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Letter
www.acsami.org
Electrochemical Capture and Release of CO2 in Aqueous Electrolytes
Using an Organic Semiconductor Electrode
Dogukan H. Apaydin,*,† Monika Gora,‡ Engelbert Portenkirchner,§ Kerstin T. Oppelt,∥
Helmut Neugebauer,† Marie Jakesova,† Eric D. Głowacki,⊥ Julia Kunze-Liebhaü ser,§
Malgorzata Zagorska,# Jozef Mieczkowski,‡ and Niyazi Serdar Sariciftci†
†
Linz Institute for Organic Solar Cells/Physical Chemistry and ∥Institute of Inorganic Chemistry, Johannes Kepler University Linz,
A-4040 Linz, Austria
‡
Faculty of Chemistry, University of Warsaw, 02-093 Warsaw, Poland
§
Institute of Physical Chemistry, University of Innsbruck, A-6020 Innsbruck, Austria
⊥
Department of Science and Technology, Linköpings Universitet, Campus Norrköping, SE-601 74 Norrköping, Sweden
#
Faculty of Chemistry, Warsaw University of Technology, 00-664 Warsaw, Poland
S Supporting Information
*
ABSTRACT: Developing efficient methods for capture and controlled release of
carbon dioxide is crucial to any carbon capture and utilization technology. Herein
we present an approach using an organic semiconductor electrode to
electrochemically capture dissolved CO2 in aqueous electrolytes. The process
relies on electrochemical reduction of a thin film of a naphthalene bisimide
derivative, 2,7-bis(4-(2-(2-ethylhexyl)thiazol-4-yl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NBIT). This molecule is specifically
tailored to afford one-electron reversible and one-electron quasi-reversible
reduction in aqueous conditions while not dissolving or degrading. The reduced
NBIT reacts with CO2 to form a stable semicarbonate salt, which can be
subsequently oxidized electrochemically to release CO2. The semicarbonate
structure is confirmed by in situ IR spectroelectrochemistry. This process of
capturing and releasing carbon dioxide can be realized in an oxygen-free
environment under ambient pressure and temperature, with uptake efficiency for CO2 capture of ∼2.3 mmol g−1. This is on par
with the best solution-phase amine chemical capture technologies available today.
KEYWORDS: carbonyl pigments, organic semiconductors, carbon dioxide capture, spectroelectrochemistry, naphthalene bisimide
T
to a direct capture and release of CO2 at low temperatures and
ambient pressures is still mostly uncharted. Earlier works
exploring the redox properties for capturing CO2 dates back to
1971 in which Reddy and co-workers made CO2 react with
benzaniline electrochemically.11 This was followed by studies of
electrochemical carboxylation of unsaturated ketones in 1984,12
Later, Wrighton and Mizen reported the electrochemical
reaction of CO2 with 9,10-phenanthrenquinone to yield a
biscarbonate dianion,13 which then was supported via
theoretical calculations.14 Buttry and co-workers also combined
the use of organic small molecules with electrochemistry and
explored the CO2 capture performance of 4,4′-bipyridine and
reported the step-by-step thermodynamical breakdown of
cycles leading to electrochemical trapping and release of carbon
dioxide.15 The same group recently reported the use of
benzylthiolate, which is generated electrochemically by
he effects of anthropogenic carbon dioxide present a
challenge to scientists in many fields today. Successful
sequestration and utilization technologies both rely on the key
steps of, controlled capture, storage, and release of carbon
dioxide (CO2). Several approaches exist in order to capture and
release CO2 on demand. The most developed technology relies
on amin-based capture agents which can capture CO 2
efficiently and release it back via a temperature swing process.1
These processes are complicated by the necessity of energyintensive heating and management of large volumes of
chemicals. This has inspired work on solid-state capturing
materials. Porous graphitic compounds, polymeric resins were
also investigated2−6 and metal organic frameworks (MOFs)7
have been optimized with respect to their ability of storing
carbon dioxide.8−10 A remarkable CO2 uptake efficiency of 33.5
mmol g−1 sorbent at 40 atm was achieved using Zn-based
MOF.9
Despite having high uptake efficiencies, most of the CO2
storing materials mentioned above only perform at high
pressure and/or temperature conditions for capturing and
releasing of carbon dioxide. The use of redox processes leading
© 2017 American Chemical Society
Received: February 8, 2017
Accepted: April 5, 2017
Published: April 5, 2017
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Figure 1. (a) Chemical structure of NBIT. (b) Cyclic voltammetry (CV) of NBIT film on a glassy carbon working electrode (WE). Electrolyte was
0.1 M Na2SO4 in water. Pt foil was used as counter electrode (CE), whereas Ag/AgCl (3 M KCl) was utilized reference electrode (CE). Inset:
Uptake of CO2 upon electrochemical reduction of NBIT. (c) Cyclic stability of NBIT under N2.
reversible one-electron reduction and at around −0.85 V a
second one-electron reversible reduction is observed. These
peaks are distinctive of many other carbonyl pigments and have
been reported previously.19−23 The molecule can withstand 20
cycles under N2 atmosphere without showing any change in its
electrochemical characteristics and up to 30 cycles with a 30%
decrease in current density (Figure 1c). When the electrolyte
solution is saturated with CO2 and the potential is cycled, a
complete loss of the peaks is observed (Figure 1b blue curve).
The stability under CO2 atmosphere is different than that of
N2. The molecule can withstand 30 times cycling of the
potential (Figure S2). The word stability here refers to the
stability of the pigment as a compact film on the surface. Due to
their nature carbonyl pigments tend to get solubilized upon
reduction or oxidation. In the case of N2 atmosphere the
molecule becomes soluble upon repetitive cycling under
reducing conditions. We can observe the reduced molecule in
solution upon UV−vis measurement.24
This phenomenon was observed previously for another
carbonyl pigment, Quinacridone, and published by our group17
signaling that the binding of CO2 to the carbonyl group, to
form a carbonate-like structure, is taking place. Reduction of
quinacridone and related carbonyl pigments is known to take
place at the carbonyl functional groups. The same behavior of
these oxygens accommodating negative charges is expected for
NBIT. To support this, Gaussian 09 was employed for basic
quantum-chemical calculations using a density functional
theory (DFT)/ HF-based method with the B3LYP hybrid
functional25 and the 3-21g basis set. For simplicity only the
naphthalene bisimide core with phenyl rings attached to the
nitrogen atoms was considered for the geometry optimization
and frequency calculation. The calculation converged and no
imaginary frequencies were obtained. The graphic representation of the electronic frontier orbitals shows, that the lowest
reduction of benzyldisulfide, as a CO2 capturing agent.16 We
have recently built on the earlier carbonyl redox work by
studying the electrochemical addition of CO2 to an industrial
carbonyl pigment quinacridone. The quinacridone was
deposited on a conducting substrate to form an organic
semiconductor electrode which could, upon reduction, capture
CO2 in acetonitrile electrolyte, which was subsequently released
by oxidation. This process had an uptake efficiency of 4.6 mmol
g−1 sorbent.17 To this end, we introduce a new molecule, 2,7bis(4-(2-(2-ethylhexyl)thiazol-4-yl)phenyl)benzo[lmn][3,8]phenanthroline-1,3,6,8(2H,7H)-tetraone (NBIT) (Figure 1a),
which is able to efficiently capture CO2 from aqueous
environment and by forming a semicarbonate structure.
Synthetic details can be found in the Supporting Information.
The naphthalene bisimide core was chosen as an electrondeficient carbonyl pigment unit. To further lower its reduction
potential to ensure reduction of the carbonyl moieties in
aqueous electrolytes at potentials more positive than the onset
of proton reduction, para-phenylene thiazole substituents were
added. This, however, might be a trade-off because with the
lowering of reduction potential might eventually affect the
nucleophilic character of the enolate forming upon reduction.18
Finally, 2-ethylhexyl termination was chosen to provide
resistance to dissolution in aqueous electrolyte upon repeated
cycling. NBIT gave an uptake efficiency of ∼2.3 mmol.g−1 in
aqueous electrolytes (at 1 atm and 22 °C in 0.1 M Na2SO4 in
water), representing a substantial step forward over our
previous efforts.
Cycling between 0 and −1 V in 0.1 M Na2SO4 in water
under nitrogen atmosphere (N2), NBIT film first yields a broad
double-peak with its minor maximum around −0.80 V and its
major maximum around −0.85 V (Figure S1). Upon
subsequent cycling NBIT shows two redox peaks (Figure 1b,
red curve). At around −0.70 V the compound shows a quasi12920
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Even though the measurements under Ar saturation can be
well-explained by a single R/C element in series with the Rs
(Figure S6a), two R/C elements have to be used, in series with
the Rs, to fit the spectra under CO2 saturation at −0.8 V and
below, indicating the presence of two time constants (Figure
S6b). The first one may be attributed to the interface between
the glassy carbon support and the NBIT film, while the second
one is indicative for the interface between the NBIT film and
the electrolyte. Because of the high resistance of the NBIT film
under Ar atmosphere, the second interface to the electrolyte is
not resolved with the performed EIS measurement. In general,
the overall Rct decreases with applied negative potential under
both, Ar and CO2 atmosphere, possibly through improved
electronic conductivity of NBIT and most likely due to
cathodic charge transfer at ≤ −1.0 V (Figure S6b). A detailed
list of all elementsand their corresponding values used to fit the
spectra, can be found in Table S1.
In order to confirm the assignment of the carbonate
structure, as the species arising upon reduction and reaction
of NBIT with CO2, schematically shown in the inset of Figure
1b, we performed in situ attenuated total reflection Fourier
transform infrared spectroelectrochemistry (ATR-FTIR-SPEC)
measurements on the NBIT films cast on germanium (Ge)
reflection element. In this configuration, the Ge crystal acts as
both, WE and the reflection element, whereas a Pt plate and a
silver chloride-coated silver wire act as CE and quasi RE
respectively (Figure 3).
Figure 3a shows the IR characteristics of NBIT under a
constant flow of CO2 saturated Na2SO4 electrolyte (flow rate =
3 mL min−1) at different applied potentials. Prior to applying an
electrochemical potential an IR spectrum was recorded as the
baseline. As the potential of the WE reached −0.8 V, where the
first reduction was observed according to the CV measurements, changes in the IR spectrum started to become
observable. Evidence for formation of a secondary-alcohol
functionality can be observed around ∼3700 cm−1, which
decreases to yield a peak around ∼3300 cm−1 corresponding to
carboxylic acid-like − OH functionality. This behavior is
attributed to the formation of carbonate-like structure upon
addition of CO2 to the now-activated carbonyl group.
Moreover, the peak around ∼1670−1680 cm−1, corresponding
to the imide carbonyl, decreases as a new peak at 1277 cm−1
rises, exhibiting formation of carbonate-like structure.24,26
Finally, we determined the uptake efficiency of NBIT, which
is the figure of merit for CO2 capture agents, of NBIT to be
∼2.3 mmol CO2 g−1. The amount of CO2 was determined by
gas chromatography (GC). After the CO2 is electrochemically
captured by the NBIT film from carbon dioxide saturated
solution, the electrolyte solution was purged with N2 for 120
min to remove residual CO2 from the solution. Upon oxidation
of the film captured CO2 is released. The release of CO2 can be
observed at around 0.24 V with a new redox peak and it was
seen that the NBIT regained its characteristic peaks (Figure
S4). A 2 mL headspace sample was taken with a gastight glass
syringe and injected into GC. The amount of NBIT molecules
in the film was measured spectrophotometrically as well as
electrochemically. The part of the film that was exposed to
electrochemical treatment was dried and then dissolved into a
UV−vis cuvette using chlorobenzene as the solvent. Absorbance measurement was performed, and the amount of NBIT on
the surface was found as 22.8 nmol using molar extinction
coefficient, which was determined via a calibration curve
(Figure S5). Integration of total charge during one CV
unoccupied molecular orbital (LUMO) is distributed over the
large π-system of the naphthalene core including the carbonyl
groups, whereas the highest occupied molecular orbital
(HOMO) is more localized on the imide nitrogens and the
attached phenyl substituents (Figure S3).
To assess the electrochemical nature of the disappearance of
the redox peaks, we conducted electrochemical impedance
spectroscopy (EIS) on NBIT films (Figure 2). EIS was
Figure 2. (a) CV of NBIT film on a glassy carbon electrode (WE)
with colored points indicating the potentials of EIS data acquisition
shown in b and c. Electrolyte was 0.1 M Na2SO4 in water. Nyquist
plots of NBIT film on a glassy carbon electrode (b) under Ar and (c)
under CO2 respectively.
performed after three CV cycles to ensure quasi-reversible
conditions. Spectra were collected in the potential range
between 0 and −1.2 V. A step size of 0.2 V was applied. Each
potential was kept constant for 5 min to ensure steady state
conditions before the impedance measurement, ranging from
500 kHz to 100 mHz with a peak amplitude of ±10 mV.
Measurements were performed under Ar and CO2 saturated
conditions.
From the EIS data, we conclude that the ohmic resistance of
the electrolyte solution (Rs) and the double layer capacitance
(Cdl) are almost equal in all measurements, whereas the charge
transfers resistance (Rct) changes substantially. Ohmic
resistances from 15.5 Ω to 17.0 Ω are measured for the
NBIT film under Ar and under CO2, respectively, whereas the
Cdl is found to range from 26 to 71 μF cm−2. The charge
transfer resistance (Rct) of the NBIT film reduction is strongly
dependent on the atmosphere present, and it decreases
significantly with the applied decreasing potential. Although
under Ar atmosphere, at high potentials between 0.0 V and
−0.6 V, the Rct is expected to be very large and could not be
measured within the given frequency range, it is found to be
2864 Ω at −1.0 V and 537 Ω at −1.2 V, respectively. Under
CO2 atmosphere the Rct changes from 3213 Ω at −0.6 V to 746
Ω at −1.0 V and finally to 96 Ω at −1.2 V.
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Figure 3. (a) IR spectrum of NBIT film under different applied potentials. (b) Schematic representation of the spectroelectrochemical cell.
measurement can be used to estimate the amount of
electrochemically active NBIT on the surface.27,28 We found
this value to be 19.1 nmol, which is in good agreement with the
obtained value via spectroscopy. The faradaic efficiency of the
process is calculated via dividing the amount of captured CO2
(3.49 × 10−8 mol) with the amount of electrons used for the
capture which is 3.82 × 10−8 mol. With this we reached a
faradaic efficiency of ∼91% for the process.
In summary, we showed the performance of a naphthalene
bisimide derivative, NBIT, as an electrochemical CO2 capturing
agent. NBIT achieved a competitive uptake efficiency of 2.3
mmol CO2 g−1, which can be advantageous over state-of-the-art
amine based capturing agents in terms of operating conditions
although the uptake efficiency is not as high (∼8 mmol g−1).29
EIS measurements indicate that the process is taking place on
the surface of the electrode instead of the bulk of the electrolyte
suggesting that CO2 is being anchored in the semiconductor
film. In situ IR spectroelectrochemistry supported this, with
evidence for formation of a carbonate-like species. In contrast
to many carbon capture processes, NBIT can realize the
capture and release of CO2 in ambient pressure and
temperature. This underscores that carbonyl pigments are
organic semiconductors,17,23,30 with suitable stability for
aqueous electrochemical applications, and are thus a promising
materials class.
■
■
visual representation of molecular frontier orbitals
(Figure S3), electrochemical behavior of NBIT before
capture, after capture and after release (Figure S4),
calibration curve for extinction coefficient (Figure S5),
and corresponding equivalent circuits for EIS fitting
(Figure S6) (PDF)
AUTHOR INFORMATION
Corresponding Author
*E-mail: [email protected]. Tel: +43 732 2468 5861.
ORCID
Dogukan H. Apaydin: 0000-0002-1075-8857
Eric D. Głowacki: 0000-0002-0280-8017
Author Contributions
D.H.A. and M.G. contributed equally to this work.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The uthors gratefully acknowledge the funding from the
Austrian Science Foundation (FWF) within the framework of
the Wittgenstein Prize of N.S. Sariciftci Solare Energie
Umwandlung Z222- N19. M.Z. is thankful for the financial
support from Warsaw University of Technology.
ASSOCIATED CONTENT
■
S Supporting Information
*
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.7b01875.
Synthetic route (Scheme S1), electrode preparation and
characterization, cyclic stability under CO2 (Figure S2),
REFERENCES
(1) D’Alessandro, D. M.; Smit, B.; Long, J. R. Carbon Dioxide
Capture: Prospects for New Materials. Angew. Chem., Int. Ed. 2010, 49,
6058−6082.
12922
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Dyes to Modern Organic Semiconductors. Isr. J. Chem. 2012, 52, 540−
551.
(21) Deblase, C. R.; Hernández-Burgos, K.; Rotter, J. M.; Fortman,
D. J.; dos S. Abreu, D.; Timm, R. A.; Diógenes, I. C. N.; Kubota, L. T.;
Abruña, H. D.; Dichtel, W. R. Cation-Dependent Stabilization of
Electrogenerated Naphthalene Diimide Dianions in Porous Polymer
Thin Films and Their Application to Electrical Energy Storage. Angew.
Chem., Int. Ed. 2015, 54, 13225−13229.
(22) Vadehra, G. S.; Maloney, R. P.; Garcia-garibay, M. A.; Dunn, B.
Naphthalene Diimide Based Materials with Adjustable Redox
Potentials: Evaluation for Organic Lithium-Ion Batteries Naphthalene
Diimide Based Materials with Adjustable Redox Poten- Tials:
Evaluation for Organic Lithium-Ion Batteries. Chem. Mater. 2014,
26, 7151−7157.
(23) Głowacki, E. D.; Apaydin, D. H.; Bozkurt, Z.; Monkowius, U.;
Demirak, K.; Tordin, E.; Himmelsbach, M.; Schwarzinger, C.; Burian,
M.; Lechner, R. T.; Demitri, N.; Voss, G.; Sariciftci, N. S. Air-Stable
Organic Semiconductors Based on 6,6′-Dithienylindigo and Polymers
Thereof. J. Mater. Chem. C 2014, 2, 8089−8097.
(24) Andric, G.; Boas, J. F.; Bond, A. M.; Fallon, G. D.; Ghiggino, K.
P.; Hogan, C. F.; Hutchison, J. A.; Lee, M. A. P.; Langford, S. J.;
Pilbrow, J. R.; Troup, G. J.; Woodward, C. P. Spectroscopy of
Naphthalene Diimides and Their Anion Radicals. Aust. J. Chem. 2004,
57, 1011−1019.
(25) Frisch, M. J.; Trucks, G. W.; Schlegel, H. B.; Scuseria, G. E.;
Robb, M. A.; Cheeseman, J. R.; Scalmani, G.; Barone, V.; Mennucci,
B.; Petersson, G. A.; Nakatsuji, H.; Caricato, M.; Li, X.; Hratchian, H.
P.; Izmaylov, A. F.; Bloino, J.; Zheng, G.; Sonnenberg, J. L.; Hada, M.;
Ehara, M.; Toyota, K.; Fukuda, R.; Hasegawa, J.; Ishida, M.; Nakajima,
T.; Honda, Y.; Kitao, O.; Nakai, H.; Vreven, T.; Montgomery, J. A., Jr.;
Peralta, J. E.; Ogliaro, F.; Bearpark, M.; Heyd, J. J.; Brothers, E.; Kudin,
K. N.; Staroverov, V. N.; Kobayashi, R.; Normand, J.; Raghavachari, K.;
Rendell, A.; Burant, J. C.; Iyengar, S. S.; Tomasi, J.; Cossi, M.; Rega,
N.; Millam, J. M.; Klene, M.; Knox, J. E.; Cross, J. B.; Bakken, V.;
Adamo, C.; Jaramillo, J.; Gomperts, R.; Stratmann, R. E.; Yazyev, O.;
Austin, A. J.; Cammi, R.; Pomelli, C.; Ochterski, J. W.; Martin, R. L.;
Morokuma, K.; Zakrzewski, V. G.; Voth, G. A.; Salvador, P.;
Dannenberg, J. J.; Dapprich, S.; Daniels, A. D.; Farkas, Ö .;
Foresman, J. B.; Ortiz, J. V.; Cioslowski, J.; Fox, D. J. Gaussian 09;
Gaussian, Inc.: Wallingford, CT, 2009.
(26) Nyquist, R. A.; Potts, W. J. Infrared Absoptions Charactertic of
Organic Carbonate Derivatives and Related Compounds. Spectrochmica Acta 1961, 17, 679−697.
(27) Barbier, B.; Pinson, J.; Desarmot, G.; Sanchez, M. Electrochemical Bonding of Amines to Carbon Fiber Surfaces Toward
Improved Carbon-Epoxy Composites. J. Electrochem. Soc. 1990, 137,
1757−1764.
(28) Sandroni, M.; Volpi, G.; Fiedler, J.; Buscaino, R.; Viscardi, G.;
Milone, L.; Gobetto, R.; Nervi, C. Iridium and Ruthenium Complexes
Covalently Bonded to Carbon Surfaces by Means of Electrochemical
Oxidation of Aromatic Amines. Catal. Today 2010, 158, 22−28.
(29) Supap, T.; Idem, R.; Tontiwachwuthikul, P.; Saiwan, C. Kinetics
of Sulfur Dioxide- and Oxygen-Induced Degradation of Aqueous
Monoethanolamine Solution during CO2 Absorption from Power
Plant Flue Gas Streams. Int. J. Greenhouse Gas Control 2009, 3, 133−
142.
(30) Jakesova, M.; Apaydin, D. H.; Sytnyk, M.; Oppelt, K.; Heiss, W.;
Sariciftci, N. S.; Glowacki, E. D. Hydrogen-Bonded Organic
Semiconductors as Stable Photoelectrocatalysts for Efficient Hydrogen
Peroxide Photosynthesis. Adv. Funct. Mater. 2016, 26, 5248−5254.
(2) Meng, L. Y.; Park, S. J. Effect of Heat Treatment on CO2
Adsorption of KOH-Activated Graphite Nanofibers. J. Colloid Interface
Sci. 2010, 352, 498−503.
(3) Mishra, A. K.; Ramaprabhu, S. Carbon Dioxide Adsorption in
Graphene Sheets Carbon Dioxide Adsorption in Graphene Sheets. AIP
Adv. 2011, 1, 032152.
(4) Presser, V.; McDonough, J.; Yeon, S.-H.; Gogotsi, Y. Effect of
Pore Size on Carbon Dioxide Sorption by Carbide Derived Carbon.
Energy Environ. Sci. 2011, 4, 3059−3066.
(5) Sevilla, M.; Fuertes, A. B. CO2 Adsorption by Activated
Templated Carbons. J. Colloid Interface Sci. 2012, 366, 147−154.
(6) Drage, T. C.; Arenillas, A.; Smith, K. M.; Pevida, C.; Piippo, S.;
Snape, C. E. Preparation of Carbon Dioxide Adsorbents from the
Chemical Activation of Urea−formaldehyde and Melamine−formaldehyde Resins. Fuel 2007, 86, 22−31.
(7) Sumida, K.; Rogow, D. L.; Mason, J. A.; McDonald, T. M.; Bloch,
E. D.; Herm, Z. R.; Bae, T. H.; Long, J. R. Carbon Dioxide Capture in
Metal-Organic Frameworks. Chem. Rev. 2012, 112, 724−781.
(8) Bae, Y. S.; Mulfort, K. L.; Frost, H.; Ryan, P.; Punnathanam, S.;
Broadbelt, L. J.; Hupp, J. T.; Snurr, R. Q. Separation of CO2 from CH4
Using Mixed-Ligand Metal-Organic Frameworks. Langmuir 2008, 24,
8592−8598.
(9) Millward, A. R.; Yaghi, O. M. Metal Organic Frameworks with
Exceptionally High Capacity for Storage of Carbon Dioxide at Room
Temperature. J. Am. Chem. Soc. 2005, 127, 17998−17999.
(10) Bourrelly, S.; Llewellyn, P. L.; Serre, C.; Millange, F.; Loiseau,
T.; Ferey, G. Different Adsorption Behaviors of Methane and Carbon
Dioxide in the Isotypic Nanoporous Metal Terephthalates MIL-53 and
MIL-47. J. Am. Chem. Soc. 2005, 127, 13519−13521.
(11) Weinberg, N. L.; Kentaro Hoffmann, A.; Reddy, T. B. The
Electrochemical Reductive Carboxylation of Benzalaniline in Molten
Tetraethyl Ammonium P-Toluenesulfonate. Tetrahedron Lett. 1971,
12, 2271−2274.
(12) Harada, J.; Sakakibara, Y.; Kunai, A.; Sasaki, K. Electrochemical
Carboxylation of A,b-Unsaturated Ketones with Carbon Dioxide. Bull.
Chem. Soc. Jpn. 1984, 57, 611−612.
(13) Mizen, M. B.; Wrighton, M. S. Reductive Addition of CO2 to
9,10-Phenanthrenequinone. J. Electrochem. Soc. 1989, 136, 941−946.
(14) Stern, M. C.; Simeon, F.; Hammer, T.; Landes, H.; Herzog, H.
J.; Hatton, T. A. Electrochemically Mediated Separation for Carbon
Capture. Energy Procedia 2011, 4, 860−867.
(15) Ranjan, R.; Olson, J.; Singh, P.; Lorance, E. D.; Buttry, D. A.;
Gould, I. R. Reversible Electrochemical Trapping of Carbon Dioxide
Using 4,4′-Bipyridine That Does Not Require Thermal Activation. J.
Phys. Chem. Lett. 2015, 6, 4943−4946.
(16) Singh, P.; Rheinhardt, J. H.; Olson, J. Z.; Tarakeshwar, P.;
Mujica, V.; Buttry, D. A. Electrochemical Capture and Release of
Carbon Dioxide Using a Disulfide-Thiocarbonate Redox Cycle
Electrochemical Capture and Release of Carbon Dioxide Us- Ing a
Disulfide-Thiocarbonate Redox Cycle. J. Am. Chem. Soc. 2017, 139,
1033−1036.
(17) Apaydin, D. H.; Głowacki, E. D.; Portenkirchner, E.; Sariciftci,
N. S. Direct Electrochemical Capture and Release of Carbon Dioxide
Using an Industrial Organic Pigment: Quinacridone **. Angew. Chem.,
Int. Ed. 2014, 53, 6819−6822.
(18) Nagaoka, T.; Nishii, N.; Fujii, K.; Ogura, K. Mechanisms of
Reductive Addition of CO2 to Quinones in Acetonitrile. J. Electroanal.
Chem. 1992, 322 (1−2), 383−389.
(19) (a) Głowacki, E. D.; Voss, G.; Demirak, K.; Havlicek, M.;
Sünger, N.; Okur, A. C.; Monkowius, U.; Gąsiorowski, J.; Leonat, L.;
Sariciftci, N. S. A Facile Protection-Deprotection Route for Obtaining
Indigo Pigments as Thin Films and Their Applications in Organic Bulk
Heterojunctions. Chem. Commun. (Cambridge, U. K.) 2013, 49, 6063−
6065. (b) Glowacki, E. D.; Leonat, L.; Voss, G.; Bodea, M.; Bozkurt,
Z.; Irimia-Vladu, M.; Bauer, S.; Sariciftci, N. S. Natural and NatureInspired Semiconductors for Organic Electronics. Proc. SPIE 2011,
8118, 81180M−81180M−10.
(20) Glowacki, E. D.; Voss, G.; Leonat, L.; Irimia-Vladu, M.; Bauer,
S.; Sariciftci, N. S. Indigo and Tyrian Purple - From Ancient Natural
12923
DOI: 10.1021/acsami.7b01875
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