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Pseudo-adsorption and long-range redox coupling during oxygen reduction reaction on single atom electrocatalyst
Fundamental understanding of the dynamic behaviors at the electrochemical interface is crucial for electrocatalyst design and optimization. Here, we revisit the oxygen reduction reaction mechanism on a series of transition metal (M = Fe, Co, Ni, Cu) single atom sites embedded in N-doped nanocarbon b...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2022
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8975818/ https://www.ncbi.nlm.nih.gov/pubmed/35365615 http://dx.doi.org/10.1038/s41467-022-29357-7 |
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author | Chen, Jie-Wei Zhang, Zisheng Yan, Hui-Min Xia, Guang-Jie Cao, Hao Wang, Yang-Gang |
author_facet | Chen, Jie-Wei Zhang, Zisheng Yan, Hui-Min Xia, Guang-Jie Cao, Hao Wang, Yang-Gang |
author_sort | Chen, Jie-Wei |
collection | PubMed |
description | Fundamental understanding of the dynamic behaviors at the electrochemical interface is crucial for electrocatalyst design and optimization. Here, we revisit the oxygen reduction reaction mechanism on a series of transition metal (M = Fe, Co, Ni, Cu) single atom sites embedded in N-doped nanocarbon by ab initio molecular dynamics simulations with explicit solvation. We have identified the dissociative pathways and the thereby emerged solvated hydroxide species for all the proton-coupled electron transfer (PCET) steps at the electrochemical interface. Such hydroxide species can be dynamically confined in a “pseudo-adsorption” state at a few water layers away from the active site and respond to the redox event at the catalytic center in a coupled manner within timescale less than 1 ps. In the PCET steps, the proton species (in form of hydronium in neutral/acidic media or water in alkaline medium) can protonate the pseudo-adsorbed hydroxide without needing to travel to the direct catalyst surface. This, therefore, expands the reactive region beyond the direct catalyst surface, boosting the reaction kinetics via alleviating mass transfer limits. Our work implies that in catalysis the reaction species may not necessarily bind to the catalyst surface but be confined in an active region. |
format | Online Article Text |
id | pubmed-8975818 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2022 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-89758182022-04-20 Pseudo-adsorption and long-range redox coupling during oxygen reduction reaction on single atom electrocatalyst Chen, Jie-Wei Zhang, Zisheng Yan, Hui-Min Xia, Guang-Jie Cao, Hao Wang, Yang-Gang Nat Commun Article Fundamental understanding of the dynamic behaviors at the electrochemical interface is crucial for electrocatalyst design and optimization. Here, we revisit the oxygen reduction reaction mechanism on a series of transition metal (M = Fe, Co, Ni, Cu) single atom sites embedded in N-doped nanocarbon by ab initio molecular dynamics simulations with explicit solvation. We have identified the dissociative pathways and the thereby emerged solvated hydroxide species for all the proton-coupled electron transfer (PCET) steps at the electrochemical interface. Such hydroxide species can be dynamically confined in a “pseudo-adsorption” state at a few water layers away from the active site and respond to the redox event at the catalytic center in a coupled manner within timescale less than 1 ps. In the PCET steps, the proton species (in form of hydronium in neutral/acidic media or water in alkaline medium) can protonate the pseudo-adsorbed hydroxide without needing to travel to the direct catalyst surface. This, therefore, expands the reactive region beyond the direct catalyst surface, boosting the reaction kinetics via alleviating mass transfer limits. Our work implies that in catalysis the reaction species may not necessarily bind to the catalyst surface but be confined in an active region. Nature Publishing Group UK 2022-04-01 /pmc/articles/PMC8975818/ /pubmed/35365615 http://dx.doi.org/10.1038/s41467-022-29357-7 Text en © The Author(s) 2022 https://creativecommons.org/licenses/by/4.0/Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons license, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons license and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/ (https://creativecommons.org/licenses/by/4.0/) . |
spellingShingle | Article Chen, Jie-Wei Zhang, Zisheng Yan, Hui-Min Xia, Guang-Jie Cao, Hao Wang, Yang-Gang Pseudo-adsorption and long-range redox coupling during oxygen reduction reaction on single atom electrocatalyst |
title | Pseudo-adsorption and long-range redox coupling during oxygen reduction reaction on single atom electrocatalyst |
title_full | Pseudo-adsorption and long-range redox coupling during oxygen reduction reaction on single atom electrocatalyst |
title_fullStr | Pseudo-adsorption and long-range redox coupling during oxygen reduction reaction on single atom electrocatalyst |
title_full_unstemmed | Pseudo-adsorption and long-range redox coupling during oxygen reduction reaction on single atom electrocatalyst |
title_short | Pseudo-adsorption and long-range redox coupling during oxygen reduction reaction on single atom electrocatalyst |
title_sort | pseudo-adsorption and long-range redox coupling during oxygen reduction reaction on single atom electrocatalyst |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC8975818/ https://www.ncbi.nlm.nih.gov/pubmed/35365615 http://dx.doi.org/10.1038/s41467-022-29357-7 |
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