Reversible and Selective CO 2 to HCO 2 − Electrocatalysis near the Thermodynamic Potential

Cunningham, Drew W.; Barlow, Jeffrey M.; Velazquez, Reyna S.; Yang, Jenny Y.

doi:10.1002/ange.201913198

Title: Reversible and Selective CO ₂ to HCO ₂ ⁻ Electrocatalysis near the Thermodynamic Potential

Abstract

Abstract Reversible catalysis is a hallmark of energy‐efficient chemical transformations, but can only be achieved if the changes in free energy of intermediate steps are minimized and the catalytic cycle is devoid of high transition‐state barriers. Using these criteria, we demonstrate reversible CO ₂ /HCO ₂ ⁻ conversion catalyzed by [Pt(depe) ₂ ] ²⁺ (depe=1,2‐ bis (diethylphosphino)ethane). Direct measurement of the free energies associated with each catalytic step correctly predicts a slight bias towards CO ₂ reduction. We demonstrate how the experimentally measured free energy of each step directly contributes to the <50 mV overpotential. We also find that for CO ₂ reduction, H ₂ evolution is negligible and the Faradaic efficiency for HCO ₂ ⁻ production is nearly quantitative. A free‐energy analysis reveals H ₂ evolution is endergonic, providing a thermodynamic basis for highly selective CO ₂ reduction.

Authors:

Cunningham, Drew W. ^[1]; Barlow, Jeffrey M. ^[1]; Velazquez, Reyna S. ^[1];

^[1]

Department of Chemistry University of California, Irvine Natural Sciences II Irvine CA 92697 USA

Publication Date:: Mon Feb 03 00:00:00 EST 2020

Sponsoring Org.:: USDOE

OSTI Identifier:: 1597157

Resource Type:: Publisher's Accepted Manuscript

Journal Name:: Angewandte Chemie

Additional Journal Information:: Journal Name: Angewandte Chemie Journal Volume: 132 Journal Issue: 11; Journal ID: ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)

Country of Publication:: Germany

Language:: English

Citation Formats


                    Cunningham, Drew W., Barlow, Jeffrey M., Velazquez, Reyna S., and Yang, Jenny Y. Reversible and Selective CO 2 to HCO 2 − Electrocatalysis near the Thermodynamic Potential.  Germany: N. p., 2020. 
Web.  doi:10.1002/ange.201913198.

Copy to clipboard


                    Cunningham, Drew W., Barlow, Jeffrey M., Velazquez, Reyna S., & Yang, Jenny Y. Reversible and Selective CO 2 to HCO 2 − Electrocatalysis near the Thermodynamic Potential.  Germany.  https://doi.org/10.1002/ange.201913198

Copy to clipboard


                    Cunningham, Drew W., Barlow, Jeffrey M., Velazquez, Reyna S., and Yang, Jenny Y. Mon .  
"Reversible and Selective CO 2 to HCO 2 − Electrocatalysis near the Thermodynamic Potential".  Germany.  https://doi.org/10.1002/ange.201913198.

Copy to clipboard


                    
@article{osti_1597157,

  title        = {Reversible and Selective CO 2 to HCO 2 − Electrocatalysis near the Thermodynamic Potential},

  author       = {Cunningham, Drew W. and Barlow, Jeffrey M. and Velazquez, Reyna S. and Yang, Jenny Y.},

  abstractNote = {Abstract Reversible catalysis is a hallmark of energy‐efficient chemical transformations, but can only be achieved if the changes in free energy of intermediate steps are minimized and the catalytic cycle is devoid of high transition‐state barriers. Using these criteria, we demonstrate reversible CO 2 /HCO 2 − conversion catalyzed by [Pt(depe) 2 ] 2+ (depe=1,2‐ bis (diethylphosphino)ethane). Direct measurement of the free energies associated with each catalytic step correctly predicts a slight bias towards CO 2 reduction. We demonstrate how the experimentally measured free energy of each step directly contributes to the <50 mV overpotential. We also find that for CO 2 reduction, H 2 evolution is negligible and the Faradaic efficiency for HCO 2 − production is nearly quantitative. A free‐energy analysis reveals H 2 evolution is endergonic, providing a thermodynamic basis for highly selective CO 2 reduction.},

  doi          = {10.1002/ange.201913198},

  journal      = {Angewandte Chemie},

  number       = 11,

  volume       = 132,

  place        = {Germany},

  year         = {Mon Feb 03 00:00:00 EST 2020},

  month        = {Mon Feb 03 00:00:00 EST 2020}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (Publisher)

Publisher's Version of Record
https://doi.org/10.1002/ange.201913198

Other availability

Search WorldCat to find libraries that may hold this journal

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Rapid Selective Electrocatalytic Reduction of Carbon Dioxide to Formate by an Iridium Pincer Catalyst Immobilized on Carbon Nanotube Electrodes
journal, June 2014

Kang, Peng; Zhang, Sheng; Meyer, Thomas J.
Angewandte Chemie International Edition, Vol. 53, Issue 33
DOI: 10.1002/anie.201310722

Thermodynamic Considerations for Optimizing Selective CO ₂ Reduction by Molecular Catalysts
journal, March 2019

Barlow, Jeffrey M.; Yang, Jenny Y.
ACS Central Science, Vol. 5, Issue 4
DOI: 10.1021/acscentsci.9b00095

Electrocatalytic Hydrogen Evolution under Acidic Aqueous Conditions and Mechanistic Studies of a Highly Stable Molecular Catalyst
journal, July 2016

Tsay, Charlene; Yang, Jenny Y.
Journal of the American Chemical Society, Vol. 138, Issue 43
DOI: 10.1021/jacs.6b05851

Direct formate fuel cells: A review
journal, July 2016

An, L.; Chen, R.
Journal of Power Sources, Vol. 320
DOI: 10.1016/j.jpowsour.2016.04.082

Renewable Formate from C–H Bond Formation with CO ₂ : Using Iron Carbonyl Clusters as Electrocatalysts
journal, August 2017

Loewen, Natalia D.; Neelakantan, Taruna V.; Berben, Louise A.
Accounts of Chemical Research, Vol. 50, Issue 9
DOI: 10.1021/acs.accounts.7b00302

Formate: an Energy Storage and Transport Bridge between Carbon Dioxide and a Formate Fuel Cell in a Single Device
journal, October 2015

Vo, Tracy; Purohit, Krutarth; Nguyen, Christopher
ChemSusChem, Vol. 8, Issue 22
DOI: 10.1002/cssc.201500958

Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO ₂ Reduction
journal, January 2018

Waldie, Kate M.; Ostericher, Andrew L.; Reineke, Mark H.
ACS Catalysis, Vol. 8, Issue 2
DOI: 10.1021/acscatal.7b03396

Measurement of the Hydride Donor Abilities of [HM(diphosphine) ₂ ] ⁺ Complexes (M = Ni, Pt) by Heterolytic Activation of Hydrogen
journal, March 2002

Curtis, Calvin J.; Miedaner, Alex; Ellis, William W.
Journal of the American Chemical Society, Vol. 124, Issue 9
DOI: 10.1021/ja0116829

Determining the Overpotential for a Molecular Electrocatalyst
journal, December 2013

Appel, Aaron M.; Helm, Monte L.
ACS Catalysis, Vol. 4, Issue 2
DOI: 10.1021/cs401013v

pH-Dependent Reactivity of a Water-Soluble Nickel Complex: Hydrogen Evolution vs Selective Electrochemical Hydride Generation
journal, October 2018

Tsay, Charlene; Ceballos, Bianca M.; Yang, Jenny Y.
Organometallics, Vol. 38, Issue 6
DOI: 10.1021/acs.organomet.8b00558

Single Iridium Pincer Complex for Roundtrip Electrochemical Conversion between Carbon Dioxide and Formate
journal, March 2019

Bi, Jiaojiao; Hou, Pengfei; Kang, Peng
ChemCatChem, Vol. 11, Issue 8
DOI: 10.1002/cctc.201900083

Relative Hydride, Proton, and Hydrogen Atom Transfer Abilities of [HM(diphosphine) ₂ ]PF ₆ Complexes (M = Pt, Ni)
journal, December 1999

Berning, Douglas E.; Noll, Bruce C.; DuBois, Daniel L.
Journal of the American Chemical Society, Vol. 121, Issue 49
DOI: 10.1021/ja991888y

Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic
journal, February 2012

Smith, Stuart E.; Yang, Jenny Y.; DuBois, Daniel L.
Angewandte Chemie, Vol. 124, Issue 13
DOI: 10.1002/ange.201108461

Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry of Systems Approaching Reversibility
journal, July 2018

Savéant, Jean-Michel
ACS Catalysis, Vol. 8, Issue 8
DOI: 10.1021/acscatal.8b02007

Reversible Interconversion of CO ₂ and Formate by a Molybdenum-Containing Formate Dehydrogenase
journal, October 2014

Bassegoda, Arnau; Madden, Christopher; Wakerley, David W.
Journal of the American Chemical Society, Vol. 136, Issue 44
DOI: 10.1021/ja508647u

Electroreduction of Carbon Dioxide to Formate by Homogeneous Ir Catalysts in Water
journal, October 2018

Kanega, Ryoichi; Onishi, Naoya; Wang, Lin
ACS Catalysis, Vol. 8, Issue 12
DOI: 10.1021/acscatal.8b02525

The kinetics and mechanism of the organo-iridium-catalysed enantioselective reduction of imines
journal, January 2016

Stirling, Matthew J.; Sweeney, Gemma; MacRory, Kerry
Organic & Biomolecular Chemistry, Vol. 14, Issue 14
DOI: 10.1039/C6OB00245E

Selective Electrocatalytic Reduction of CO ₂ to Formate by Water-Stable Iridium Dihydride Pincer Complexes
journal, March 2012

Kang, Peng; Cheng, Chen; Chen, Zuofeng
Journal of the American Chemical Society, Vol. 134, Issue 12
DOI: 10.1021/ja300543s

Directing the reactivity of metal hydrides for selective CO ₂ reduction
journal, November 2018

Ceballos, Bianca M.; Yang, Jenny Y.
Proceedings of the National Academy of Sciences, Vol. 115, Issue 50
DOI: 10.1073/pnas.1811396115

CO ₂ reduction or HCO ₂ ⁻ oxidation? Solvent-dependent thermochemistry of a nickel hydride complex
journal, January 2017

Ceballos, Bianca M.; Tsay, Charlene; Yang, Jenny Y.
Chemical Communications, Vol. 53, Issue 53
DOI: 10.1039/C7CC02511D

Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic
journal, February 2012

Smith, Stuart E.; Yang, Jenny Y.; DuBois, Daniel L.
Angewandte Chemie International Edition, Vol. 51, Issue 13, p. 3152-3155
DOI: 10.1002/anie.201108461

Electrochemical CO ₂ Reduction to Formic Acid at Low Overpotential and with High Faradaic Efficiency on Carbon-Supported Bimetallic Pd–Pt Nanoparticles
journal, June 2015

Kortlever, Ruud; Peters, Ines; Koper, Sander
ACS Catalysis, Vol. 5, Issue 7
DOI: 10.1021/acscatal.5b00602

Rapid Selective Electrocatalytic Reduction of Carbon Dioxide to Formate by an Iridium Pincer Catalyst Immobilized on Carbon Nanotube Electrodes
journal, June 2014

Kang, Peng; Zhang, Sheng; Meyer, Thomas J.
Angewandte Chemie, Vol. 126, Issue 33
DOI: 10.1002/ange.201310722

Designing electrochemically reversible H2 oxidation and production catalysts
journal, August 2018

Dutta, Arnab; Appel, Aaron M.; Shaw, Wendy J.
Nature Reviews Chemistry, Vol. 2, Issue 9
DOI: 10.1038/s41570-018-0032-8

H ₂ Evolution and Molecular Electrocatalysts: Determination of Overpotentials and Effect of Homoconjugation
journal, November 2010

Fourmond, Vincent; Jacques, Pierre-André; Fontecave, Marc
Inorganic Chemistry, Vol. 49, Issue 22
DOI: 10.1021/ic101187v

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
DOI: 10.1002/1099-0739(200012)14:12<860::AID-AOC87>3.0.CO;2-A

Thermodynamic Hydricity of Transition Metal Hydrides
journal, June 2016

Wiedner, Eric S.; Chambers, Matthew B.; Pitman, Catherine L.
Chemical Reviews, Vol. 116, Issue 15
DOI: 10.1021/acs.chemrev.6b00168

Direct Determination of Equilibrium Potentials for Hydrogen Oxidation/Production by Open Circuit Potential Measurements in Acetonitrile
journal, June 2012

Roberts, John A. S.; Bullock, R. Morris
Inorganic Chemistry, Vol. 52, Issue 7
DOI: 10.1021/ic302461q

Development of Molecular Electrocatalysts for CO₂ Reduction and H₂ Production/Oxidation
journal, December 2009

Rakowski Dubois, M.; Dubois, Daniel L.
Accounts of Chemical Research, Vol. 42, Issue 12, p. 1974-1982
DOI: 10.1021/ar900110c

Tailoring Electrocatalysts for Selective CO ₂ or H ⁺ Reduction: Iron Carbonyl Clusters as a Case Study
journal, November 2015

Taheri, Atefeh; Berben, Louise A.
Inorganic Chemistry, Vol. 55, Issue 2
DOI: 10.1021/acs.inorgchem.5b02293

Achieving Reversible H ₂ /H ⁺ Interconversion at Room Temperature with Enzyme-Inspired Molecular Complexes: A Mechanistic Study
journal, August 2016

Priyadarshani, Nilusha; Dutta, Arnab; Ginovska, Bojana
ACS Catalysis, Vol. 6, Issue 9
DOI: 10.1021/acscatal.6b01433

Molecular Cobalt Complexes with Pendant Amines for Selective Electrocatalytic Reduction of Carbon Dioxide to Formic Acid
journal, March 2017

Roy, Souvik; Sharma, Bhaskar; Pécaut, Jacques
Journal of the American Chemical Society, Vol. 139, Issue 10
DOI: 10.1021/jacs.6b11474

Reversible interconversion of carbon dioxide and formate by an electroactive enzyme
journal, July 2008

Reda, T.; Plugge, C. M.; Abram, N. J.
Proceedings of the National Academy of Sciences, Vol. 105, Issue 31, p. 10654-10658
DOI: 10.1073/pnas.0801290105

Combining theory and experiment in electrocatalysis: Insights into materials design
journal, January 2017

Seh, Zhi Wei; Kibsgaard, Jakob; Dickens, Colin F.
Science, Vol. 355, Issue 6321
DOI: 10.1126/science.aad4998

Understanding and Tuning the Catalytic Bias of Hydrogenase
journal, May 2012

Abou Hamdan, Abbas; Dementin, Sébastien; Liebgott, Pierre-Pol
Journal of the American Chemical Society, Vol. 134, Issue 20
DOI: 10.1021/ja301802r

Electrocatalysts for hydrogen evolution reaction
journal, April 2017

Eftekhari, Ali
International Journal of Hydrogen Energy, Vol. 42, Issue 16
DOI: 10.1016/j.ijhydene.2017.02.125

Understanding and Design of Bidirectional and Reversible Catalysts of Multielectron, Multistep Reactions
journal, June 2019

Fourmond, Vincent; Wiedner, Eric S.; Shaw, Wendy J.
Journal of the American Chemical Society, Vol. 141, Issue 28
DOI: 10.1021/jacs.9b04854

Electrocatalytic mechanism of reversible hydrogen cycling by enzymes and distinctions between the major classes of hydrogenases
journal, July 2012

Hexter, S. V.; Grey, F.; Happe, T.
Proceedings of the National Academy of Sciences, Vol. 109, Issue 29
DOI: 10.1073/pnas.1204770109

Solvation Effects on Transition Metal Hydricity
journal, November 2015

Tsay, Charlene; Livesay, Brooke N.; Ruelas, Samantha
Journal of the American Chemical Society, Vol. 137, Issue 44
DOI: 10.1021/jacs.5b07777

Similar Records in DOE PAGES and OSTI.GOV collections:

Reversible and Selective CO₂ to HCO₂^- Electrocatalysis near the Thermodynamic Potential

Journal Article Cunningham, Drew W. ; Barlow, Jeffrey M. ; Velazquez, Reyna S. ; ... - Angewandte Chemie (International Edition)

Reversible catalysis is an emblem of energy-efficient chemical transformations, but can only be achieved if the changes in free energy of intermediate steps are minimized and the catalytic cycle is devoid of high transition-state barriers. Using these criteria, we show reversible CO₂/HCO₂^- conversion catalyzed by [Pt(depe)₂]²⁺ (depe=1,2-bis(diethylphosphino)ethane). Direct measurement of the free energies associated with each catalytic step correctly predicts a slight bias towards CO₂ reduction. We demonstrate how the experimentally measured free energy of each step directly contributes to the <50mV overpotential. We also find that for CO₂ reduction, H₂ evolution is negligible and the Faradaic efficiency for HCO₂^-more »« less
Cited by 28
https://doi.org/10.1002/anie.201913198

Full Text Available
Kinetic and mechanistic analysis of a synthetic reversible CO₂/HCO₂^- electrocatalyst

Journal Article Cunningham, Drew W. ; Yang, Jenny Y. - ChemComm

[Pt(depe)₂](PF₆)₂ electrocatalyzes the reversible conversion between CO₂ and HCO₂^- with high selectivity and low overpotential but low rates. A comprehensive kinetic analysis indicates the rate determining step for CO₂ reduction is the reactivity of a Pt hydride intermediate to produce HCO₂^-. To accelerate catalysis, the use of cationic and hydrogen-bond donor additives are explored.
https://doi.org/10.1039/d0cc05556e

Full Text Available
2D Copper Tetrahydroxyquinone Conductive Metal–Organic Framework for Selective CO ₂ Electrocatalysis at Low Overpotentials

Journal Article Majidi, Leily ; Ahmadiparidari, Alireza ; Shan, Nannan ; ... - Advanced Materials

Abstract Metal–organic frameworks (MOFs) are promising materials for electrocatalysis; however, lack of electrical conductivity in the majority of existing MOFs limits their effective utilization in the field. Herein, an excellent catalytic activity of a 2D copper (Cu)‐based conductive MOF, copper tetrahydroxyquinone (CuTHQ), is reported for aqueous CO ₂ reduction reaction (CO ₂ RR) at low overpotentials. It is revealed that CuTHQ nanoflakes (NFs) with an average lateral size of 140 nm exhibit a negligible overpotential of 16 mV for the activation of this reaction, a high current density of ≈173 mA cm ⁻² at −0.45 V versus RHE, an average Faradaic efficiency (F.E.) ofmore »« less
https://doi.org/10.1002/adma.202004393
Structure Activity Relationships for Second‐Coordination Sphere Functional Group Dependent CO ₂ Reduction by Manganese Bipyridyl Electrocatalysts

Journal Article Blasczak, Vanna ; Murphy, Alana ; Suntrup, Lisa ; ... - ChemCatChem

Abstract A series of twelve second coordination sphere (SCS) functionalized manganese tricarbonyl bipyridyl complexes are investigated for their electrocatalytic CO ₂ reduction properties in acetonitrile. A qualitative and quantitative assessment of the SCS functional groups is discussed with respect to the catalysts’ thermodynamic and kinetic efficiencies, and their product selectivities. In probing a broad scope of functional groups, it is clear that only the aprotic ortho‐arylester SCS is capable of promoting the highly desired low‐overpotential proton‐transfer electron‐transfer (PT‐ET) pathway for selective CO production. The ortho‐phenolic analogues cause an increase in overpotential with a product selectivity favoring H ₂ evolution, consistentmore »« less
https://doi.org/10.1002/cctc.202301388
Thiolato-technetium complexes. 1. Synthesis and characterization of bis(tertiary diphosphine)technetium(III) complexes containing methanethiolato ligands. Single-crystal structural analyses of trans-(Tc/sup III/(SCH/sub 3/)/sub 2/(DMPE)/sub 2/)CF/sub 3/SO/sub 3/ and trans-(Tc/sup III/(SCH/sub 3/)/sub 2/(DEPE)/sub 2/)PF/sub 6/, where DMPE = 1,2-bis(dimethylphosphino)ethane and DEPE = 1,2-bis(diethylphosphino)ethane

Journal Article Konno, T ; Heeg, M J ; Deutsch, E - Inorg. Chem.; (United States)

The Tc(III) methanethiolato complexes trans-(Tc(SCH/sub 3/)/sub 2/D/sub 2/)/sup +/, where D is either 1,2-bis(dimethylphosphino)ethane (DMPE) or 1,2-bis(diethylphosphino)ethane (DEPE), have been synthesized and characterized. Preparation of these complexes from (Tc/sup V/(O)(OH)D/sub 2/)/sup 2+/ utilizes excess NaSCH/sub 3/ as reductant and ligand. The x-ray crystal structures of both title complexes are examined, and the crystal parameters are reported. In both structures the Tc atom occupies an inversion center. The visible spectra of these trans-(Tc(SCH/sub 3/)/sub 2/D/sub 2/)/sup +/ complexes in acetonitrile show sulfur-technetium charge-transfer bands at 16,810 and 28,490 cm/sup /minus/1/ for D = DMPE and at 16,610 and 28,830 cm/sup /minus/1/more »« less
https://doi.org/10.1021/ic00296a008

Similar Records

Title: Reversible and Selective CO 2 to HCO 2 − Electrocatalysis near the Thermodynamic Potential

Abstract

Citation Formats

Rapid Selective Electrocatalytic Reduction of Carbon Dioxide to Formate by an Iridium Pincer Catalyst Immobilized on Carbon Nanotube Electrodes journal, June 2014

Thermodynamic Considerations for Optimizing Selective CO 2 Reduction by Molecular Catalysts journal, March 2019

Electrocatalytic Hydrogen Evolution under Acidic Aqueous Conditions and Mechanistic Studies of a Highly Stable Molecular Catalyst journal, July 2016

Direct formate fuel cells: A review journal, July 2016

Renewable Formate from C–H Bond Formation with CO 2 : Using Iron Carbonyl Clusters as Electrocatalysts journal, August 2017

Formate: an Energy Storage and Transport Bridge between Carbon Dioxide and a Formate Fuel Cell in a Single Device journal, October 2015

Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO 2 Reduction journal, January 2018

Measurement of the Hydride Donor Abilities of [HM(diphosphine) 2 ] + Complexes (M = Ni, Pt) by Heterolytic Activation of Hydrogen journal, March 2002

Determining the Overpotential for a Molecular Electrocatalyst journal, December 2013

pH-Dependent Reactivity of a Water-Soluble Nickel Complex: Hydrogen Evolution vs Selective Electrochemical Hydride Generation journal, October 2018

Single Iridium Pincer Complex for Roundtrip Electrochemical Conversion between Carbon Dioxide and Formate journal, March 2019

Relative Hydride, Proton, and Hydrogen Atom Transfer Abilities of [HM(diphosphine) 2 ]PF 6 Complexes (M = Pt, Ni) journal, December 1999

Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic journal, February 2012

Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry of Systems Approaching Reversibility journal, July 2018

Reversible Interconversion of CO 2 and Formate by a Molybdenum-Containing Formate Dehydrogenase journal, October 2014

Electroreduction of Carbon Dioxide to Formate by Homogeneous Ir Catalysts in Water journal, October 2018

The kinetics and mechanism of the organo-iridium-catalysed enantioselective reduction of imines journal, January 2016

Selective Electrocatalytic Reduction of CO 2 to Formate by Water-Stable Iridium Dihydride Pincer Complexes journal, March 2012

Directing the reactivity of metal hydrides for selective CO 2 reduction journal, November 2018

CO 2 reduction or HCO 2 − oxidation? Solvent-dependent thermochemistry of a nickel hydride complex journal, January 2017

Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic journal, February 2012

Electrochemical CO 2 Reduction to Formic Acid at Low Overpotential and with High Faradaic Efficiency on Carbon-Supported Bimetallic Pd–Pt Nanoparticles journal, June 2015

Rapid Selective Electrocatalytic Reduction of Carbon Dioxide to Formate by an Iridium Pincer Catalyst Immobilized on Carbon Nanotube Electrodes journal, June 2014

Designing electrochemically reversible H2 oxidation and production catalysts journal, August 2018

H 2 Evolution and Molecular Electrocatalysts: Determination of Overpotentials and Effect of Homoconjugation journal, November 2010

Hydricity of transition-metal hydrides and its role in CO2 reduction journal, January 2000

Thermodynamic Hydricity of Transition Metal Hydrides journal, June 2016

Direct Determination of Equilibrium Potentials for Hydrogen Oxidation/Production by Open Circuit Potential Measurements in Acetonitrile journal, June 2012

Development of Molecular Electrocatalysts for CO2 Reduction and H2 Production/Oxidation journal, December 2009

Tailoring Electrocatalysts for Selective CO 2 or H + Reduction: Iron Carbonyl Clusters as a Case Study journal, November 2015

Achieving Reversible H 2 /H + Interconversion at Room Temperature with Enzyme-Inspired Molecular Complexes: A Mechanistic Study journal, August 2016

Molecular Cobalt Complexes with Pendant Amines for Selective Electrocatalytic Reduction of Carbon Dioxide to Formic Acid journal, March 2017

Reversible interconversion of carbon dioxide and formate by an electroactive enzyme journal, July 2008

Combining theory and experiment in electrocatalysis: Insights into materials design journal, January 2017

Understanding and Tuning the Catalytic Bias of Hydrogenase journal, May 2012

Electrocatalysts for hydrogen evolution reaction journal, April 2017

Understanding and Design of Bidirectional and Reversible Catalysts of Multielectron, Multistep Reactions journal, June 2019

Electrocatalytic mechanism of reversible hydrogen cycling by enzymes and distinctions between the major classes of hydrogenases journal, July 2012

Solvation Effects on Transition Metal Hydricity journal, November 2015

Title: Reversible and Selective CO ₂ to HCO ₂ ⁻ Electrocatalysis near the Thermodynamic Potential

Rapid Selective Electrocatalytic Reduction of Carbon Dioxide to Formate by an Iridium Pincer Catalyst Immobilized on Carbon Nanotube Electrodes
journal, June 2014

Thermodynamic Considerations for Optimizing Selective CO ₂ Reduction by Molecular Catalysts
journal, March 2019

Electrocatalytic Hydrogen Evolution under Acidic Aqueous Conditions and Mechanistic Studies of a Highly Stable Molecular Catalyst
journal, July 2016

Direct formate fuel cells: A review
journal, July 2016

Renewable Formate from C–H Bond Formation with CO ₂ : Using Iron Carbonyl Clusters as Electrocatalysts
journal, August 2017

Formate: an Energy Storage and Transport Bridge between Carbon Dioxide and a Formate Fuel Cell in a Single Device
journal, October 2015

Hydricity of Transition-Metal Hydrides: Thermodynamic Considerations for CO ₂ Reduction
journal, January 2018

Measurement of the Hydride Donor Abilities of [HM(diphosphine) ₂ ] ⁺ Complexes (M = Ni, Pt) by Heterolytic Activation of Hydrogen
journal, March 2002

Determining the Overpotential for a Molecular Electrocatalyst
journal, December 2013

pH-Dependent Reactivity of a Water-Soluble Nickel Complex: Hydrogen Evolution vs Selective Electrochemical Hydride Generation
journal, October 2018

Single Iridium Pincer Complex for Roundtrip Electrochemical Conversion between Carbon Dioxide and Formate
journal, March 2019

Relative Hydride, Proton, and Hydrogen Atom Transfer Abilities of [HM(diphosphine) ₂ ]PF ₆ Complexes (M = Pt, Ni)
journal, December 1999

Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic
journal, February 2012

Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry of Systems Approaching Reversibility
journal, July 2018

Reversible Interconversion of CO ₂ and Formate by a Molybdenum-Containing Formate Dehydrogenase
journal, October 2014

Electroreduction of Carbon Dioxide to Formate by Homogeneous Ir Catalysts in Water
journal, October 2018

The kinetics and mechanism of the organo-iridium-catalysed enantioselective reduction of imines
journal, January 2016

Selective Electrocatalytic Reduction of CO ₂ to Formate by Water-Stable Iridium Dihydride Pincer Complexes
journal, March 2012

Directing the reactivity of metal hydrides for selective CO ₂ reduction
journal, November 2018

CO ₂ reduction or HCO ₂ ⁻ oxidation? Solvent-dependent thermochemistry of a nickel hydride complex
journal, January 2017

Reversible Electrocatalytic Production and Oxidation of Hydrogen at Low Overpotentials by a Functional Hydrogenase Mimic
journal, February 2012

Electrochemical CO ₂ Reduction to Formic Acid at Low Overpotential and with High Faradaic Efficiency on Carbon-Supported Bimetallic Pd–Pt Nanoparticles
journal, June 2015

Rapid Selective Electrocatalytic Reduction of Carbon Dioxide to Formate by an Iridium Pincer Catalyst Immobilized on Carbon Nanotube Electrodes
journal, June 2014

Designing electrochemically reversible H2 oxidation and production catalysts
journal, August 2018

H ₂ Evolution and Molecular Electrocatalysts: Determination of Overpotentials and Effect of Homoconjugation
journal, November 2010

Hydricity of transition-metal hydrides and its role in CO2 reduction
journal, January 2000

Thermodynamic Hydricity of Transition Metal Hydrides
journal, June 2016

Direct Determination of Equilibrium Potentials for Hydrogen Oxidation/Production by Open Circuit Potential Measurements in Acetonitrile
journal, June 2012

Development of Molecular Electrocatalysts for CO₂ Reduction and H₂ Production/Oxidation
journal, December 2009

Tailoring Electrocatalysts for Selective CO ₂ or H ⁺ Reduction: Iron Carbonyl Clusters as a Case Study
journal, November 2015

Achieving Reversible H ₂ /H ⁺ Interconversion at Room Temperature with Enzyme-Inspired Molecular Complexes: A Mechanistic Study
journal, August 2016

Molecular Cobalt Complexes with Pendant Amines for Selective Electrocatalytic Reduction of Carbon Dioxide to Formic Acid
journal, March 2017

Reversible interconversion of carbon dioxide and formate by an electroactive enzyme
journal, July 2008

Combining theory and experiment in electrocatalysis: Insights into materials design
journal, January 2017

Understanding and Tuning the Catalytic Bias of Hydrogenase
journal, May 2012

Electrocatalysts for hydrogen evolution reaction
journal, April 2017

Understanding and Design of Bidirectional and Reversible Catalysts of Multielectron, Multistep Reactions
journal, June 2019

Electrocatalytic mechanism of reversible hydrogen cycling by enzymes and distinctions between the major classes of hydrogenases
journal, July 2012

Solvation Effects on Transition Metal Hydricity
journal, November 2015