact
The β‐O‐4 linkage is the most abundant repeating subunit of the lignin macromolecule. Devising a catalyst that can selectively cleave this type of ether linkage and undergo hydrodeoxygenation provides a means of unzipping the very complex polymeric structure into smaller, manageable molecules that have higher energy value.
Research Details
− In a typical experiment: substrate, 5 wt% Zn/Pd/C, and methanol (15 mL) were added to a dry glass sleeve, placed into a stainless steel Parr reactor and sealed. While stirring, the mixture was purged with UHP grade H2 for ca. 1–2 min., pressurized with H2 (30–300 psi, 2–20.4 bar), and heated to 150⁰C.
− The monomeric lignin surrogate substrates were 4‐(hydroxymethyl)‐2‐methoxyphenol, 4‐hydroxy‐3‐
methoxybenzaldehyde, and 4‐(methoxymethyl)‐2‐methoxyphenol. The dimeric lignin surrogate was guaiacylglycerol‐β‐guaiacyl.
− Reaction products were characterized using HPLC coupled to an LQIT mass spectrometer equipped with an ESI source using negative ion mode.
Parsell TH, Owen BC, Klein I, Jarrell TM, Marcum CL, Haupert LJ, Amundson LM, Kenttämaa HI Ribeiro F, Miller JT, Abu‐
Omar MM. Cleavage and hydrodeoxygenation (HDO) of C–O bonds relevant to lignin conversion using Pd/Zn synergistic catalysis. Chem. Sci., 4, 806‐813 (2013). [10.1039/C2SC21657D]
Work was performed at Purdue University and Argonne National Lab
Cobalt‐Catalyzed Oxidative Cleavage of Lignin Models
Scientific Achievement
G models of lignin are slow to react.
However, we developed a new catalyst that transforms both S and G subunits lignin models into benzoquinones in high yields.
Significance and Impact
Lignin, a macromolecule of syringyl
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L i g n i n M o d e l s
C h e m i c a l s
(S) and guaiacyl (G) subunits, is an underused product of biorefinery operations. Optimal reaction conditions for the conversion of lignin models to quinones were determined. Internal ligand and aliphatic base on the ligand allow for a much stronger catalytic activity. This methodology is highly applicable to the oxidative cleavage of lignin. ‐ Cedeno, D.; Bozell, J. J.; Research Details
Tetrahedron Lett. 2012, 53, 2380‐2383.
‐ Previous studies from our laboratory showed that G lignin models undergo oxidation in presence ‐ Biannic, B.; Bozell, J. J. of Co‐salen catalyst and a hindered base in 50% yield. manuscript in preparation
‐ This new unsymmetrical Co‐salen catalyst oxidizes each of the lignin primary units.
Work was performed at: ‐ The catalyst contains an internal nitrogen ligand (needed for S and G subunits) and an internal
University of Tennessee,
bulky base (needed for G subunit).
Center for Renewable ‐ An efficient protecting group‐free strategy for the synthesis of lignin models has also been developed. Carbon
Selective cobalt catalyzed oxidations of biorefinery lignin
Scientific Achievement
New processes promote oxidation of both general types of aromatic structure in lignin models (S and G) that are verified in oxidation of actual biorefinery lignin samples (organosolv and extracted kraft) without Research Details
compromising yield.
₋ In order to assess the involvement of the sterically hindered base, we Significance and Impact
studied the interaction between DIPEA and Co(salen) using NMR and UV–vis spectroscopy Instead of burning ₋ Although S subunit models from guaiacyl unit models were easily biorefinery ‘waste’ lignin as converted into their corresponding p‐quinones, the same approach with vanillyl alcohol, a model of the G subunit, gave the corresponding a $0.05/lb fuel, we have 2‐methoxybenzoquinone in only 21% yield. G models are more identified processes that difficult to oxidize than S models because formation of the key position lignin as a chemical phenoxy radical is slower.
₋ Molecular modeling studies (DFT) have provided new insight into the feedstock, opening new mechanism and its control
opportunities in biobased ₋ Mass spectrometry development at Purdue has identified new products resulting from lignin oxidation
chemical production
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Diana C, and Bozell JJ. Catalytic oxidation of para‐substituted phenols with cobalt‐
Schiff base complexes/O2 ‐
selective conversion of syringyl and guaiacyl
lignin models to benzoquinones. Tetrahedron Letters 53, 2380‐2383 (2012).
Work was performed at the University of Tennessee, Knoxville Center for Renewable Carbon
Solvent‐free methods for making biomass‐derived acetals
Scientific Achievement
Demonstrated solvent‐free synthesis of acetals prepared from furfural and glycerol using a variety of common Lewis acids and solid acids
Significance and Impact
Acetals are produced in high yields under mild reaction conditions, allowing for a new route for the utilization of glycerol. Acetal products are potentially useful synthetic platforms and potential fuel additives
Research Details
‐ Reactions between furfural and glycerol are performed at 100°C with a five‐
fold excess of furfural, allowing for yields up to 90%
‐ The addition of a dry stream of nitrogen purging the headspace improves yields and allows for a reduced excess of furfural
‐ The novel reaction methods are applicable to crude glycerol
‐ Acetal products were successfully hydrogenated and acetylated, and the resulting material tested as fuel additives in biodiesel
Wegenhart, Benjamin L.; Liu, Shuo; Thom, Melanie; Stanley, David; and Abu‐Omar, Mahdi M. SOLVENT‐FREE METHODS FOR MAKING ACETALS DERIVED
FROM GLYCEROL AND FURFURAL AND THEIR USE AS A
BIODIESEL FUEL COMPONENT, ACS Catalysis, 2, 2524‐
2530 (2012). [10.1021/cs300562e]
Work was performed at Purdue University