Combining scaling relationships overcomes rate versus overpotential trade-offs in O 2 molecular electrocatalysis

Martin, Daniel J.; Mercado, Brandon Q.; Mayer, James M.

doi:10.1126/sciadv.aaz3318

Title: Combining scaling relationships overcomes rate versus overpotential trade-offs in O ₂ molecular electrocatalysis

Abstract

The development of advanced chemical-to-electrical energy conversions requires fast and efficient electrocatalysis of multielectron/multiproton reactions, such as the oxygen reduction reaction (ORR). Using molecular catalysts, correlations between the reaction rate and energy efficiency have recently been identified. Improved catalysis requires circumventing the rate versus overpotential trade-offs implied by such “scaling relationships.” Described here is an ORR system—using a soluble iron porphyrin and weak acids—with the best reported combination of rate and efficiency for a soluble ORR catalyst. This advance is achieved not by “breaking” scaling relationships but rather by combining two of them. Key to this behavior is a polycationic ligand, which enhances anionic ligand binding and changes the catalyst E_1/2. These results show how combining scaling relationships is a powerful way toward improved electrocatalysis.

Authors:

^[1];

^[1]

Yale Univ., New Haven, CT (United States). Dept. of Chemistry

Publication Date:: 2020-03-13

Research Org.:: Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Yale Univ., New Haven, CT (United States)

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

OSTI Identifier:: 1626058

Grant/Contract Number:: FG02-00ER41132

Resource Type:: Accepted Manuscript

Journal Name:: Science Advances

Additional Journal Information:: Journal Volume: 6; Journal Issue: 11; Journal ID: ISSN 2375-2548

Publisher:: AAAS

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Science & Technology - Other Topics

Citation Formats


                    Martin, Daniel J., Mercado, Brandon Q., and Mayer, James M. Combining scaling relationships overcomes rate versus overpotential trade-offs in O 2 molecular electrocatalysis.  United States: N. p., 2020. 
Web.  doi:10.1126/sciadv.aaz3318.

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                    Martin, Daniel J., Mercado, Brandon Q., & Mayer, James M. Combining scaling relationships overcomes rate versus overpotential trade-offs in O 2 molecular electrocatalysis.  United States.  https://doi.org/10.1126/sciadv.aaz3318

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                    Martin, Daniel J., Mercado, Brandon Q., and Mayer, James M. Fri .  
"Combining scaling relationships overcomes rate versus overpotential trade-offs in O 2 molecular electrocatalysis".  United States.  https://doi.org/10.1126/sciadv.aaz3318.  https://www.osti.gov/servlets/purl/1626058.

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@article{osti_1626058,

  title        = {Combining scaling relationships overcomes rate versus overpotential trade-offs in O 2 molecular electrocatalysis},

  author       = {Martin, Daniel J. and Mercado, Brandon Q. and Mayer, James M.},

  abstractNote = {The development of advanced chemical-to-electrical energy conversions requires fast and efficient electrocatalysis of multielectron/multiproton reactions, such as the oxygen reduction reaction (ORR). Using molecular catalysts, correlations between the reaction rate and energy efficiency have recently been identified. Improved catalysis requires circumventing the rate versus overpotential trade-offs implied by such “scaling relationships.” Described here is an ORR system—using a soluble iron porphyrin and weak acids—with the best reported combination of rate and efficiency for a soluble ORR catalyst. This advance is achieved not by “breaking” scaling relationships but rather by combining two of them. Key to this behavior is a polycationic ligand, which enhances anionic ligand binding and changes the catalyst E1/2. These results show how combining scaling relationships is a powerful way toward improved electrocatalysis.},

  doi          = {10.1126/sciadv.aaz3318},

  journal      = {Science Advances},

  number       = 11,

  volume       = 6,

  place        = {United States},

  year         = {2020},

  month        = {3}

}

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Fig. 1: Catalytic system efficiencies, reaction mechanism, and structure of catalyst 1. (A) Plot of log(TOF_max)/$η$_eff values and fits (dashed lines) for 1 (diamonds; data and conditions in Table 1) and for previously reported iron porphyrin [Fe(por)] catalysts (circles; 0.1 M [DMF-H⁺] in DMF or MeCN) (5). The uncertainties aremore »

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Title: Combining scaling relationships overcomes rate versus overpotential trade-offs in O 2 molecular electrocatalysis

Abstract

Citation Formats

Figures / Tables:

Brønsted Acid Scaling Relationships Enable Control Over Product Selectivity from O 2 Reduction with a Mononuclear Cobalt Porphyrin Catalyst journal, June 2019

New protic salts of aprotic polar solvents journal, April 2004

Identifying and Breaking Scaling Relations in Molecular Catalysis of Electrochemical Reactions journal, August 2017

A short history of SHELX journal, December 2007

Oxygen Reduction by Homogeneous Molecular Catalysts and Electrocatalysts journal, December 2017

Determining the Overpotential for a Molecular Electrocatalyst journal, December 2013

Understanding Catalytic Activity Trends in the Oxygen Reduction Reaction journal, December 2017

Molecular Cobalt Catalysts for O 2 Reduction: Low-Overpotential Production of H 2 O 2 and Comparison with Iron-Based Catalysts journal, November 2017

Electrochemical Reduction of Brønsted Acids by Glassy Carbon in Acetonitrile—Implications for Electrocatalytic Hydrogen Evolution journal, July 2014

Electrocatalytic Oxygen Reduction by Iron Tetra-arylporphyrins Bearing Pendant Proton Relays journal, March 2012

High Catalytic Rates for Hydrogen Production Using Nickel Electrocatalysts with Seven-Membered Cyclic Diphosphine Ligands Containing One Pendant Amine journal, February 2013

A Synthetic Nickel Electrocatalyst with a Turnover Frequency Above 100,000 s-1 for H2 Production journal, August 2011

Benchmarking of Homogeneous Electrocatalysts: Overpotential, Turnover Frequency, Limiting Turnover Number journal, April 2015

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 journal, December 2016

Homogeneous, Heterogeneous, and Biological Catalysts for Electrochemical N 2 Reduction toward NH 3 under Ambient Conditions journal, April 2019

Understanding the apparent fractional charge of protons in the aqueous electrochemical double layer journal, August 2018

Titration of bases in acetonitrile journal, November 1967

Decoding Proton-Coupled Electron Transfer with Potential–p K a Diagrams journal, January 2017

Electrodeposition from Acidic Solutions of Nickel Bis(benzenedithiolate) Produces a Hydrogen-Evolving Ni–S Film on Glassy Carbon journal, December 2013

Oxygen Reduction Catalysis at a Dicobalt Center: The Relationship of Faradaic Efficiency to Overpotential journal, February 2016

A Comprehensive Self-Consistent Spectrophotometric Acidity Scale of Neutral Brønsted Acids in Acetonitrile journal, March 2006

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

Toward the rational benchmarking of homogeneous H 2 -evolving catalysts journal, January 2014

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

Multielectron, Multistep Molecular Catalysis of Electrochemical Reactions: Benchmarking of Homogeneous Catalysts journal, June 2014

Reversing the Tradeoff between Rate and Overpotential in Molecular Electrocatalysts for H 2 Production journal, March 2018

Homogeneous Molecular Catalysis of Electrochemical Reactions: Manipulating Intrinsic and Operational Factors for Catalyst Improvement journal, November 2018

Standard Reduction Potentials for Oxygen and Carbon Dioxide Couples in Acetonitrile and N , N -Dimethylformamide journal, December 2015

Supramolecular assemblies of carbon nanocoils and tetraphenylporphyrin derivatives for sensing of catechol and hydroquinone in aqueous solution journal, March 2021

Nonprecious Metal Catalysts for Oxygen Reduction in Heterogeneous Aqueous Systems journal, December 2017

Turnover Numbers, Turnover Frequencies, and Overpotential in Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis journal, June 2012

Introduction: Oxygen Reduction and Activation in Catalysis journal, December 2017

A Practical Beginner’s Guide to Cyclic Voltammetry journal, November 2017

Oxygen Reduction Reaction Promoted by Manganese Porphyrins journal, July 2018

Evaluation of Homogeneous Electrocatalysts by Cyclic Voltammetry journal, September 2014

Dioxygen Reduction to Hydrogen Peroxide by a Molecular Mn Complex: Mechanistic Divergence between Homogeneous and Heterogeneous Reductants journal, February 2019

Homogenous Electrocatalytic Oxygen Reduction Rates Correlate with Reaction Overpotential in Acidic Organic Solutions journal, October 2016

Mechanism of Catalytic O 2 Reduction by Iron Tetraphenylporphyrin journal, May 2019

Solar fuels generation and molecular systems: is it homogeneous or heterogeneous catalysis? journal, January 2013

Title: Combining scaling relationships overcomes rate versus overpotential trade-offs in O ₂ molecular electrocatalysis

Brønsted Acid Scaling Relationships Enable Control Over Product Selectivity from O 2 Reduction with a Mononuclear Cobalt Porphyrin Catalyst
journal, June 2019

New protic salts of aprotic polar solvents
journal, April 2004

Identifying and Breaking Scaling Relations in Molecular Catalysis of Electrochemical Reactions
journal, August 2017

A short history of SHELX
journal, December 2007

Oxygen Reduction by Homogeneous Molecular Catalysts and Electrocatalysts
journal, December 2017

Determining the Overpotential for a Molecular Electrocatalyst
journal, December 2013

Understanding Catalytic Activity Trends in the Oxygen Reduction Reaction
journal, December 2017

Molecular Cobalt Catalysts for O 2 Reduction: Low-Overpotential Production of H 2 O 2 and Comparison with Iron-Based Catalysts
journal, November 2017

Electrochemical Reduction of Brønsted Acids by Glassy Carbon in Acetonitrile—Implications for Electrocatalytic Hydrogen Evolution
journal, July 2014

Electrocatalytic Oxygen Reduction by Iron Tetra-arylporphyrins Bearing Pendant Proton Relays
journal, March 2012

High Catalytic Rates for Hydrogen Production Using Nickel Electrocatalysts with Seven-Membered Cyclic Diphosphine Ligands Containing One Pendant Amine
journal, February 2013

A Synthetic Nickel Electrocatalyst with a Turnover Frequency Above 100,000 s^-1 for H₂ Production
journal, August 2011

Benchmarking of Homogeneous Electrocatalysts: Overpotential, Turnover Frequency, Limiting Turnover Number
journal, April 2015

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
journal, December 2016

Homogeneous, Heterogeneous, and Biological Catalysts for Electrochemical N ₂ Reduction toward NH ₃ under Ambient Conditions
journal, April 2019

Understanding the apparent fractional charge of protons in the aqueous electrochemical double layer
journal, August 2018

Titration of bases in acetonitrile
journal, November 1967

Decoding Proton-Coupled Electron Transfer with Potential–p K _a Diagrams
journal, January 2017

Electrodeposition from Acidic Solutions of Nickel Bis(benzenedithiolate) Produces a Hydrogen-Evolving Ni–S Film on Glassy Carbon
journal, December 2013

Oxygen Reduction Catalysis at a Dicobalt Center: The Relationship of Faradaic Efficiency to Overpotential
journal, February 2016

A Comprehensive Self-Consistent Spectrophotometric Acidity Scale of Neutral Brønsted Acids in Acetonitrile
journal, March 2006

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

Toward the rational benchmarking of homogeneous H ₂ -evolving catalysts
journal, January 2014

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

Multielectron, Multistep Molecular Catalysis of Electrochemical Reactions: Benchmarking of Homogeneous Catalysts
journal, June 2014

Reversing the Tradeoff between Rate and Overpotential in Molecular Electrocatalysts for H ₂ Production
journal, March 2018

Homogeneous Molecular Catalysis of Electrochemical Reactions: Manipulating Intrinsic and Operational Factors for Catalyst Improvement
journal, November 2018

Standard Reduction Potentials for Oxygen and Carbon Dioxide Couples in Acetonitrile and N , N -Dimethylformamide
journal, December 2015

Supramolecular assemblies of carbon nanocoils and tetraphenylporphyrin derivatives for sensing of catechol and hydroquinone in aqueous solution
journal, March 2021

Nonprecious Metal Catalysts for Oxygen Reduction in Heterogeneous Aqueous Systems
journal, December 2017

Turnover Numbers, Turnover Frequencies, and Overpotential in Molecular Catalysis of Electrochemical Reactions. Cyclic Voltammetry and Preparative-Scale Electrolysis
journal, June 2012

Introduction: Oxygen Reduction and Activation in Catalysis
journal, December 2017

A Practical Beginner’s Guide to Cyclic Voltammetry
journal, November 2017

Oxygen Reduction Reaction Promoted by Manganese Porphyrins
journal, July 2018

Evaluation of Homogeneous Electrocatalysts by Cyclic Voltammetry
journal, September 2014

Dioxygen Reduction to Hydrogen Peroxide by a Molecular Mn Complex: Mechanistic Divergence between Homogeneous and Heterogeneous Reductants
journal, February 2019

Homogenous Electrocatalytic Oxygen Reduction Rates Correlate with Reaction Overpotential in Acidic Organic Solutions
journal, October 2016

Mechanism of Catalytic O ₂ Reduction by Iron Tetraphenylporphyrin
journal, May 2019

Solar fuels generation and molecular systems: is it homogeneous or heterogeneous catalysis?
journal, January 2013