Benzimidazoles as Metal-Free and Recyclable Hydrides for CO2 Reduction to Formate
Abstract
We report a novel metal-free chemical reduction of CO2 by a recyclable benzimidazole-based organo-hydride, whose choice was guided by quantum chemical calculations. Notably, benzimidazole-based hydride donors rival the hydride-donating abilities of noble-metal-based hydrides such as [Ru(tpy)(bpy)H]+ and [Pt(depe)2H]+. Chemical CO2 reduction to the formate anion (HCOO–) was carried out in the absence of biological enzymes, a sacrificial Lewis acid, or a base to activate the substrate or reductant. 13CO2 experiments confirmed the formation of H13COO– by CO2 reduction with the formate product characterized by 1H NMR and 13C NMR spectroscopy and ESI-MS. The highest formate yield of 66% was obtained in the presence of potassium tetrafluoroborate under mild conditions. The likely role of exogenous salt additives in this reaction is to stabilize and shift the equilibrium toward the ionic products. After CO2 reduction, the benzimidazole-based hydride donor was quantitatively oxidized to its aromatic benzimidazolium cation, establishing its recyclability. In addition, we electrochemically reduced the benzimidazolium cation to its organo-hydride form in quantitative yield, demonstrating its potential for electrocatalytic CO2 reduction. These results serve as a proof of concept for the electrocatalytic reduction of CO2 by sustainable, recyclable, and metal-free organo-hydrides.
- Authors:
-
- Univ. of Colorado, Boulder, CO (United States)
- Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
- Univ. of Colorado, Boulder, CO (United States); Pasteur Inst., Paris (France)
- Univ. of Colorado, Boulder, CO (United States); National Renewable Energy Lab. (NREL), Golden, CO (United States)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- National Science Foundation (NSF); Petroleum Research Fund (PRF); USDOE
- OSTI Identifier:
- 1558602
- Grant/Contract Number:
- AC02-06CH11357; CHE-1214131; CHE-1112564; 54436-ND4
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 141; Journal Issue: 1; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; CO2 reduction; benzimidazole; metal-free; organo-hydride; solar fuels
Citation Formats
Lim, Chern-Hooi, Ilic, Stefan, Alherz, Abdulaziz, Worrell, Brady T., Bacon, Samuel S., Hynes, James T., Glusac, Ksenija D., and Musgrave, Charles B. Benzimidazoles as Metal-Free and Recyclable Hydrides for CO2 Reduction to Formate. United States: N. p., 2018.
Web. doi:10.1021/jacs.8b09653.
Lim, Chern-Hooi, Ilic, Stefan, Alherz, Abdulaziz, Worrell, Brady T., Bacon, Samuel S., Hynes, James T., Glusac, Ksenija D., & Musgrave, Charles B. Benzimidazoles as Metal-Free and Recyclable Hydrides for CO2 Reduction to Formate. United States. https://doi.org/10.1021/jacs.8b09653
Lim, Chern-Hooi, Ilic, Stefan, Alherz, Abdulaziz, Worrell, Brady T., Bacon, Samuel S., Hynes, James T., Glusac, Ksenija D., and Musgrave, Charles B. Tue .
"Benzimidazoles as Metal-Free and Recyclable Hydrides for CO2 Reduction to Formate". United States. https://doi.org/10.1021/jacs.8b09653. https://www.osti.gov/servlets/purl/1558602.
@article{osti_1558602,
title = {Benzimidazoles as Metal-Free and Recyclable Hydrides for CO2 Reduction to Formate},
author = {Lim, Chern-Hooi and Ilic, Stefan and Alherz, Abdulaziz and Worrell, Brady T. and Bacon, Samuel S. and Hynes, James T. and Glusac, Ksenija D. and Musgrave, Charles B.},
abstractNote = {We report a novel metal-free chemical reduction of CO2 by a recyclable benzimidazole-based organo-hydride, whose choice was guided by quantum chemical calculations. Notably, benzimidazole-based hydride donors rival the hydride-donating abilities of noble-metal-based hydrides such as [Ru(tpy)(bpy)H]+ and [Pt(depe)2H]+. Chemical CO2 reduction to the formate anion (HCOO–) was carried out in the absence of biological enzymes, a sacrificial Lewis acid, or a base to activate the substrate or reductant. 13CO2 experiments confirmed the formation of H13COO– by CO2 reduction with the formate product characterized by 1H NMR and 13C NMR spectroscopy and ESI-MS. The highest formate yield of 66% was obtained in the presence of potassium tetrafluoroborate under mild conditions. The likely role of exogenous salt additives in this reaction is to stabilize and shift the equilibrium toward the ionic products. After CO2 reduction, the benzimidazole-based hydride donor was quantitatively oxidized to its aromatic benzimidazolium cation, establishing its recyclability. In addition, we electrochemically reduced the benzimidazolium cation to its organo-hydride form in quantitative yield, demonstrating its potential for electrocatalytic CO2 reduction. These results serve as a proof of concept for the electrocatalytic reduction of CO2 by sustainable, recyclable, and metal-free organo-hydrides.},
doi = {10.1021/jacs.8b09653},
journal = {Journal of the American Chemical Society},
number = 1,
volume = 141,
place = {United States},
year = {Tue Nov 27 00:00:00 EST 2018},
month = {Tue Nov 27 00:00:00 EST 2018}
}
Web of Science
Works referenced in this record:
Frontiers, Opportunities, and Challenges in Biochemical and Chemical Catalysis of CO 2 Fixation
journal, June 2013
- Appel, Aaron M.; Bercaw, John E.; Bocarsly, Andrew B.
- Chemical Reviews, Vol. 113, Issue 8
Powering the planet: Chemical challenges in solar energy utilization
journal, October 2006
- Lewis, N. S.; Nocera, D. G.
- Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735
The Hydride-Transfer Reaction.
journal, February 1960
- Deno, N. C.; Peterson, Henry J.; Saines, George S.
- Chemical Reviews, Vol. 60, Issue 1
Towards a Comprehensive Hydride Donor Ability Scale
journal, November 2012
- Horn, Markus; Schappele, Ludwig H.; Lang-Wittkowski, Gabriele
- Chemistry - A European Journal, Vol. 19, Issue 1
Hydride-Donor Abilities of 1,4-Dihydropyridines: A Comparison with π Nucleophiles and Borohydride Anions
journal, March 2009
- Richter, Dorothea; Mayr, Herbert
- Angewandte Chemie International Edition, Vol. 48, Issue 11
Direct synthesis of formic acid from carbon dioxide by hydrogenation in acidic media
journal, June 2014
- Moret, Séverine; Dyson, Paul J.; Laurenczy, Gábor
- Nature Communications, Vol. 5, Issue 1
A Cobalt-Based Catalyst for the Hydrogenation of CO 2 under Ambient Conditions
journal, July 2013
- Jeletic, Matthew S.; Mock, Michael T.; Appel, Aaron M.
- Journal of the American Chemical Society, Vol. 135, Issue 31
An Organic Hydride Transfer Reaction of a Ruthenium NAD Model Complex Leading to Carbon Dioxide Reduction
journal, September 2012
- Ohtsu, Hideki; Tanaka, Koji
- Angewandte Chemie International Edition, Vol. 51, Issue 39
Catalytic Reduction of CO 2 by Renewable Organohydrides
journal, December 2015
- Lim, Chern-Hooi; Holder, Aaron M.; Hynes, James T.
- The Journal of Physical Chemistry Letters, Vol. 6, Issue 24
Reduction of CO 2 to Methanol Catalyzed by a Biomimetic Organo-Hydride Produced from Pyridine
journal, November 2014
- Lim, Chern-Hooi; Holder, Aaron M.; Hynes, James T.
- Journal of the American Chemical Society, Vol. 136, Issue 45
Dihydropteridine/Pteridine as a 2H + /2e – Redox Mediator for the Reduction of CO 2 to Methanol: A Computational Study
journal, April 2017
- Lim, Chern-Hooi; Holder, Aaron M.; Hynes, James T.
- The Journal of Physical Chemistry B, Vol. 121, Issue 16
Carbon Dioxide Reduction by Pincer Rhodium η 2 -Dihydrogen Complexes: Hydrogen-Binding Modes and Mechanistic Studies by Density Functional Theory Calculations
journal, January 2007
- Huang, Kuo-Wei; Han, Joseph H.; Musgrave, Charles B.
- Organometallics, Vol. 26, Issue 3
Calculation of thermodynamic hydricities and the design of hydride donors for CO2 reduction
journal, July 2012
- Muckerman, J. T.; Achord, P.; Creutz, C.
- Proceedings of the National Academy of Sciences, Vol. 109, Issue 39
Thermodynamic and Kinetic Hydricity of Ruthenium(II) Hydride Complexes
journal, September 2012
- Matsubara, Yasuo; Fujita, Etsuko; Doherty, Mark D.
- Journal of the American Chemical Society, Vol. 134, Issue 38
Hydricity of transition-metal hydrides and its role in CO2 reduction
journal, January 2000
- DuBois, Daniel L.; Berning, Douglas E.
- Applied Organometallic Chemistry, Vol. 14, Issue 12
An Iron Electrocatalyst for Selective Reduction of CO 2 to Formate in Water: Including Thermochemical Insights
journal, November 2015
- Taheri, Atefeh; Thompson, Emily J.; Fettinger, James C.
- ACS Catalysis, Vol. 5, Issue 12
Remarkable accelerating and decelerating effects of the bases on CO2 reduction using a ruthenium NADH model complex
journal, December 2015
- Ohtsu, Hideki; Tsuge, Kiyoshi; Tanaka, Koji
- Journal of Photochemistry and Photobiology A: Chemistry, Vol. 313
Recent Advances in Inorganic Heterogeneous Electrocatalysts for Reduction of Carbon Dioxide
journal, March 2016
- Zhu, Dong Dong; Liu, Jin Long; Qiao, Shi Zhang
- Advanced Materials, Vol. 28, Issue 18
Catalysis of the electrochemical reduction of carbon dioxide
journal, January 2013
- Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel
- Chem. Soc. Rev., Vol. 42, Issue 6
A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels
journal, January 2014
- Qiao, Jinli; Liu, Yuyu; Hong, Feng
- Chem. Soc. Rev., Vol. 43, Issue 2
Homogeneously Catalyzed Electroreduction of Carbon Dioxide—Methods, Mechanisms, and Catalysts
journal, January 2018
- Francke, Robert; Schille, Benjamin; Roemelt, Michael
- Chemical Reviews, Vol. 118, Issue 9
Homogeneous Catalysis for Sustainable Hydrogen Storage in Formic Acid and Alcohols
journal, October 2017
- Sordakis, Katerina; Tang, Conghui; Vogt, Lydia K.
- Chemical Reviews, Vol. 118, Issue 2
Formic Acid as a Hydrogen Energy Carrier
journal, December 2016
- Eppinger, Jörg; Huang, Kuo-Wei
- ACS Energy Letters, Vol. 2, Issue 1
Formic acid as a hydrogen storage material – development of homogeneous catalysts for selective hydrogen release
journal, January 2016
- Mellmann, Dörthe; Sponholz, Peter; Junge, Henrik
- Chemical Society Reviews, Vol. 45, Issue 14
The Crystal Structure of [Fe]-Hydrogenase Reveals the Geometry of the Active Site
journal, July 2008
- Shima, S.; Pilak, O.; Vogt, S.
- Science, Vol. 321, Issue 5888
Thermodynamic and kinetic hydricities of metal-free hydrides
journal, January 2018
- Ilic, Stefan; Alherz, Abdulaziz; Musgrave, Charles B.
- Chemical Society Reviews, Vol. 47, Issue 8
Thermodynamic Hydricities of Biomimetic Organic Hydride Donors
journal, March 2018
- Ilic, Stefan; Pandey Kadel, Usha; Basdogan, Yasemin
- Journal of the American Chemical Society, Vol. 140, Issue 13
Hydride, Hydrogen Atom, Proton, and Electron Transfer Driving Forces of Various Five-Membered Heterocyclic Organic Hydrides and Their Reaction Intermediates in Acetonitrile
journal, February 2008
- Zhu, Xiao-Qing; Zhang, Ming-Tian; Yu, Ao
- Journal of the American Chemical Society, Vol. 130, Issue 8
Formal Transfers of Hydride from Carbon−Hydrogen Bonds. Generation of H 2 from Orthoformamides Designed To Undergo Intramolecular Protonolyses of Activated Carbon−Hydrogen Bonds
journal, January 1996
- Brunet, Philippe; Wuest, James D.
- The Journal of Organic Chemistry, Vol. 61, Issue 6
The Path of Carbon in Photosynthesis: The carbon cycle is a tool for exploring chemical biodynamics and the mechanism of quantum conversion
journal, March 1962
- Calvin, M.
- Science, Vol. 135, Issue 3507
Roles of the Lewis Acid and Base in the Chemical Reduction of CO 2 Catalyzed by Frustrated Lewis Pairs
journal, August 2013
- Lim, Chern-Hooi; Holder, Aaron M.; Hynes, James T.
- Inorganic Chemistry, Vol. 52, Issue 17
An Efficient Iridium Catalyst for Reduction of Carbon Dioxide to Methane with Trialkylsilanes
journal, July 2012
- Park, Sehoon; Bézier, David; Brookhart, Maurice
- Journal of the American Chemical Society, Vol. 134, Issue 28
Room Temperature Reduction of CO 2 to Methanol by Al-Based Frustrated Lewis Pairs and Ammonia Borane
journal, February 2010
- Ménard, Gabriel; Stephan, Douglas W.
- Journal of the American Chemical Society, Vol. 132, Issue 6
Aromaticity as Stabilizing Element in the Bidentate Activation for the Catalytic Reduction of Carbon Dioxide
journal, April 2015
- Lu, Zhenpin; Hausmann, Heike; Becker, Sabine
- Journal of the American Chemical Society, Vol. 137, Issue 16
Alkali Metal Hydridotriphenylborates [(L)M][HBPh 3 ] (M = Li, Na, K): Chemoselective Catalysts for Carbonyl and CO 2 Hydroboration
journal, August 2016
- Mukherjee, Debabrata; Osseili, Hassan; Spaniol, Thomas P.
- Journal of the American Chemical Society, Vol. 138, Issue 34
Selective Reduction of CO 2 to CH 4 by Tandem Hydrosilylation with Mixed Al/B Catalysts
journal, January 2016
- Chen, Jiawei; Falivene, Laura; Caporaso, Lucia
- Journal of the American Chemical Society, Vol. 138, Issue 16
From Carbon Dioxide to Methane: Homogeneous Reduction of Carbon Dioxide with Hydrosilanes Catalyzed by Zirconium−Borane Complexes
journal, September 2006
- Matsuo, Tsukasa; Kawaguchi, Hiroyuki
- Journal of the American Chemical Society, Vol. 128, Issue 38
A Highly Active Phosphine–Borane Organocatalyst for the Reduction of CO 2 to Methanol Using Hydroboranes
journal, June 2013
- Courtemanche, Marc-André; Légaré, Marc-André; Maron, Laurent
- Journal of the American Chemical Society, Vol. 135, Issue 25
Tandem Frustrated Lewis Pair/Tris(pentafluorophenyl)borane-Catalyzed Deoxygenative Hydrosilylation of Carbon Dioxide
journal, August 2010
- Berkefeld, Andreas; Piers, Warren E.; Parvez, Masood
- Journal of the American Chemical Society, Vol. 132, Issue 31
An Efficient Nickel Catalyst for the Reduction of Carbon Dioxide with a Borane
journal, July 2010
- Chakraborty, Sumit; Zhang, Jie; Krause, Jeanette A.
- Journal of the American Chemical Society, Vol. 132, Issue 26
Ruthenium-Catalyzed Reduction of Carbon Dioxide to Formaldehyde
journal, March 2014
- Bontemps, Sébastien; Vendier, Laure; Sabo-Etienne, Sylviane
- Journal of the American Chemical Society, Vol. 136, Issue 11
Simultaneous Two-Hydrogen Transfer as a Mechanism for Efficient CO 2 Reduction
journal, October 2010
- Zimmerman, Paul M.; Zhang, Zhiyong; Musgrave, Charles B.
- Inorganic Chemistry, Vol. 49, Issue 19
Intramolecular B/N frustrated Lewis pairs and the hydrogenation of carbon dioxide
journal, January 2015
- Courtemanche, Marc-André; Pulis, Alexander P.; Rochette, Étienne
- Chemical Communications, Vol. 51, Issue 48
Screening Lewis Pair Moieties for Catalytic Hydrogenation of CO 2 in Functionalized UiO-66
journal, September 2015
- Ye, Jingyun; Johnson, J. Karl
- ACS Catalysis, Vol. 5, Issue 10
Non-Metal-Mediated Homogeneous Hydrogenation of CO2 to CH3OH
journal, December 2009
- Ashley, Andrewâ E.; Thompson, Amberâ L.; O'Hare, Dermot
- Angewandte Chemie International Edition, Vol. 48, Issue 52
The M06 suite of density functionals for main group thermochemistry, thermochemical kinetics, noncovalent interactions, excited states, and transition elements: two new functionals and systematic testing of four M06-class functionals and 12 other functionals
journal, July 2007
- Zhao, Yan; Truhlar, Donald G.
- Theoretical Chemistry Accounts, Vol. 120, Issue 1-3
The influence of polarization functions on molecular orbital hydrogenation energies
journal, January 1973
- Hariharan, P. C.; Pople, J. A.
- Theoretica Chimica Acta, Vol. 28, Issue 3
Improving the efficiency and convergence of geometry optimization with the polarizable continuum model: New energy gradients and molecular surface tessellation
journal, January 2004
- Li, Hui; Jensen, Jan H.
- Journal of Computational Chemistry, Vol. 25, Issue 12
Continuum solvation of large molecules described by QM/MM: a semi-iterative implementation of the PCM/EFP interface
journal, March 2003
- Li, Hui; Pomelli, Christian S.; Jensen, Jan H.
- Theoretical Chemistry Accounts: Theory, Computation, and Modeling (Theoretica Chimica Acta), Vol. 109, Issue 2
Palladium Complexes with N-Heterocyclic Carbene Ligands As Catalysts for the Alkoxycarbonylation of Olefins
journal, February 2013
- Roberts, Gina M.; Pierce, Philip J.; Woo, L. Keith
- Organometallics, Vol. 32, Issue 6
Marcus Theory of a Parallel Effect on α for Hydride Transfer Reaction between NAD + Analogues
journal, March 1997
- Lee, In-Sook Han; Jeoung, Eun Hee; Kreevoy, Maurice M.
- Journal of the American Chemical Society, Vol. 119, Issue 11
Predicting Hydride Donor Strength via Quantum Chemical Calculations of Hydride Transfer Activation Free Energy
journal, January 2018
- Alherz, Abdulaziz; Lim, Chern-Hooi; Hynes, James T.
- The Journal of Physical Chemistry B, Vol. 122, Issue 3
The redox potential for dimethyl sulphoxide reduction to dimethyl sulphide: Evaluation and biochemical implications
journal, February 1981
- Wood, Paul M.
- FEBS Letters, Vol. 124, Issue 1
13C nuclear magnetic resonance study of the CO2 activation of ribulosebisphosphate carboxylase from Rhodospirillum rubrum
journal, February 1979
- O'Leary, M. H.; Jaworski, R. J.; Hartman, F. C.
- Proceedings of the National Academy of Sciences, Vol. 76, Issue 2
Photochemical Reduction of Carbon Dioxide to Methanol and Formate in a Homogeneous System with Pyridinium Catalysts
journal, October 2013
- Boston, David J.; Xu, Chengdong; Armstrong, Daniel W.
- Journal of the American Chemical Society, Vol. 135, Issue 44
The First Catalytic Synthesis of an Acrylate from CO 2 and an Alkene-A Rational Approach
journal, September 2012
- Lejkowski, Michael L.; Lindner, Ronald; Kageyama, Takeharu
- Chemistry - A European Journal, Vol. 18, Issue 44
Classification of the solvent properties of common liquids
journal, May 1974
- Snyder, L. R.
- Journal of Chromatography A, Vol. 92, Issue 2
Chemical transformations of 7,9-disubstituted purines and related heterocycles. Selective reduction of imines and immonium salts
journal, June 1976
- Hecht, Sidney M.; Adams, Benjamin L.; Kozarich, John W.
- The Journal of Organic Chemistry, Vol. 41, Issue 13
Hydrogen evolution from organic “hydrides”
journal, January 2005
- Schwarz, Daniel E.; Cameron, Thomas M.; Hay, P. Jeffrey
- Chemical Communications, Issue 47
Selective Solar-Driven Reduction of CO 2 to Methanol Using a Catalyzed p-GaP Based Photoelectrochemical Cell
journal, May 2008
- Barton, Emily E.; Rampulla, David M.; Bocarsly, Andrew B.
- Journal of the American Chemical Society, Vol. 130, Issue 20
Electrosynthesis of Imidazolium Carboxylates
journal, August 2013
- de Robillard, Guillaume; Devillers, Charles H.; Kunz, Doris
- Organic Letters, Vol. 15, Issue 17
Electrochemical reduction of 1-benzyl-3-carbamoylpyridinium chloride, a nicotinamide adenine dinucleotide model compound
journal, August 1978
- Micheletti Moracci, Franco; Liberatore, Felice; Carelli, Vincenzo
- The Journal of Organic Chemistry, Vol. 43, Issue 17
Electrochemical reduction of 3-cyano-1-methylpyridinium iodide, a nicotinamide adenine dinucleotide model compound
journal, December 1976
- Carelli, Italo; Cardinali, Marlo E.; Casini, Antonio
- The Journal of Organic Chemistry, Vol. 41, Issue 25
Electrochemical Reduction of Nicotinamide Adenine Dinucleotide in Dimethylsulfoxide: Ion‐Pair, Protonation, and Adsorption Effects
journal, September 1982
- Malinski, Tadeusz; Elving, Philip J.
- Journal of The Electrochemical Society, Vol. 129, Issue 9
Nicotinamide adenine dinucleotide (NAD+) and related compounds. Electrochemical redox pattern and allied chemical behavior
journal, September 1975
- Schmakel, Conrad O.; Santhanam, K. S. V.; Elving, Philip J.
- Journal of the American Chemical Society, Vol. 97, Issue 18
Electrochemical redox pattern for nicotinamide species in nonaqueous media
journal, August 1973
- Santhanam, K. S. V.; Elving, Philip J.
- Journal of the American Chemical Society, Vol. 95, Issue 17
Works referencing / citing this record:
Conformational analysis of diols: Role of the linker on the relative orientation of hydroxyl groups
journal, June 2019
- Zoric, Marija R.; Singh, Varun; Zeller, Matthias
- Journal of Physical Organic Chemistry, Vol. 32, Issue 10
Importance of proton-coupled electron transfer in cathodic regeneration of organic hydrides
journal, January 2019
- Ilic, Stefan; Alherz, Abdulaziz; Musgrave, Charles B.
- Chemical Communications, Vol. 55, Issue 39
Front Cover: Addressing the Reproducibility of Photocatalytic Carbon Dioxide Reduction (ChemCatChem 6/2020)
journal, March 2020
- Marx, Maximilian; Mele, Andrea; Spannenberg, Anke
- ChemCatChem, Vol. 12, Issue 6
Addressing the Reproducibility of Photocatalytic Carbon Dioxide Reduction
journal, March 2020
- Marx, Maximilian; Mele, Andrea; Spannenberg, Anke
- ChemCatChem, Vol. 12, Issue 6
Addressing the Reproducibility of Photocatalytic Carbon Dioxide Reduction
journal, March 2020
- Marx, Maximilian; Mele, Andrea; Spannenberg, Anke
- ChemCatChem, Vol. 12, Issue 6