Chemical and Electrochemical O2 Reduction on Earth-Abundant M-N-C Catalysts and Implications for Mediated Electrolysis

Bates, Jason S.; Biswas, Sourav; Suh, Sung-Eun; Johnson, Mathew R.; Mondal, Biswajit; Root, Thatcher W.; Stahl, Shannon S.

doi:10.1021/jacs.1c11126

Title: Chemical and Electrochemical O₂ Reduction on Earth-Abundant M-N-C Catalysts and Implications for Mediated Electrolysis

Journal Article · 04 January 2022 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.1c11126 · OSTI ID:1865652

^[1];

^[2];

^[2]; Johnson, Mathew R. ^[2]; Mondal, Biswajit ^[2];

^[2];

^[2]

Univ. of Wisconsin, Madison, WI (United States); Northwestern University, Evanston, IL, United States
Univ. of Wisconsin, Madison, WI (United States)

M-N-C catalysts, incorporating non-precious-metal ions (e.g. M = Fe, Co) within a nitrogen-doped carbon support, have been the focus of broad interest for electrochemical O₂ reduction and aerobic oxidation reactions. The present study explores the mechanistic relationship between the O₂ reduction mechanism under electrochemical and chemical conditions. In this work, chemical O₂ reduction is investigated via the aerobic oxidation of a hydroquinone, in which the O–H bonds supply the protons and electrons needed for O₂ reduction to water. Mechanistic studies have been conducted to elucidate whether the M-N-C catalyst couples two independent half-reactions (IHR), similar to electrode-mediated processes, or mediates a direct inner-sphere reaction (ISR) between O₂ and the organic molecule. Kinetic data support the latter ISR pathway. This conclusion is reinforced by rate/potential correlations that reveal significantly different Tafel slopes, implicating different mechanisms for chemical and electrochemical O₂ reduction.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: Northwestern Univ., Evanston, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institutes of Health (NIH); National Science Foundation (NSF)

Grant/Contract Number:: SC0021314

OSTI ID:: 1865652

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 2 Vol. 144; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

References (46)

Nonprecious Metal Catalysts for Oxygen Reduction in Heterogeneous Aqueous Systems Gewirth, Andrew A.; Varnell, Jason A.; DiAscro, Angela M. Chemical Reviews, Vol. 118, Issue 5 https://doi.org/10.1021/acs.chemrev.7b00335	journal	December 2017
Contrast and Synergy between Electrocatalysis and Heterogeneous Catalysis Wieckowski, Andrzej; Neurock, Matthew Advances in Physical Chemistry, Vol. 2011 https://doi.org/10.1155/2011/907129	journal	November 2011
Turnover rates on complex heterogeneous catalysts Davis, Robert AIChE Journal, Vol. 64, Issue 11 https://doi.org/10.1002/aic.16385	journal	September 2018
Recent Advances in Immobilized Metal Catalysts for Environmentally Benign Oxidation of Alcohols Matsumoto, Tsutomu; Ueno, Masaharu; Wang, Naiwei Chemistry - An Asian Journal, Vol. 3, Issue 2 https://doi.org/10.1002/asia.200700359	journal	February 2008
Ultra-Sensitive Potentiometric Measurements of Dilute Redox Molecule Solutions and Determination of Sensitivity Factors at Platinum Ultramicroelectrodes Percival, Stephen J.; Bard, Allen J. Analytical Chemistry, Vol. 89, Issue 18 https://doi.org/10.1021/acs.analchem.7b01856	journal	August 2017
Inertia and driving force of chemical reactions Evans, M. G.; Polanyi, M. Transactions of the Faraday Society, Vol. 34 https://doi.org/10.1039/tf9383400011	journal	January 1938
Deciphering the oxygen activation mechanism at the CuC site of particulate methane monooxygenase Peng, Wei; Qu, Xiaoyang; Shaik, Sason Nature Catalysis, Vol. 4, Issue 4 https://doi.org/10.1038/s41929-021-00591-4	journal	April 2021
Co–N–C Catalyst for C–C Coupling Reactions: On the Catalytic Performance and Active Sites Zhang, Leilei; Wang, Aiqin; Wang, Wentao ACS Catalysis, Vol. 5, Issue 11 https://doi.org/10.1021/acscatal.5b01223	journal	October 2015
Progress in the Development of Fe‐Based PGM‐Free Electrocatalysts for the Oxygen Reduction Reaction Martinez, Ulises; Komini Babu, Siddharth; Holby, Edward F. Advanced Materials, Vol. 31, Issue 31 https://doi.org/10.1002/adma.201806545	journal	December 2018
A universal ligand mediated method for large scale synthesis of transition metal single atom catalysts Yang, Hongzhou; Shang, Lu; Zhang, Qinghua Nature Communications, Vol. 10, Issue 1 https://doi.org/10.1038/s41467-019-12510-0	journal	October 2019
Oxidation of Alcohols with Molecular Oxygen on Solid Catalysts Mallat, Tamas; Baiker, Alfons Chemical Reviews, Vol. 104, Issue 6 https://doi.org/10.1021/cr0200116	journal	June 2004
Direct Synthesis of H ₂ O ₂ from H ₂ and O ₂ on Pd Catalysts: Current Understanding, Outstanding Questions, and Research Needs Flaherty, David W. ACS Catalysis, Vol. 8, Issue 2 https://doi.org/10.1021/acscatal.7b04107	journal	January 2018
Reactivity of the Gold/Water Interface During Selective Oxidation Catalysis Zope, B. N.; Hibbitts, D. D.; Neurock, M. Science, Vol. 330, Issue 6000 https://doi.org/10.1126/science.1195055	journal	September 2010
Comparison of Quinone‐Based Catholytes for Aqueous Redox Flow Batteries and Demonstration of Long‐Term Stability with Tetrasubstituted Quinones Gerken, James B.; Anson, Colin W.; Preger, Yuliya Advanced Energy Materials, Vol. 10, Issue 20 https://doi.org/10.1002/aenm.202000340	journal	April 2020
Cooperative Electrocatalytic O ₂ Reduction Involving Co(salophen) with p- Hydroquinone as an Electron–Proton Transfer Mediator Anson, Colin W.; Stahl, Shannon S. Journal of the American Chemical Society, Vol. 139, Issue 51 https://doi.org/10.1021/jacs.7b11362	journal	December 2017
Selective oxidation of alcohols and aldehydes over supported metal nanoparticles Davis, Sara E.; Ide, Matthew S.; Davis, Robert J. Green Chem., Vol. 15, Issue 1 https://doi.org/10.1039/C2GC36441G	journal	January 2013
Thermochemical aerobic oxidation catalysis in water can be analysed as two coupled electrochemical half-reactions Ryu, Jaeyune; Bregante, Daniel T.; Howland, William C. Nature Catalysis, Vol. 4, Issue 9 https://doi.org/10.1038/s41929-021-00666-2	journal	September 2021
Activity benchmarks and requirements for Pt, Pt-alloy, and non-Pt oxygen reduction catalysts for PEMFCs Gasteiger, Hubert A.; Kocha, Shyam S.; Sompalli, Bhaskar Applied Catalysis B: Environmental, Vol. 56, Issue 1-2, p. 9-35 https://doi.org/10.1016/j.apcatb.2004.06.021	journal	March 2005
Synthesis, Characterization, and Application of Metal Nanoparticles Supported on Nitrogen-Doped Carbon: Catalysis beyond Electrochemistry He, Lin; Weniger, Florian; Neumann, Helfried Angewandte Chemie International Edition, Vol. 55, Issue 41 https://doi.org/10.1002/anie.201603198	journal	September 2016
Chemical vapour deposition of Fe–N–C oxygen reduction catalysts with full utilization of dense Fe–N4 sites Jiao, Li; Li, Jingkun; Richard, Lynne LaRochelle Nature Materials https://doi.org/10.1038/s41563-021-01030-2	journal	June 2021
Recent Advances in the Direct Synthesis of H ₂ O ₂ Lewis, Richard J.; Hutchings, Graham J. ChemCatChem, Vol. 11, Issue 1 https://doi.org/10.1002/cctc.201801435	journal	October 2018
Turnover Rates in Heterogeneous Catalysis Boudart, M. Chemical Reviews, Vol. 95, Issue 3 https://doi.org/10.1021/cr00035a009	journal	May 1995
Recent advances in non-precious metal catalysis for oxygen-reduction reaction in polymer electrolyte fuelcells Jaouen, Frédéric; Proietti, Eric; Lefèvre, Michel Energy Environ. Sci., Vol. 4, Issue 1, p. 114-130 https://doi.org/10.1039/C0EE00011F	journal	January 2011
Oxygen Reduction by Iron Porphyrins with Covalently Attached Pendent Phenol and Quinol Singha, Asmita; Mondal, Arnab; Nayek, Abhijit Journal of the American Chemical Society, Vol. 142, Issue 52 https://doi.org/10.1021/jacs.0c10385	journal	December 2020
Alkaline Anion-Exchange Membrane Fuel Cells: Challenges in Electrocatalysis and Interfacial Charge Transfer Ramaswamy, Nagappan; Mukerjee, Sanjeev Chemical Reviews, Vol. 119, Issue 23 https://doi.org/10.1021/acs.chemrev.9b00157	journal	November 2019
The theory of reactions involving proton transfers Bell, Ronald Percy Proceedings of the Royal Society of London. Series A - Mathematical and Physical Sciences, Vol. 154, Issue 882, p. 414-429 https://doi.org/10.1098/rspa.1936.0060	journal	April 1936
Co(salophen)-Catalyzed Aerobic Oxidation of p -Hydroquinone: Mechanism and Implications for Aerobic Oxidation Catalysis Anson, Colin W.; Ghosh, Soumya; Hammes-Schiffer, Sharon Journal of the American Chemical Society, Vol. 138, Issue 12 https://doi.org/10.1021/jacs.6b00254	journal	March 2016
Non-covalent assembly of proton donors and p- benzoquinone anions for co-electrocatalytic reduction of dioxygen Hooe, Shelby L.; Cook, Emma N.; Reid, Amelia G. Chemical Science, Vol. 12, Issue 28 https://doi.org/10.1039/D1SC01271A	journal	January 2021
Solvent molecules form surface redox mediators in situ and cocatalyze O ₂ reduction on Pd Adams, Jason S.; Chemburkar, Ashwin; Priyadarshini, Pranjali Science, Vol. 371, Issue 6529 https://doi.org/10.1126/science.abc1339	journal	February 2021
Efficient electrochemical synthesis of robust, densely functionalized water soluble quinones Gerken, James B.; Stamoulis, Alexios; Suh, Sung-Eun Chemical Communications, Vol. 56, Issue 8 https://doi.org/10.1039/C9CC08878D	journal	January 2020
Atomically Dispersed Co and Cu on N-Doped Carbon for Reactions Involving C–H Activation Xie, Jiahan; Kammert, James D.; Kaylor, Nicholas ACS Catalysis, Vol. 8, Issue 5 https://doi.org/10.1021/acscatal.8b00141	journal	March 2018
Mediated Fuel Cells: Soluble Redox Mediators and Their Applications to Electrochemical Reduction of O ₂ and Oxidation of H ₂ , Alcohols, Biomass, and Complex Fuels Anson, Colin W.; Stahl, Shannon S. Chemical Reviews, Vol. 120, Issue 8 https://doi.org/10.1021/acs.chemrev.9b00717	journal	March 2020
Mechanism for the Direct Synthesis of H ₂ O ₂ on Pd Clusters: Heterolytic Reaction Pathways at the Liquid–Solid Interface Wilson, Neil M.; Flaherty, David W. Journal of the American Chemical Society, Vol. 138, Issue 2 https://doi.org/10.1021/jacs.5b10669	journal	December 2015
Iron-Nitrogen-Carbon Catalysts for Proton Exchange Membrane Fuel Cells Asset, Tristan; Atanassov, Plamen Joule, Vol. 4, Issue 1 https://doi.org/10.1016/j.joule.2019.12.002	journal	January 2020
Selective Oxidation of Alcohols to Esters Using Heterogeneous Co ₃ O ₄ –N@C Catalysts under Mild Conditions Jagadeesh, Rajenahally V.; Junge, Henrik; Pohl, Marga-Martina Journal of the American Chemical Society, Vol. 135, Issue 29 https://doi.org/10.1021/ja403615c	journal	July 2013
Stable Tetrasubstituted Quinone Redox Reservoir for Enhancing Decoupled Hydrogen and Oxygen Evolution Wang, Fei; Sheng, Hongyuan; Li, Wenjie ACS Energy Letters https://doi.org/10.1021/acsenergylett.1c00236	journal	March 2021
“On the Interpretation of Corrosion Processes through the Superposition of Electrochemical Partial Processes and on the Potential of Mixed Electrodes,” with a Perspective by F. Mansfeld Wagner, C.; Traud, W. CORROSION, Vol. 62, Issue 10 https://doi.org/10.5006/1.3279894	journal	October 2006
Unraveling molecular transformations on surfaces: a critical comparison of oxidation reactions on coinage metals Liu, Xiaoying; Madix, Robert J.; Friend, Cynthia M. Chemical Society Reviews, Vol. 37, Issue 10 https://doi.org/10.1039/b800309m	journal	January 2008
Unifying Concepts in Electro- and Thermocatalysis toward Hydrogen Peroxide Production Adams, Jason S.; Kromer, Matthew L.; Rodríguez-López, Joaquín Journal of the American Chemical Society, Vol. 143, Issue 21 https://doi.org/10.1021/jacs.0c13399	journal	May 2021
Quinone-Mediated Electrochemical O2 Reduction Accessing High Power Density with an Off-Electrode Co-N/C Catalyst Preger, Yuliya; Gerken, James B.; Biswas, Sourav Joule, Vol. 2, Issue 12 https://doi.org/10.1016/j.joule.2018.09.010	journal	December 2018
The Important Role of Hydroxyl on Oxidation Catalysis by Gold Nanoparticles Ide, Matthew S.; Davis, Robert J. Accounts of Chemical Research, Vol. 47, Issue 3 https://doi.org/10.1021/ar4001907	journal	November 2013
Elucidating Proton Involvement in the Rate-Determining Step for Pt/Pd-Based and Non-Precious-Metal Oxygen Reduction Reaction Catalysts Using the Kinetic Isotope Effect Tse, Edmund C. M.; Varnell, Jason A.; Hoang, Thao T. H. The Journal of Physical Chemistry Letters, Vol. 7, Issue 18 https://doi.org/10.1021/acs.jpclett.6b01235	journal	August 2016
Recent Advances in Electrocatalysts for Oxygen Reduction Reaction Shao, Minhua; Chang, Qiaowan; Dodelet, Jean-Pol Chemical Reviews, Vol. 116, Issue 6 https://doi.org/10.1021/acs.chemrev.5b00462	journal	February 2016
Iron-Based Catalysts with Improved Oxygen Reduction Activity in Polymer Electrolyte Fuel Cells Lefèvre, Michel; Proietti, Eric; Jaouen, Frédéric Science, Vol. 324, Issue 5923, p. 71-74 https://doi.org/10.1126/science.1170051	journal	April 2009
Competitive adsorption on single-atom catalysts: Mechanistic insights into the aerobic oxidation of alcohols over Co N C Huang, Kuntao; Fu, Hongquan; Shi, Wen Journal of Catalysis, Vol. 377 https://doi.org/10.1016/j.jcat.2019.06.047	journal	September 2019
Reproducibility of Turnover Rates in Heterogeneous Metal Catalysis: Compilation of Data and Guidelines for Data Analysis Ribeiro∗, Fabio H.; Schach Von Wittenau, Alexis E.; Bartholomew, Calvin H. Catalysis Reviews, Vol. 39, Issue 1-2 https://doi.org/10.1080/01614949708006468	journal	February 1997

Similar Records

Chemical Kinetic Method for Active-Site Quantification in Fe-N-C Catalysts and Correlation with Molecular Probe and Spectroscopic Site-Counting Methods

Journal Article · 2023 · Journal of the American Chemical Society · OSTI ID:2274937

Bates, Jason S.; Martinez, Jesse J.; Hall, Melissa N.; +16 more

Thermal Hydroquinone Oxidation on Co/N-doped Carbon Proceeds by a Band-Mediated Electrochemical Mechanism

Journal Article · 2022 · Journal of the American Chemical Society · OSTI ID:1893523

Howland, William C.; Gerken, James B.; Stahl, Shannon S.; +1 more

High-Potential Electrocatalytic O2 Reduction with Nitroxyl / NOx Mediators: Implications for Fuel Cells and Aerobic Oxidation Catalysis

Journal Article · 2015 · ACS Central Science (Online) · OSTI ID:1229947

Gerken, James B.; Stahl, Shannon S.

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Title: Chemical and Electrochemical O2 Reduction on Earth-Abundant M-N-C Catalysts and Implications for Mediated Electrolysis

Citation Formats

References (46)

Similar Records

Related Subjects

Title: Chemical and Electrochemical O₂ Reduction on Earth-Abundant M-N-C Catalysts and Implications for Mediated Electrolysis