Kinetics of Hydride Transfer from Catalytic Metal-Free Hydride Donors to CO2

Weerasooriya, Ravindra B.; Gesiorski, Jonathan L.; Alherz, Abdulaziz; Ilic, Stefan; Hargenrader, George N.; Musgrave, Charles B.; Glusac, Ksenija D.

doi:10.1021/acs.jpclett.0c03662

Kinetics of Hydride Transfer from Catalytic Metal-Free Hydride Donors to CO2

Journal Article · Mon Mar 01 23:00:00 EST 2021 · Journal of Physical Chemistry Letters

DOI:https://doi.org/10.1021/acs.jpclett.0c03662· OSTI ID:1798205

Weerasooriya, Ravindra B. ^[1]; Gesiorski, Jonathan L. ^[1]; ^[2]; ^[3]; Hargenrader, George N. ^[1]; ^[2]; ^[1]

Univ. of Illinois, Chicago, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Univ. of Colorado, Boulder, CO (United States)
Virginia Polytechnic Inst. and State Univ. (Virginia Tech), Blacksburg, VA (United States)

Selective reduction of CO₂ to formate represents an ongoing challenge in photoelectrocatalysis. To provide mechanistic insights, we investigate the kinetics of hydride transfer (HT) from a series of metal-free hydride donors to CO₂. The observed dependence of experimental and calculated HT barriers on the thermodynamic driving force was modeled by using the Marcus hydride transfer formalism to obtain the insights into the effect of reorganization energies on the reaction kinetics. Our results indicate that even if the most ideal hydride donor were discovered, the HT to CO₂ would exhibit sluggish kinetics (<100 turnovers per second at -0.1 eV driving force), indicating that the conventional HT may not be an appropriate mechanism for solar conversion of CO₂ to formate. We propose that the conventional HT mechanism should not be considered for CO₂ reduction catalysis and argue that the orthogonal HT mechanism, previously proposed to address thermodynamic limitations of this reaction, may also lead to lower kinetic barriers for CO₂ reduction to formate.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE; National Science Foundation (NSF)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1798205

Journal Information:: Journal of Physical Chemistry Letters, Journal Name: Journal of Physical Chemistry Letters Journal Issue: 9 Vol. 12; ISSN 1948-7185

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (58)

Reversible and Selective CO ₂ to HCO ₂ ⁻ Electrocatalysis near the Thermodynamic Potential Cunningham, Drew W.; Barlow, Jeffrey M.; Velazquez, Reyna S. Angewandte Chemie International Edition, Vol. 59, Issue 11 https://doi.org/10.1002/anie.201913198	journal	February 2020
Single Iridium Pincer Complex for Roundtrip Electrochemical Conversion between Carbon Dioxide and Formate Bi, Jiaojiao; Hou, Pengfei; Kang, Peng ChemCatChem, Vol. 11, Issue 8 https://doi.org/10.1002/cctc.201900083	journal	March 2019
Improving the Photocatalytic Reduction of CO ₂ to CO through Immobilisation of a Molecular Re Catalyst on TiO ₂ Windle, Christopher D.; Pastor, Ernest; Reynal, Anna Chemistry - A European Journal, Vol. 21, Issue 9 https://doi.org/10.1002/chem.201405041	journal	January 2015
Making a Splash in Homogeneous CO ₂ Hydrogenation: Elucidating the Impact of Solvent on Catalytic Mechanisms Wiedner, Eric S.; Linehan, John C. Chemistry – A European Journal, Vol. 24, Issue 64 https://doi.org/10.1002/chem.201801759	journal	July 2018
Synthesis and properties of [Ru(tpy)(4,4′-X2bpy)H]+ (tpy=2,2′:6′,2″-terpyridine, bpy=2,2′-bipyridine, X=H and MeO), and their reactions with CO2 Konno, Hideo; Kobayashi, Atsuo; Sakamoto, Kazuhiko Inorganica Chimica Acta, Vol. 299, Issue 2 https://doi.org/10.1016/S0020-1693(99)00488-0	journal	March 2000
Renewable Formate from C–H Bond Formation with CO ₂ : Using Iron Carbonyl Clusters as Electrocatalysts Loewen, Natalia D.; Neelakantan, Taruna V.; Berben, Louise A. Accounts of Chemical Research, Vol. 50, Issue 9 https://doi.org/10.1021/acs.accounts.7b00302	journal	August 2017
Control in the Rate-Determining Step Provides a Promising Strategy To Develop New Catalysts for CO ₂ Hydrogenation: A Local Pair Natural Orbital Coupled Cluster Theory Study Mondal, Bhaskar; Neese, Frank; Ye, Shengfa Inorganic Chemistry, Vol. 54, Issue 15 https://doi.org/10.1021/acs.inorgchem.5b00469	journal	July 2015
Tailoring Electrocatalysts for Selective CO ₂ or H ⁺ Reduction: Iron Carbonyl Clusters as a Case Study Taheri, Atefeh; Berben, Louise A. Inorganic Chemistry, Vol. 55, Issue 2 https://doi.org/10.1021/acs.inorgchem.5b02293	journal	November 2015
Experimental and Theoretical Study of CO ₂ Insertion into Ruthenium Hydride Complexes Ramakrishnan, Srinivasan; Waldie, Kate M.; Warnke, Ingolf Inorganic Chemistry, Vol. 55, Issue 4 https://doi.org/10.1021/acs.inorgchem.5b02556	journal	February 2016
Highly Selective Electrocatalytic CO ₂ Reduction by [Pt(dmpe) ₂ ] ²⁺ through Kinetic and Thermodynamic Control Ceballos, Bianca M.; Yang, Jenny Y. Organometallics, Vol. 39, Issue 9 https://doi.org/10.1021/acs.organomet.9b00720	journal	February 2020
Photoregeneration of Biomimetic Nicotinamide Adenine Dinucleotide Analogues via a Dye-Sensitized Approach Hargenrader, George N.; Weerasooriya, Ravindra B.; Ilic, Stefan ACS Applied Energy Materials, Vol. 2, Issue 1 https://doi.org/10.1021/acsaem.8b01574	journal	November 2018
An Iron Electrocatalyst for Selective Reduction of CO ₂ to Formate in Water: Including Thermochemical Insights Taheri, Atefeh; Thompson, Emily J.; Fettinger, James C. ACS Catalysis, Vol. 5, Issue 12 https://doi.org/10.1021/acscatal.5b01708	journal	November 2015
Selectivity for HCO ₂ ^– over H ₂ in the Electrochemical Catalytic Reduction of CO ₂ by (POCOP)IrH ₂ Johnson, Samantha I.; Nielsen, Robert J.; Goddard, William A. ACS Catalysis, Vol. 6, Issue 10 https://doi.org/10.1021/acscatal.6b01755	journal	August 2016
Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO ₂ Reduction Waldie, Kate M.; Ostericher, Andrew L.; Reineke, Mark H. ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b03396	journal	January 2018
Electrochemical Methods for Assessing Kinetic Factors in the Reduction of CO ₂ to Formate: Implications for Improving Electrocatalyst Design Taheri, Atefeh; Carr, Cody R.; Berben, Louise A. ACS Catalysis, Vol. 8, Issue 7 https://doi.org/10.1021/acscatal.8b01799	journal	May 2018
Thermodynamic Considerations for Optimizing Selective CO ₂ Reduction by Molecular Catalysts Barlow, Jeffrey M.; Yang, Jenny Y. ACS Central Science, Vol. 5, Issue 4 https://doi.org/10.1021/acscentsci.9b00095	journal	March 2019
Tertiary Amine-Assisted Electroreduction of Carbon Dioxide to Formate Catalyzed by Iron Tetraphenylporphyrin Margarit, Charles G.; Asimow, Naomi G.; Costentin, Cyrille ACS Energy Letters, Vol. 5, Issue 1 https://doi.org/10.1021/acsenergylett.9b02093	journal	November 2019
Transition Metal Hydride Catalysts for Sustainable Interconversion of CO ₂ and Formate: Thermodynamic and Mechanistic Considerations Waldie, Kate M.; Brunner, Felix M.; Kubiak, Clifford P. ACS Sustainable Chemistry & Engineering, Vol. 6, Issue 5 https://doi.org/10.1021/acssuschemeng.8b00628	journal	March 2018
Catalysis Research of Relevance to Carbon Management: Progress, Challenges, and Opportunities Arakawa, Hironori; Aresta, Michele; Armor, John N. Chemical Reviews, Vol. 101, Issue 4 https://doi.org/10.1021/cr000018s	journal	April 2001
Electron transfer to ozone: outer-sphere reactivities of the ozone/ozonide and related non-metal redox couples Bennett, Larry E.; Warlop, Philip Inorganic Chemistry, Vol. 29, Issue 10 https://doi.org/10.1021/ic00335a040	journal	May 1990
Solvent modulation of the dynamics of hydride transfer Kotchevar, Ann T.; Kreevoy, Maurice M. The Journal of Physical Chemistry, Vol. 95, Issue 25 https://doi.org/10.1021/j100178a021	journal	December 1991
Phenomenological manifestations of large-curvature tunneling in hydride-transfer reactions Kreevoy, Maurice M.; Ostovic, Drazen; Truhlar, Donald G. The Journal of Physical Chemistry, Vol. 90, Issue 16 https://doi.org/10.1021/j100407a052	journal	July 1986
An experimentally based family of potential energy surfaces for hydride transfer between NAD+ analogs Kim, Yongho; Truhlar, Donald G.; Kreevoy, Maurice M. Journal of the American Chemical Society, Vol. 113, Issue 21 https://doi.org/10.1021/ja00021a002	journal	October 1991
Dynamics of hydride transfer between NAD+ analogs Kreevoy, Maurice M.; Kotchevar, Ann T. Journal of the American Chemical Society, Vol. 112, Issue 9 https://doi.org/10.1021/ja00165a049	journal	April 1990
Structure sensitivity of the Marcus .lambda. for hydride transfer between NAD+ analogs Kreevoy, Maurice M.; Ostovic, Drazen.; Lee, In Sook Han. Journal of the American Chemical Society, Vol. 110, Issue 2 https://doi.org/10.1021/ja00210a036	journal	January 1988
Marcus theory of hydride transfer from an anionic reduced deazaflavin to NAD+ analogs Lee, In Sook Han.; Ostovic, Drazen.; Kreevoy, Maurice. Journal of the American Chemical Society, Vol. 110, Issue 12 https://doi.org/10.1021/ja00220a043	journal	June 1988
Primary Kinetic Isotope Effects on Hydride Transfer from 1,3-Dimethyl-2-phenylbenzimidazoline to NAD⁺ Analogues Han Lee, In-Sook; Jeoung, Eun Hee; Kreevoy, Maurice M. Journal of the American Chemical Society, Vol. 123, Issue 31 https://doi.org/10.1021/ja004232+	journal	July 2001
Determination of a Large Reorganization Energy Barrier for Hydride Abstraction by Glucose Oxidase Brinkley, David W.; Roth, Justine P. Journal of the American Chemical Society, Vol. 127, Issue 45 https://doi.org/10.1021/ja056025l	journal	November 2005
Rapid Transfer of Hydride Ion from a Ruthenium Complex to C ₁ Species in Water Creutz, Carol; Chou, Mei H. Journal of the American Chemical Society, Vol. 129, Issue 33 https://doi.org/10.1021/ja074158w	journal	August 2007
Selective Electrocatalytic Reduction of CO ₂ to Formate by Water-Stable Iridium Dihydride Pincer Complexes Kang, Peng; Cheng, Chen; Chen, Zuofeng Journal of the American Chemical Society, Vol. 134, Issue 12 https://doi.org/10.1021/ja300543s	journal	March 2012
Thermodynamic and Kinetic Hydricity of Ruthenium(II) Hydride Complexes Matsubara, Yasuo; Fujita, Etsuko; Doherty, Mark D. Journal of the American Chemical Society, Vol. 134, Issue 38 https://doi.org/10.1021/ja302937q	journal	September 2012
Photochemical Reduction of Carbon Dioxide to Methanol and Formate in a Homogeneous System with Pyridinium Catalysts Boston, David J.; Xu, Chengdong; Armstrong, Daniel W. Journal of the American Chemical Society, Vol. 135, Issue 44 https://doi.org/10.1021/ja406074w	journal	October 2013
Reduction of CO ₂ to Methanol Catalyzed by a Biomimetic Organo-Hydride Produced from Pyridine Lim, Chern-Hooi; Holder, Aaron M.; Hynes, James T. Journal of the American Chemical Society, Vol. 136, Issue 45 https://doi.org/10.1021/ja510131a	journal	November 2014
Efficient and Clean Photoreduction of CO ₂ to CO by Enzyme-Modified TiO ₂ Nanoparticles Using Visible Light Woolerton, Thomas W.; Sheard, Sally; Reisner, Erwin Journal of the American Chemical Society, Vol. 132, Issue 7 https://doi.org/10.1021/ja910091z	journal	February 2010
Marcus Theory of a Parallel Effect on α for Hydride Transfer Reaction between NAD ⁺ Analogues Lee, In-Sook Han; Jeoung, Eun Hee; Kreevoy, Maurice M. Journal of the American Chemical Society, Vol. 119, Issue 11 https://doi.org/10.1021/ja963768l	journal	March 1997
Reducing CO ₂ to HCO ₂ ^– at Mild Potentials: Lessons from Formate Dehydrogenase Yang, Jenny Y.; Kerr, Tyler A.; Wang, Xinran S. Journal of the American Chemical Society, Vol. 142, Issue 46 https://doi.org/10.1021/jacs.0c07965	journal	November 2020
Electrocatalytic Hydrogen Evolution under Acidic Aqueous Conditions and Mechanistic Studies of a Highly Stable Molecular Catalyst Tsay, Charlene; Yang, Jenny Y. Journal of the American Chemical Society, Vol. 138, Issue 43 https://doi.org/10.1021/jacs.6b05851	journal	July 2016
Molecular Cobalt Complexes with Pendant Amines for Selective Electrocatalytic Reduction of Carbon Dioxide to Formic Acid Roy, Souvik; Sharma, Bhaskar; Pécaut, Jacques Journal of the American Chemical Society, Vol. 139, Issue 10 https://doi.org/10.1021/jacs.6b11474	journal	March 2017
Selective Photocatalytic CO ₂ Reduction in Water through Anchoring of a Molecular Ni Catalyst on CdS Nanocrystals Kuehnel, Moritz F.; Orchard, Katherine L.; Dalle, Kristian E. Journal of the American Chemical Society, Vol. 139, Issue 21 https://doi.org/10.1021/jacs.7b00369	journal	May 2017
Thermodynamic Hydricities of Biomimetic Organic Hydride Donors Ilic, Stefan; Pandey Kadel, Usha; Basdogan, Yasemin Journal of the American Chemical Society, Vol. 140, Issue 13 https://doi.org/10.1021/jacs.7b13526	journal	March 2018
Benzimidazoles as Metal-Free and Recyclable Hydrides for CO ₂ Reduction to Formate Lim, Chern-Hooi; Ilic, Stefan; Alherz, Abdulaziz Journal of the American Chemical Society, Vol. 141, Issue 1 https://doi.org/10.1021/jacs.8b09653	journal	November 2018
Understanding the Individual and Combined Effects of Solvent and Lewis Acid on CO ₂ Insertion into a Metal Hydride Heimann, Jessica E.; Bernskoetter, Wesley H.; Hazari, Nilay Journal of the American Chemical Society, Vol. 141, Issue 26 https://doi.org/10.1021/jacs.9b05192	journal	May 2019
Re(tBu-bpy)(CO) 3 Cl Supported on Multi-Walled Carbon Nanotubes Selectively Reduces CO 2 in Water Zhanaidarova, Almagul; Jones, Simon C.; Despagnet-Ayoub, Emmanuelle Journal of the American Chemical Society, Vol. 141, Issue 43 https://doi.org/10.1021/jacs.9b08445	journal	October 2019
Efficient Photocatalytic CO ₂ Reduction by a Ni(II) Complex Having Pyridine Pendants through Capturing a Mg ²⁺ Ion as a Lewis-Acid Cocatalyst Hong, Dachao; Kawanishi, Takuya; Tsukakoshi, Yuto Journal of the American Chemical Society, Vol. 141, Issue 51 https://doi.org/10.1021/jacs.9b10597	journal	November 2019
Unexpected Roles of Triethanolamine in the Photochemical Reduction of CO ₂ to Formate by Ruthenium Complexes Sampaio, Renato N.; Grills, David C.; Polyansky, Dmitry E. Journal of the American Chemical Society, Vol. 142, Issue 5 https://doi.org/10.1021/jacs.9b11897	journal	December 2019
Catalysis of the Electrochemical Reduction of Carbon Dioxide by Iron(0) Porphyrins. Synergistic Effect of Lewis Acid Cations Bhugun, Iqbal; Lexa, Doris; Savéant, Jean-Michel The Journal of Physical Chemistry, Vol. 100, Issue 51 https://doi.org/10.1021/jp9618486	journal	January 1996
Simple Marcus-Theory-Type Model for Hydrogen-Atom Transfer/Proton-Coupled Electron Transfer Mayer, James M. The Journal of Physical Chemistry Letters, Vol. 2, Issue 12 https://doi.org/10.1021/jz200021y	journal	May 2011
Kinetics and mechanism of carbon dioxide insertion into a metal-hydride bond. A large solvent effect and an inverse kinetic isotope effect Sullivan, B. Patrick.; Meyer, Thomas J. Organometallics, Vol. 5, Issue 7 https://doi.org/10.1021/om00138a035	journal	July 1986
Making syngas electrocatalytically using a polypyridyl ruthenium catalyst Chen, Zuofeng; Kang, Peng; Zhang, Ming-Tian Chem. Commun., Vol. 50, Issue 3 https://doi.org/10.1039/C3CC47251E	journal	January 2014
A review of catalysts for the electroreduction of carbon dioxide to produce low-carbon fuels Qiao, Jinli; Liu, Yuyu; Hong, Feng Chem. Soc. Rev., Vol. 43, Issue 2 https://doi.org/10.1039/C3CS60323G	journal	January 2014
Formic acid as a hydrogen storage material – development of homogeneous catalysts for selective hydrogen release Mellmann, Dörthe; Sponholz, Peter; Junge, Henrik Chemical Society Reviews, Vol. 45, Issue 14 https://doi.org/10.1039/C5CS00618J	journal	January 2016
Thermodynamic and kinetic hydricities of metal-free hydrides Ilic, Stefan; Alherz, Abdulaziz; Musgrave, Charles B. Chemical Society Reviews, Vol. 47, Issue 8 https://doi.org/10.1039/C7CS00171A	journal	January 2018
Importance of proton-coupled electron transfer in cathodic regeneration of organic hydrides Ilic, Stefan; Alherz, Abdulaziz; Musgrave, Charles B. Chemical Communications, Vol. 55, Issue 39 https://doi.org/10.1039/C9CC00928K	journal	January 2019
Mapping free energy regimes in electrocatalytic reductions to screen transition metal-based catalysts Ramakrishnan, Srinivasan; Moretti, Ross A.; Chidsey, Christopher E. D. Chemical Science, Vol. 10, Issue 32 https://doi.org/10.1039/C9SC01766F	journal	January 2019
Electrocatalytic reduction of CO2 to CO by polypyridyl ruthenium complexes Chen, Zuofeng; Chen, Chuncheng; Weinberg, David R. Chemical Communications, Vol. 47, Issue 47 https://doi.org/10.1039/c1cc15071e	journal	January 2011
Hydride transfer between NAD+ analogues Roberts, R. M. G.; Ostovi?, D.; Kreevoy, M. M. Faraday Discussions of the Chemical Society, Vol. 74 https://doi.org/10.1039/dc9827400257	journal	January 1982
Directing the reactivity of metal hydrides for selective CO ₂ reduction Ceballos, Bianca M.; Yang, Jenny Y. Proceedings of the National Academy of Sciences, Vol. 115, Issue 50 https://doi.org/10.1073/pnas.1811396115	journal	November 2018
Rubisco: Structure and Mechanism Schneider, G.; Lindqvist, Y.; Branden, C. I. Annual Review of Biophysics and Biomolecular Structure, Vol. 21, Issue 1 https://doi.org/10.1146/annurev.bb.21.060192.001003	journal	June 1992

Similar Records

Biomimetic Metal-Free Hydride Donor Catalysts for CO₂ Reduction

Journal Article · Wed Feb 23 23:00:00 EST 2022 · Accounts of Chemical Research · OSTI ID:1870120

Elucidation of Marcus Relationships for Hydride Transfer Reactions Involving Transition Metal Hydrides

Journal Article · Mon Aug 25 00:00:00 EDT 2025 · Journal of the American Chemical Society · OSTI ID:2997742

Correlating Thermodynamic and Kinetic Hydricities of Rhenium Hydrides

Journal Article · Wed Sep 21 00:00:00 EDT 2022 · Journal of the American Chemical Society · OSTI ID:1900392

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
CO2 reduction
organo-hydrides
Marcus theory
product selectivity
hydride transfer
formate

Kinetics of Hydride Transfer from Catalytic Metal-Free Hydride Donors to CO2

Citation Formats

References (58)

Similar Records

Related Subjects