Metal–Ligand Cooperativity via Exchange Coupling Promotes Iron- Catalyzed Electrochemical CO2 Reduction at Low Overpotentials

Derrick, Jeffrey S.; Loipersberger, Matthias; Chatterjee, Ruchira; Iovan, Diana A.; Smith, Peter T.; Chakarawet, Khetpakorn; Yano, Junko; Long, Jeffrey R.; Head-Gordon, Martin; Chang, Christopher J.

doi:10.1021/jacs.0c10664

Title: Metal–Ligand Cooperativity via Exchange Coupling Promotes Iron- Catalyzed Electrochemical CO₂ Reduction at Low Overpotentials

Journal Article · Wed Nov 18 00:00:00 EST 2020 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.0c10664· OSTI ID:1844513

Derrick, Jeffrey S. ^[1];

^[2]; Chatterjee, Ruchira ^[3];

^[2]; Smith, Peter T. ^[1];

^[2];

^[3];

^[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)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Biological and heterogeneous catalysts for the electrochemical CO₂ reduction reaction (CO₂RR) often exhibit a high degree of electronic delocalization that serves to minimize overpotential and maximize selectivity over the hydrogen evolution reaction (HER). Here, we report a molecular iron(II) system that captures this design concept in a homogeneous setting through the use of a redox non-innocent terpyridine-based pentapyridine ligand (tpyPY2Me). As a result of strong metal-ligand exchange coupling between the Fe(II) center and ligand, [Fe(tpyPY2Me)]²⁺ exhibits redox behavior at potentials 640 mV more positive than the isostructural [Zn(tpyPY2Me)]²⁺ analog containing the redox-inactive Zn(II) ion. This shift in redox potential is attributed to the requirement for both an open-shell metal ion and a redox non-innocent ligand. The metal-ligand cooperativity in [Fe(tpyPY2Me)]²⁺ drives the electrochemical reduction of CO₂ to CO at low overpotentials with high selectivity for CO₂RR (>90%) and turnover frequencies of 100,000 s^-1 with no degradation over 20 h. The decrease in the thermodynamic barrier engendered by this coupling also enables homogeneous CO₂ reduction catalysis in water without compromising selectivity or rates. Synthesis of the two-electron reduction product, [Fe(tpyPY2Me)]^o, and characterization by X-ray crystallography, Mössbauer spectroscopy, X-ray absorption spectroscopy (XAS), variable temperature NMR, and density functional theory (DFT) calculations, support assignment of an open-shell singlet electronic structure that maintains a formal Fe(II) oxidation state with a doubly reduced ligand system. Furthermore, this work provides a starting point for the design of systems that exploit metal-ligand cooperativity for electrocatalysis where the electrochemical potential of redox non-innocent ligands can be tuned through secondary metal-dependent interactions.

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

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1844513

Journal Information:: Journal of the American Chemical Society, Vol. 142, Issue 48; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (78)

Nickel(ii) macrocycles: highly efficient electrocatalysts for the selective reduction of CO2 to CO Schneider, Jacob; Jia, Hongfei; Kobiro, Kazuya Energy & Environmental Science, Vol. 5, Issue 11 https://doi.org/10.1039/c2ee22528j	journal	January 2012
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
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
Kinetic and Mechanistic Effects of Bipyridine (bpy) Substituent, Labile Ligand, and Brønsted Acid on Electrocatalytic CO ₂ Reduction by Re(bpy) Complexes Clark, Melissa L.; Cheung, Po Ling; Lessio, Martina ACS Catalysis, Vol. 8, Issue 3 https://doi.org/10.1021/acscatal.7b03971	journal	January 2018
What would it take for renewably powered electrosynthesis to displace petrochemical processes? De Luna, Phil; Hahn, Christopher; Higgins, Drew Science, Vol. 364, Issue 6438 https://doi.org/10.1126/science.aav3506	journal	April 2019
Electronic Structures of the Electron Transfer Series [M(bpy) ₃ ] ⁿ , [M(tpy) ₂ ] ⁿ , and [Fe( ^t bpy) ₃ ] ⁿ (M = Fe, Ru; n = 3+, 2+, 1+, 0, 1-): A Mössbauer Spectroscopic and DFT Study : [M(bpy) England, Jason; Scarborough, Christopher C.; Weyhermüller, Thomas European Journal of Inorganic Chemistry, Vol. 2012, Issue 29 https://doi.org/10.1002/ejic.201200232	journal	June 2012
Standard Electrode Potentials for the Reduction of CO ₂ to CO in Acetonitrile–Water Mixtures Determined Using a Generalized Method for Proton-Coupled Electron-Transfer Reactions Matsubara, Yasuo ACS Energy Letters, Vol. 2, Issue 8 https://doi.org/10.1021/acsenergylett.7b00548	journal	August 2017
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
The Electronic States of Rhenium Bipyridyl Electrocatalysts for CO ₂ Reduction as Revealed by X-ray Absorption Spectroscopy and Computational Quantum Chemistry Benson, Eric E.; Sampson, Matthew D.; Grice, Kyle A. Angewandte Chemie International Edition, Vol. 52, Issue 18 https://doi.org/10.1002/anie.201209911	journal	March 2013
Heterogeneous molecular catalysts for electrocatalytic CO2 reduction Corbin, Nathan; Zeng, Joy; Williams, Kindle Nano Research, Vol. 12, Issue 9 https://doi.org/10.1007/s12274-019-2403-y	journal	May 2019
Through-Space Charge Interaction Substituent Effects in Molecular Catalysis Leading to the Design of the Most Efficient Catalyst of CO ₂ -to-CO Electrochemical Conversion Azcarate, Iban; Costentin, Cyrille; Robert, Marc Journal of the American Chemical Society, Vol. 138, Issue 51 https://doi.org/10.1021/jacs.6b07014	journal	December 2016
Electrocatalysis by metal phthalocyanines in the reduction of carbon dioxide Meshitsuka, Shunsuke; Ichikawa, Masaru; Tamaru, Kenzi Journal of the Chemical Society, Chemical Communications, Issue 5 https://doi.org/10.1039/c39740000158	journal	January 1974
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
Elucidation of the Selectivity of Proton-Dependent Electrocatalytic CO ₂ Reduction by fac -Re(bpy)(CO) ₃ Cl Keith, John A.; Grice, Kyle A.; Kubiak, Clifford P. Journal of the American Chemical Society, Vol. 135, Issue 42 https://doi.org/10.1021/ja406456g	journal	October 2013
Water-Soluble Iron(IV)-Oxo Complexes Supported by Pentapyridine Ligands: Axial Ligand Effects on Hydrogen Atom and Oxygen Atom Transfer Reactivity Chantarojsiri, Teera; Sun, Yujie; Long, Jeffrey R. Inorganic Chemistry, Vol. 54, Issue 12 https://doi.org/10.1021/acs.inorgchem.5b00658	journal	May 2015
Noninnocence in Metal Complexes: A Dithiolene Dawn Eisenberg, Richard; Gray, Harry B. Inorganic Chemistry, Vol. 50, Issue 20 https://doi.org/10.1021/ic2011748	journal	October 2011
A Cobalt–Dithiolene Complex for the Photocatalytic and Electrocatalytic Reduction of Protons McNamara, William R.; Han, Zhiji; Alperin, Paul J. Journal of the American Chemical Society, Vol. 133, Issue 39 https://doi.org/10.1021/ja207842r	journal	October 2011
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
Activation of Co(I) State in a Cobalt-Dithiolato Catalyst for Selective and Efficient CO ₂ Reduction to CO Dey, Subal; Ahmed, Md Estak; Dey, Abhishek Inorganic Chemistry, Vol. 57, Issue 10 https://doi.org/10.1021/acs.inorgchem.8b00450	journal	May 2018
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
Density Functional Calculations for Prediction of ⁵⁷ Fe Mössbauer Isomer Shifts and Quadrupole Splittings in β-Diketiminate Complexes McWilliams, Sean F.; Brennan-Wydra, Emma; MacLeod, K. Cory ACS Omega, Vol. 2, Issue 6 https://doi.org/10.1021/acsomega.7b00595	journal	June 2017
Molecular electrocatalysts can mediate fast, selective CO ₂ reduction in a flow cell Ren, Shaoxuan; Joulié, Dorian; Salvatore, Danielle Science, Vol. 365, Issue 6451 https://doi.org/10.1126/science.aax4608	journal	July 2019
Electrocatalytic reduction of carbon dioxide mediated by Re(bipy)(CO) ₃ Cl (bipy = 2,2′-bipyridine) Hawecker, Jeannot; Lehn, Jean-Marie; Ziessel, Raymond J. Chem. Soc., Chem. Commun., Issue 6 https://doi.org/10.1039/C39840000328	journal	January 1984
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
Turnover Numbers, Turnover Frequencies, and Overpotential in Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis Costentin, Cyrille; Drouet, Samuel; Robert, Marc Journal of the American Chemical Society, Vol. 134, Issue 27, p. 11235-11242 https://doi.org/10.1021/ja303560c	journal	June 2012
Atomically dispersed Fe ³⁺ sites catalyze efficient CO ₂ electroreduction to CO Gu, Jun; Hsu, Chia-Shuo; Bai, Lichen Science, Vol. 364, Issue 6445 https://doi.org/10.1126/science.aaw7515	journal	June 2019
A Thiourea Tether in the Second Coordination Sphere as a Binding Site for CO ₂ and a Proton Donor Promotes the Electrochemical Reduction of CO ₂ to CO Catalyzed by a Rhenium Bipyridine-Type Complex Haviv, Eynat; Azaiza-Dabbah, Dima; Carmieli, Raanan Journal of the American Chemical Society, Vol. 140, Issue 39 https://doi.org/10.1021/jacs.8b05658	journal	September 2018
Electrocatalysis on gold Rodriguez, Paramaconi; Koper, Marc T. M. Phys. Chem. Chem. Phys., Vol. 16, Issue 27 https://doi.org/10.1039/C4CP00394B	journal	January 2014
On decomposition, degradation, and voltammetric deviation: the electrochemist's field guide to identifying precatalyst transformation Lee, Katherine J.; McCarthy, Brian D.; Dempsey, Jillian L. Chemical Society Reviews, Vol. 48, Issue 11 https://doi.org/10.1039/C8CS00851E	journal	January 2019
Mononuclear iron hydrogenase Dey, Subal; Das, Pradip K.; Dey, Abhishek Coordination Chemistry Reviews, Vol. 257, Issue 1 https://doi.org/10.1016/j.ccr.2012.04.021	journal	January 2013
Evaluation of Homogeneous Electrocatalysts by Cyclic Voltammetry Rountree, Eric S.; McCarthy, Brian D.; Eisenhart, Thomas T. Inorganic Chemistry, Vol. 53, Issue 19 https://doi.org/10.1021/ic500658x	journal	September 2014
Covalent organic frameworks comprising cobalt porphyrins for catalytic CO ₂ reduction in water Lin, Song; Diercks, Christian S.; Zhang, Yue-Biao Science, Vol. 349, Issue 6253 https://doi.org/10.1126/science.aac8343	journal	August 2015
Progress and Perspectives of Electrochemical CO ₂ Reduction on Copper in Aqueous Electrolyte Nitopi, Stephanie; Bertheussen, Erlend; Scott, Soren B. Chemical Reviews, Vol. 119, Issue 12 https://doi.org/10.1021/acs.chemrev.8b00705	journal	April 2019
Reticular Electronic Tuning of Porphyrin Active Sites in Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction Diercks, Christian S.; Lin, Song; Kornienko, Nikolay Journal of the American Chemical Society, Vol. 140, Issue 3 https://doi.org/10.1021/jacs.7b11940	journal	January 2018
Homogeneous CO ₂ Reduction by Ni(cyclam) at a Glassy Carbon Electrode Froehlich, Jesse D.; Kubiak, Clifford P. Inorganic Chemistry, Vol. 51, Issue 7 https://doi.org/10.1021/ic3001619	journal	March 2012
Mechanistic Understanding of CO ₂ Reduction Reaction (CO2RR) Toward Multicarbon Products by Heterogeneous Copper-Based Catalysts Todorova, Tanya K.; Schreiber, Moritz W.; Fontecave, Marc ACS Catalysis, Vol. 10, Issue 3 https://doi.org/10.1021/acscatal.9b04746	journal	December 2019
Conversion constants for redox potentials measured versus different reference electrodes in acetonitrile solutions at 25°C Pavlishchuk, Vitaly V.; Addison, Anthony W. Inorganica Chimica Acta, Vol. 298, Issue 1 https://doi.org/10.1016/S0020-1693(99)00407-7	journal	January 2000
Pendant Hydrogen-Bond Donors in Cobalt Catalysts Independently Enhance CO ₂ Reduction Chapovetsky, Alon; Welborn, Matthew; Luna, John M. ACS Central Science, Vol. 4, Issue 3 https://doi.org/10.1021/acscentsci.7b00607	journal	February 2018
Mechanism of the Electrocatalytic Reduction of Protons with Diaryldithiolene Cobalt Complexes Letko, Christopher S.; Panetier, Julien A.; Head-Gordon, Martin Journal of the American Chemical Society, Vol. 136, Issue 26 https://doi.org/10.1021/ja5019755	journal	June 2014
Thermodynamic Aspects of Electrocatalytic CO ₂ Reduction in Acetonitrile and with an Ionic Liquid as Solvent or Electrolyte Matsubara, Yasuo; Grills, David C.; Kuwahara, Yutaka ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b00656	journal	October 2015
Correction to Turnover Numbers, Turnover Frequencies, and Overpotential in Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis Costentin, Cyrille; Drouet, Samuel; Robert, Marc Journal of the American Chemical Society, Vol. 134, Issue 48 https://doi.org/10.1021/ja3106187	journal	November 2012
Mössbauer Spectroscopy and Transition Metal Chemistry: Fundamentals and Applications Gütlich, Philipp; Bill, Eckhard; Trautwein, Alfred X. https://doi.org/10.1007/978-3-540-88428-6	book	January 2011
Selective Electrocatalysis of a Water-Soluble Rhenium(I) Complex for CO ₂ Reduction Using Water As an Electron Donor Nakada, Akinobu; Ishitani, Osamu ACS Catalysis, Vol. 8, Issue 1 https://doi.org/10.1021/acscatal.7b03275	journal	December 2017
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
Electrocatalytic CO ₂ reduction with nickel complexes supported by tunable bipyridyl-N-heterocyclic carbene donors: understanding redox-active macrocycles Su, Xiaojun; McCardle, Kaitlin M.; Panetier, Julien A. Chemical Communications, Vol. 54, Issue 27 https://doi.org/10.1039/C8CC00266E	journal	January 2018
Structure, Function, and Mechanism of the Nickel Metalloenzymes, CO Dehydrogenase, and Acetyl-CoA Synthase Can, Mehmet; Armstrong, Fraser A.; Ragsdale, Stephen W. Chemical Reviews, Vol. 114, Issue 8 https://doi.org/10.1021/cr400461p	journal	February 2014
Selective electrocatalytic reduction of carbon dioxide to formate by a water-soluble iridium pincer catalyst Kang, Peng; Meyer, Thomas J.; Brookhart, Maurice Chemical Science, Vol. 4, Issue 9 https://doi.org/10.1039/c3sc51339d	journal	January 2013
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
Metal–Polypyridyl Catalysts for Electro- and Photochemical Reduction of Water to Hydrogen Zee, David Z.; Chantarojsiri, Teera; Long, Jeffrey R. Accounts of Chemical Research, Vol. 48, Issue 7 https://doi.org/10.1021/acs.accounts.5b00082	journal	June 2015
An NADH-Inspired Redox Mediator Strategy to Promote Second-Sphere Electron and Proton Transfer for Cooperative Electrochemical CO ₂ Reduction Catalyzed by Iron Porphyrin Smith, Peter T.; Weng, Sophia; Chang, Christopher J. Inorganic Chemistry, Vol. 59, Issue 13 https://doi.org/10.1021/acs.inorgchem.0c01162	journal	June 2020
The Trans Effect in Electrocatalytic CO ₂ Reduction: Mechanistic Studies of Asymmetric Ruthenium Pyridyl-Carbene Catalysts Gonell, Sergio; Massey, Marsha D.; Moseley, Ian P. Journal of the American Chemical Society, Vol. 141, Issue 16 https://doi.org/10.1021/jacs.9b01735	journal	April 2019
Efficient and selective molecular catalyst for the CO ₂ -to-CO electrochemical conversion in water Costentin, Cyrille; Robert, Marc; Savéant, Jean-Michel Proceedings of the National Academy of Sciences, Vol. 112, Issue 22 https://doi.org/10.1073/pnas.1507063112	journal	May 2015
Cobalt-dithiolene complexes for the photocatalytic and electrocatalytic reduction of protons in aqueous solutions McNamara, W. R.; Han, Z.; Yin, C. -J. Proceedings of the National Academy of Sciences, Vol. 109, Issue 39 https://doi.org/10.1073/pnas.1120757109	journal	June 2012
A Local Proton Source Enhances CO ₂ Electroreduction to CO by a Molecular Fe Catalyst Costentin, Cyrille; Drouet, Samuel; Robert, Marc Science, Vol. 338, Issue 6103 https://doi.org/10.1126/science.1224581	journal	October 2012
Electroreduction of CO ₂ Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center Wu, Yueshen; Jiang, Jianbing; Weng, Zhe ACS Central Science, Vol. 3, Issue 8 https://doi.org/10.1021/acscentsci.7b00160	journal	July 2017
Catalysis of the electrochemical reduction of carbon dioxide by iron(“0”) porphyrins Hammouche, M.; Lexa, D.; Savéant, J. M. Journal of Electroanalytical Chemistry and Interfacial Electrochemistry, Vol. 249, Issue 1-2 https://doi.org/10.1016/0022-0728(88)80372-3	journal	July 1988
Electrocatalytic Oxidation of Formate by [Ni(P ^R ₂ N ^R′ ₂ ) ₂ (CH ₃ CN)] ²⁺ Complexes Galan, Brandon R.; Schöffel, Julia; Linehan, John C. Journal of the American Chemical Society, Vol. 133, Issue 32 https://doi.org/10.1021/ja204489e	journal	August 2011
Spectroscopic and Computational Studies of a Ru(II) Terpyridine Complex: The Importance of Weak Intermolecular Forces to Photophysical Properties Garino, Claudio; Gobetto, Roberto; Nervi, Carlo Inorganic Chemistry, Vol. 46, Issue 21 https://doi.org/10.1021/ic7010343	journal	September 2007
Homogeneous Electrochemical Reduction of CO ₂ to CO by a Cobalt Pyridine Thiolate Complex Ahmed, Md Estak; Rana, Atanu; Saha, Rajat Inorganic Chemistry, Vol. 59, Issue 8 https://doi.org/10.1021/acs.inorgchem.9b03056	journal	April 2020
Homogeneously Catalyzed Electroreduction of Carbon Dioxide—Methods, Mechanisms, and Catalysts Francke, Robert; Schille, Benjamin; Roemelt, Michael Chemical Reviews, Vol. 118, Issue 9 https://doi.org/10.1021/acs.chemrev.7b00459	journal	January 2018
Turning on the Protonation-First Pathway for Electrocatalytic CO ₂ Reduction by Manganese Bipyridyl Tricarbonyl Complexes Ngo, Ken T.; McKinnon, Meaghan; Mahanti, Bani Journal of the American Chemical Society, Vol. 139, Issue 7 https://doi.org/10.1021/jacs.6b08776	journal	February 2017
A molecular molybdenum-oxo catalyst for generating hydrogen from water Karunadasa, Hemamala I.; Chang, Christopher J.; Long, Jeffrey R. Nature, Vol. 464, Issue 7293 https://doi.org/10.1038/nature08969	journal	April 2010
Bioinspired design of redox-active ligands for multielectron catalysis: effects of positioning pyrazine reservoirs on cobalt for electro- and photocatalytic generation of hydrogen from water Jurss, Jonah W.; Khnayzer, Rony S.; Panetier, Julien A. Chemical Science, Vol. 6, Issue 8 https://doi.org/10.1039/C5SC01414J	journal	January 2015
Standard Reduction Potentials for Oxygen and Carbon Dioxide Couples in Acetonitrile and N , N -Dimethylformamide Pegis, Michael L.; Roberts, John A. S.; Wasylenko, Derek J. Inorganic Chemistry, Vol. 54, Issue 24 https://doi.org/10.1021/acs.inorgchem.5b02136	journal	December 2015
Experimental Fingerprints for Redox-Active Terpyridine in [Cr(tpy) ₂ ](PF ₆ ) _n ( n = 3–0), and the Remarkable Electronic Structure of [Cr(tpy) ₂ ] ^1– Scarborough, Christopher C.; Lancaster, Kyle M.; DeBeer, Serena Inorganic Chemistry, Vol. 51, Issue 6 https://doi.org/10.1021/ic2027219	journal	March 2012
Electrocatalytic reduction of carbon dioxide by using macrocycles of nickel and cobalt Fisher, Barbara J.; Eisenberg, Richard Journal of the American Chemical Society, Vol. 102, Issue 24, p. 7361-7363 https://doi.org/10.1021/ja00544a035	journal	September 1980
Positional effects of second-sphere amide pendants on electrochemical CO ₂ reduction catalyzed by iron porphyrins Nichols, Eva M.; Derrick, Jeffrey S.; Nistanaki, Sepand K. Chemical Science, Vol. 9, Issue 11 https://doi.org/10.1039/C7SC04682K	journal	January 2018
Kinetics of the Trans Effect in Ruthenium Complexes Provide Insight into the Factors That Control Activity and Stability in CO ₂ Electroreduction Gonell, Sergio; Assaf, Eric A.; Duffee, Kyle D. Journal of the American Chemical Society, Vol. 142, Issue 19 https://doi.org/10.1021/jacs.0c02912	journal	April 2020
Steering CO ₂ electroreduction toward ethanol production by a surface-bound Ru polypyridyl carbene catalyst on N-doped porous carbon Liu, Yanming; Fan, Xinfei; Nayak, Animesh Proceedings of the National Academy of Sciences, Vol. 116, Issue 52 https://doi.org/10.1073/pnas.1907740116	journal	December 2019
A Molecular MoS2 Edge Site Mimic for Catalytic Hydrogen Generation Karunadasa, H. I.; Montalvo, E.; Sun, Y. Science, Vol. 335, Issue 6069 https://doi.org/10.1126/science.1215868	journal	February 2012
Reversible interconversion of carbon dioxide and formate by an electroactive enzyme Reda, T.; Plugge, C. M.; Abram, N. J. Proceedings of the National Academy of Sciences, Vol. 105, Issue 31, p. 10654-10658 https://doi.org/10.1073/pnas.0801290105	journal	July 2008
Electrocatalytic CO ₂ Reduction with a Ruthenium Catalyst in Solution and on Nanocrystalline TiO ₂ Li, Ting‐Ting; Shan, Bing; Xu, Wei ChemSusChem https://doi.org/10.1002/cssc.201900730	journal	May 2019
Electronic Structure of a Formal Iron(0) Porphyrin Complex Relevant to CO ₂ Reduction Römelt, Christina; Song, Jinshuai; Tarrago, Maxime Inorganic Chemistry, Vol. 56, Issue 8 https://doi.org/10.1021/acs.inorgchem.7b00401	journal	April 2017
The value of enzymes in solar fuels research – efficient electrocatalysts through evolution Evans, Rhiannon M.; Siritanaratkul, Bhavin; Megarity, Clare F. Chemical Society Reviews, Vol. 48, Issue 7 https://doi.org/10.1039/C8CS00546J	journal	January 2019
Calibration of Modern Density Functional Theory Methods for the Prediction of ⁵⁷ Fe Mössbauer Isomer Shifts: Meta-GGA and Double-Hybrid Functionals Römelt, Michael; Ye, Shengfa; Neese, Frank Inorganic Chemistry, Vol. 48, Issue 3 https://doi.org/10.1021/ic801535v	journal	February 2009
Nickel(II)-cyclam: an extremely selective electrocatalyst for reduction of CO2 in water Beley, Marc; Collin, Jean-Paul; Ruppert, Romain Journal of the Chemical Society, Chemical Communications, Issue 19 https://doi.org/10.1039/c39840001315	journal	January 1984
X-ray Absorption Spectroscopic Investigation of the Spin-Transition Character in a Series of Single-Site Perturbed Iron(II) Complexes Rudd, Deanne Jackson; Goldsmith, Christian R.; Cole, Adam P. Inorganic Chemistry, Vol. 44, Issue 5 https://doi.org/10.1021/ic048765l	journal	March 2005
Highly Efficient Electrocatalytic Reduction of CO ₂ to CO by a Molecular Chromium Complex Hooe, Shelby L.; Dressel, Julia M.; Dickie, Diane A. ACS Catalysis, Vol. 10, Issue 2 https://doi.org/10.1021/acscatal.9b04687	journal	December 2019

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Title: Metal–Ligand Cooperativity via Exchange Coupling Promotes Iron- Catalyzed Electrochemical CO2 Reduction at Low Overpotentials

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Title: Metal–Ligand Cooperativity via Exchange Coupling Promotes Iron- Catalyzed Electrochemical CO₂ Reduction at Low Overpotentials