Exchange Coupling Determines Metal-Dependent Efficiency for Iron- and Cobalt-Catalyzed Photochemical CO2 Reduction

De La Torre, Patricia; Derrick, Jeffrey S.; Snider, Andrew; Smith, Peter T.; Loipersberger, Matthias; Head-Gordon, Martin; Chang, Christopher J.

doi:10.1021/acscatal.2c02072

Exchange Coupling Determines Metal-Dependent Efficiency for Iron- and Cobalt-Catalyzed Photochemical CO₂ Reduction

Journal Article · Fri Jul 01 00:00:00 EDT 2022 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.2c02072· OSTI ID:1963456

De La Torre, Patricia ^[1]; Derrick, Jeffrey S. ^[1]; Snider, Andrew ^[2]; Smith, Peter T. ^[1]; ^[2]; ^[1]; ^[1]

Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Univ. of California, Berkeley, CA (United States)

Catalysts promoting multielectron charge delocalization offer selectivity for the CO₂ reduction reaction (CO₂RR) over the competing hydrogen evolution reaction. Here, we show metal–ligand exchange coupling as an example of charge delocalization that can determine the efficiency for photocatalytic CO₂RR. A comparative evaluation of iron and cobalt complexes supported by the redox-active ligand tpyPY2Me establishes that the two-electron reduction of [Co(tpyPY2Me)]²⁺ ([Co]²⁺) occurs at potentials 770 mV more negative than the [Fe(tpyPY2Me)]²⁺ ([Fe]²⁺) analogue by maximizing the exchange coupling in the latter compound. The positive shift in the reduction potential promoted by metal–ligand exchange coupling drives [Fe]²⁺ to be among the most active and selective molecular catalysts for photochemical CO₂RR reported to date, maintaining up to 99% CO product selectivity with total turnover numbers (TONs) and initial turnover frequencies exceeding 30,000 and 900 min^–1, respectively. In contrast, [Co]²⁺ shows much lower CO₂RR activity, reaching only ca. 600 TON at 83% CO product selectivity under similar conditions accompanied by rapid catalyst decomposition. Further, the spin density plots of the two-electron reduced [Co]⁰ complex implicate a paramagnetic open-shell doublet ground state compared to the diamagnetic open-shell singlet ground state of reduced [Fe]⁰, rationalizing the observed negative shift in two-electron reduction potentials from the [M]²⁺ species and lowered CO₂RR efficiency for the cobalt complex relative to its iron congener. This work emphasizes the contributions of multielectron metal–ligand exchange coupling in promoting effective CO₂RR and provides a starting point for the broader incorporation of this strategy in catalyst design.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: Canadian Institute for Advanced Research (CIFAR); Chevron; National Science Foundation (NSF); USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR). Scientific Discovery through Advanced Computing (SciDAC); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1963456

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Journal Issue: 14 Vol. 12; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (62)

[Mn(bipyridyl)(CO)3Br]: An Abundant Metal Carbonyl Complex as Efficient Electrocatalyst for CO2 Reduction Bourrez, Marc; Molton, Florian; Chardon-Noblat, Sylvie Angewandte Chemie International Edition, Vol. 50, Issue 42 https://doi.org/10.1002/anie.201103616	journal	September 2011
Coupling of Solar Energy and Thermal Energy for Carbon Dioxide Reduction: Status and Prospects Wang, Zhou-jun; Song, Hui; Liu, Huimin Angewandte Chemie International Edition https://doi.org/10.1002/anie.201907443	journal	February 2020
Host–Guest Interactions in a Metal–Organic Framework Isoreticular Series for Molecular Photocatalytic CO ₂ Reduction Stanley, Philip M.; Haimerl, Johanna; Thomas, Christopher Angewandte Chemie International Edition, Vol. 60, Issue 33 https://doi.org/10.1002/anie.202102729	journal	June 2021
Mechanistic Insights Into Iron(II) Bis(pyridyl)amine‐Bipyridine Skeleton for Selective CO ₂ Photoreduction Wang, Xu‐Zhe; Meng, Shu‐Lin; Chen, Jia‐Yi Angewandte Chemie International Edition, Vol. 60, Issue 50 https://doi.org/10.1002/anie.202107386	journal	November 2021
Homogeneous Photocatalytic H ₂ Production Using a Ru ^II Bathophenanthroline Metal‐to‐Ligand Charge‐Transfer Photosensitizer Khnayzer, Rony S.; Olaiya, Babatunde S.; El Roz, Karim A. ChemPlusChem, Vol. 81, Issue 10 https://doi.org/10.1002/cplu.201600227	journal	October 2016
Photocatalytic Conversion of CO₂ to CO by a Copper(II) Quaterpyridine Complex Guo, Zhenguo; Yu, Fei; Yang, Ying ChemSusChem, Vol. 10, Issue 20 https://doi.org/10.1002/cssc.201701354	journal	September 2017
Recent Advances of Cobalt(II/III) Redox Couples for Dye-Sensitized Solar Cell Applications Giribabu, Lingamallu; Bolligarla, Ramababu; Panigrahi, Mallika The Chemical Record, Vol. 15, Issue 4 https://doi.org/10.1002/tcr.201402098	journal	June 2015
Acriflavine–cobaloxime–triethanolamine homogeneous photocatalytic system for water splitting and the multiple effects of cobaloxime and triethanolamine Gong, Liming; Wang, Jian; Li, Hui Catalysis Communications, Vol. 12, Issue 12 https://doi.org/10.1016/j.catcom.2011.03.024	journal	July 2011
Highly selective electrocatalysis for carbon dioxide reduction to formic acid by a Co(II) complex with an equatorial N4 ligand Tsubonouchi, Yuta; Takahashi, Daiki; Berber, Mohamed R. Electrochimica Acta, Vol. 387 https://doi.org/10.1016/j.electacta.2021.138545	journal	August 2021
Turning off hydrogen evolution via an organic dye photosensitizer in aqueous acetonitrile solution during photocatalytic CO2 reduction to CO Chen, Xuyang; Wei, Yu; Sun, Wenxuan Molecular Catalysis, Vol. 500 https://doi.org/10.1016/j.mcat.2020.111299	journal	January 2021
Solar Fuels and Solar Chemicals Industry Nocera, Daniel G. Accounts of Chemical Research, Vol. 50, Issue 3 https://doi.org/10.1021/acs.accounts.6b00615	journal	March 2017
Hybrid Catalysts for Artificial Photosynthesis: Merging Approaches from Molecular, Materials, and Biological Catalysis Smith, Peter T.; Nichols, Eva M.; Cao, Zhi Accounts of Chemical Research, Vol. 53, Issue 3 https://doi.org/10.1021/acs.accounts.9b00619	journal	March 2020
Direct Capture of CO₂ from Ambient Air Sanz-Pérez, Eloy S.; Murdock, Christopher R.; Didas, Stephanie A. Chemical Reviews, Vol. 116, Issue 19, p. 11840-11876 https://doi.org/10.1021/acs.chemrev.6b00173	journal	August 2016
Organic Photosensitizers for Catalytic Solar Fuel Generation Leung, Chi-Fai; Lau, Tai-Chu Energy & Fuels, Vol. 35, Issue 23 https://doi.org/10.1021/acs.energyfuels.1c02675	journal	October 2021
Methane Generation from CO ₂ with a Molecular Rhenium Catalyst Nganga, John K.; Wolf, Lucienna M.; Mullick, Kankana Inorganic Chemistry, Vol. 60, Issue 6 https://doi.org/10.1021/acs.inorgchem.0c02579	journal	February 2021
Highly Efficient and Selective Visible-Light Driven CO₂ Reduction by Two Co-Based Catalysts in Aqueous Solution Zhang, Liyan; Li, Shiwei; Liu, Huiping Inorganic Chemistry, Vol. 59, Issue 23 https://doi.org/10.1021/acs.inorgchem.0c02733	journal	November 2020
Molecular and Electronic Structures of Homoleptic Six-Coordinate Cobalt(I) Complexes of 2,2′:6′,2″-Terpyridine, 2,2′-Bipyridine, and 1,10-Phenanthroline. An Experimental and Computational Study England, Jason; Bill, Eckhard; Weyhermüller, Thomas Inorganic Chemistry, Vol. 54, Issue 24 https://doi.org/10.1021/acs.inorgchem.5b02415	journal	December 2015
Electrocatalytic Reduction of CO ₂ to CO With Re-Pyridyl-NHCs: Proton Source Influence on Rates and Product Selectivities Liyanage, Nalaka P.; Dulaney, Hunter A.; Huckaba, Aron J. Inorganic Chemistry, Vol. 55, Issue 12 https://doi.org/10.1021/acs.inorgchem.6b00626	journal	June 2016
Reductive Disproportionation of Carbon Dioxide by an Alkyl-Functionalized Pyridine Monoimine Re(I) fac -Tricarbonyl Electrocatalyst Machan, Charles W.; Chabolla, Steven A.; Kubiak, Clifford P. Organometallics, Vol. 34, Issue 19 https://doi.org/10.1021/acs.organomet.5b00406	journal	July 2015
An Iron Pyridyl-Carbene Electrocatalyst for Low Overpotential CO ₂ Reduction to CO Gonell, Sergio; Lloret-Fillol, Julio; Miller, Alexander J. M. ACS Catalysis, Vol. 11, Issue 2 https://doi.org/10.1021/acscatal.0c03798	journal	December 2020
Redox-Active Ligands in Electroassisted Catalytic H ⁺ and CO ₂ Reductions: Benefits and Risks Queyriaux, Nicolas ACS Catalysis, Vol. 11, Issue 7 https://doi.org/10.1021/acscatal.1c00237	journal	March 2021
Electrons, Photons, Protons and Earth-Abundant Metal Complexes for Molecular Catalysis of CO ₂ Reduction Takeda, Hiroyuki; Cometto, Claudio; Ishitani, Osamu ACS Catalysis, Vol. 7, Issue 1 https://doi.org/10.1021/acscatal.6b02181	journal	November 2016
Supramolecular Photocatalysts for the Reduction of CO ₂ Tamaki, Yusuke; Ishitani, Osamu ACS Catalysis, Vol. 7, Issue 5 https://doi.org/10.1021/acscatal.7b00440	journal	April 2017
Highly Efficient and Selective Photocatalytic CO ₂ Reduction to CO in Water by a Cobalt Porphyrin Molecular Catalyst Call, Arnau; Cibian, Mihaela; Yamamoto, Keiya ACS Catalysis, Vol. 9, Issue 6 https://doi.org/10.1021/acscatal.8b04975	journal	April 2019
Robust and Selective Cobalt Catalysts Bearing Redox-Active Bipyridyl- N -heterocyclic Carbene Frameworks for Electrochemical CO ₂ Reduction in Aqueous Solutions Su, Xiaojun; McCardle, Kaitlin M.; Chen, Lizhu ACS Catalysis, Vol. 9, Issue 8 https://doi.org/10.1021/acscatal.9b00708	journal	June 2019
Photochemical CO ₂ Reduction Driven by Water-Soluble Copper(I) Photosensitizer with the Catalysis Accelerated by Multi-Electron Chargeable Cobalt Porphyrin Zhang, Xian; Cibian, Mihaela; Call, Arnau ACS Catalysis, Vol. 9, Issue 12 https://doi.org/10.1021/acscatal.9b04023	journal	October 2019
Photocatalytically Active Superstructures of Quantum Dots and Iron Porphyrins for Reduction of CO ₂ to CO in Water Lian, Shichen; Kodaimati, Mohamad S.; Weiss, Emily A. ACS Nano, Vol. 12, Issue 1 https://doi.org/10.1021/acsnano.7b07377	journal	January 2018
Chemical approaches to artificial photosynthesis Meyer, Thomas J. Accounts of Chemical Research, Vol. 22, Issue 5 https://doi.org/10.1021/ar00161a001	journal	May 1989
The Artificial Leaf Nocera, Daniel G. Accounts of Chemical Research, Vol. 45, Issue 5 https://doi.org/10.1021/ar2003013	journal	January 2012
Molecular Approaches to the Photocatalytic Reduction of Carbon Dioxide for Solar Fuels Morris, Amanda J.; Meyer, Gerald J.; Fujita, Etsuko Accounts of Chemical Research, Vol. 42, Issue 12 https://doi.org/10.1021/ar9001679	journal	December 2009
Re(bipy-tBu)(CO) ₃ Cl−improved Catalytic Activity for Reduction of Carbon Dioxide: IR-Spectroelectrochemical and Mechanistic Studies Smieja, Jonathan M.; Kubiak, Clifford P. Inorganic Chemistry, Vol. 49, Issue 20 https://doi.org/10.1021/ic1008363	journal	October 2010
Manganese as a Substitute for Rhenium in CO ₂ Reduction Catalysts: The Importance of Acids Smieja, Jonathan M.; Sampson, Matthew D.; Grice, Kyle A. Inorganic Chemistry, Vol. 52, Issue 5 https://doi.org/10.1021/ic302391u	journal	February 2013
Chemistry of Personalized Solar Energy Nocera, Daniel G. Inorganic Chemistry, Vol. 48, Issue 21 https://doi.org/10.1021/ic901328v	journal	November 2009
Photochemistry of tris(2,2'-bipyridine)ruthenium(2+) ion Durham, Bill; Caspar, Jonathan V.; Nagle, Jeffrey K. Journal of the American Chemical Society, Vol. 104, Issue 18 https://doi.org/10.1021/ja00382a012	journal	September 1982
Molecular Cobalt Pentapyridine Catalysts for Generating Hydrogen from Water Sun, Yujie; Bigi, Julian P.; Piro, Nicholas A. Journal of the American Chemical Society, Vol. 133, Issue 24 https://doi.org/10.1021/ja202743r	journal	June 2011
A New Direction in Dye-Sensitized Solar Cells Redox Mediator Development: In Situ Fine-Tuning of the Cobalt(II)/(III) Redox Potential through Lewis Base Interactions Kashif, Muhammad K.; Axelson, Jordan C.; Duffy, Noel W. Journal of the American Chemical Society, Vol. 134, Issue 40 https://doi.org/10.1021/ja305897k	journal	October 2012
Visible-Light Photoredox Catalysis: Selective Reduction of Carbon Dioxide to Carbon Monoxide by a Nickel N -Heterocyclic Carbene–Isoquinoline Complex Thoi, V. Sara; Kornienko, Nikolay; Margarit, Charles G. Journal of the American Chemical Society, Vol. 135, Issue 38 https://doi.org/10.1021/ja4074003	journal	September 2013
Toward Combined Carbon Capture and Recycling: Addition of an Amine Alters Product Selectivity from CO to Formic Acid in Manganese Catalyzed Reduction of CO ₂ Bhattacharya, Moumita; Sebghati, Sepehr; VanderLinden, Ryan T. Journal of the American Chemical Society, Vol. 142, Issue 41 https://doi.org/10.1021/jacs.0c07763	journal	September 2020
Mechanistic Insights into Co and Fe Quaterpyridine-Based CO ₂ Reduction Catalysts: Metal–Ligand Orbital Interaction as the Key Driving Force for Distinct Pathways Loipersberger, Matthias; Cabral, Delmar G. A.; Chu, Daniel B. K. Journal of the American Chemical Society, Vol. 143, Issue 2 https://doi.org/10.1021/jacs.0c09380	journal	January 2021
Metal–Ligand Cooperativity via Exchange Coupling Promotes Iron- Catalyzed Electrochemical CO ₂ Reduction at Low Overpotentials Derrick, Jeffrey S.; Loipersberger, Matthias; Chatterjee, Ruchira Journal of the American Chemical Society, Vol. 142, Issue 48 https://doi.org/10.1021/jacs.0c10664	journal	November 2020
Controlled Single-Electron Transfer via Metal–Ligand Cooperativity Drives Divergent Nickel-Electrocatalyzed Radical Pathways Wuttig, Anna; Derrick, Jeffrey S.; Loipersberger, Matthias Journal of the American Chemical Society, Vol. 143, Issue 18 https://doi.org/10.1021/jacs.1c01487	journal	April 2021
Quantum Dot-Sensitized Photoreduction of CO ₂ in Water with Turnover Number > 80,000 Arcudi, Francesca; Đorđević, Luka; Nagasing, Benjamin Journal of the American Chemical Society, Vol. 143, Issue 43 https://doi.org/10.1021/jacs.1c06961	journal	October 2021
Proton-Coupled Electron Transfer: The Engine of Energy Conversion and Storage Nocera, Daniel G. Journal of the American Chemical Society, Vol. 144, Issue 3 https://doi.org/10.1021/jacs.1c10444	journal	January 2022
Utilization of Low-Concentration CO₂ with Molecular Catalysts Assisted by CO₂-Capturing Ability of Catalysts, Additives, or Reaction Media Yamazaki, Yasuomi; Miyaji, Masahiko; Ishitani, Osamu Journal of the American Chemical Society, Vol. 144, Issue 15 https://doi.org/10.1021/jacs.2c02245	journal	April 2022
Highly Efficient and Selective Photocatalytic CO ₂ Reduction by Iron and Cobalt Quaterpyridine Complexes Guo, Zhenguo; Cheng, Siwei; Cometto, Claudio Journal of the American Chemical Society, Vol. 138, Issue 30 https://doi.org/10.1021/jacs.6b06002	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
Electrocatalytic CO ₂ Reduction by Imidazolium-Functionalized Molecular Catalysts Sung, Siyoung; Kumar, Davinder; Gil-Sepulcre, Marcos Journal of the American Chemical Society, Vol. 139, Issue 40 https://doi.org/10.1021/jacs.7b07709	journal	September 2017
Visible-Light-Driven Conversion of CO ₂ to CH ₄ with an Organic Sensitizer and an Iron Porphyrin Catalyst Rao, Heng; Lim, Chern-Hooi; Bonin, Julien Journal of the American Chemical Society, Vol. 140, Issue 51 https://doi.org/10.1021/jacs.8b09740	journal	December 2018
Synergistic Effects of Imidazolium-Functionalization on fac -Mn(CO) ₃ Bipyridine Catalyst Platforms for Electrocatalytic Carbon Dioxide Reduction Sung, Siyoung; Li, Xiaohui; Wolf, Lucienna M. Journal of the American Chemical Society, Vol. 141, Issue 16 https://doi.org/10.1021/jacs.8b13657	journal	March 2019
Improving Photocatalysis for the Reduction of CO ₂ through Non-covalent Supramolecular Assembly Cheung, Po Ling; Kapper, Savannah C.; Zeng, Tian Journal of the American Chemical Society, Vol. 141, Issue 38 https://doi.org/10.1021/jacs.9b07067	journal	September 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
Visible-light-driven methane formation from CO2 with a molecular iron catalyst Rao, Heng; Schmidt, Luciana C.; Bonin, Julien Nature, Vol. 548, Issue 7665 https://doi.org/10.1038/nature23016	journal	July 2017
Powering the planet with solar fuel Gray, Harry B. Nature Chemistry, Vol. 1, Issue 1 https://doi.org/10.1038/nchem.141	journal	April 2009
Promoting photocatalytic CO2 reduction with a molecular copper purpurin chromophore Yuan, Huiqing; Cheng, Banggui; Lei, Jingxiang Nature Communications, Vol. 12, Issue 1 https://doi.org/10.1038/s41467-021-21923-9	journal	March 2021
Bioinspiration in light harvesting and catalysis Proppe, Andrew H.; Li, Yuguang C.; Aspuru-Guzik, Alán Nature Reviews Materials, Vol. 5, Issue 11 https://doi.org/10.1038/s41578-020-0222-0	journal	August 2020
The technological and economic prospects for CO2 utilization and removal Hepburn, Cameron; Adlen, Ella; Beddington, John Nature, Vol. 575, Issue 7781 https://doi.org/10.1038/s41586-019-1681-6	journal	November 2019
A robust and efficient cobalt molecular catalyst for CO ₂ reduction Chan, Sharon Lai-Fung; Lam, Tsz Lung; Yang, Chen Chemical Communications, Vol. 51, Issue 37 https://doi.org/10.1039/c5cc00566c	journal	January 2015
A highly active and robust iron quinquepyridine complex for photocatalytic CO₂ reduction in aqueous acetonitrile solution Qin, Yanfei; Chen, Lingjing; Chen, Gui Chemical Communications, Vol. 56, Issue 46 https://doi.org/10.1039/d0cc01930e	journal	January 2020
Photophysical Properties and Redox Potentials of Photosensitizers for Organic Photoredox Transformations Teets, Thomas S.; Wu, Yanyu; Kim, Dooyoung Synlett, Vol. 33, Issue 12 https://doi.org/10.1055/a-1390-9065	journal	March 2021
Software for the frontiers of quantum chemistry: An overview of developments in the Q-Chem 5 package Epifanovsky, Evgeny; Gilbert, Andrew T. B.; Feng, Xintian The Journal of Chemical Physics, Vol. 155, Issue 8 https://doi.org/10.1063/5.0055522	journal	August 2021
Powering the planet: Chemical challenges in solar energy utilization Lewis, N. S.; Nocera, D. G. Proceedings of the National Academy of Sciences, Vol. 103, Issue 43, p. 15729-15735 https://doi.org/10.1073/pnas.0603395103	journal	October 2006
Electrochemical Reduction of Carbamates and Carbamic Acids: Implications for Combined Carbon Capture and Electrochemical CO₂ Recycling Bhattacharya, Moumita; Sebghati, Sepehr; Vercella, Yvensha Madeika Journal of The Electrochemical Society, Vol. 167, Issue 8 https://doi.org/10.1149/1945-7111/ab8ed0	journal	January 2020

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Exchange Coupling Determines Metal-Dependent Efficiency for Iron- and Cobalt-Catalyzed Photochemical CO2 Reduction

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