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In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation
Single-atom catalysts have recently been applied in many applications such as CO oxidation. Experimental in situ investigations into this reaction, however, are limited. Hereby, we present a suite of operando/in situ spectroscopic experiments for structurally well-defined atomically dispersed Rh on...
Autores principales: | , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
Nature Publishing Group UK
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6430772/ https://www.ncbi.nlm.nih.gov/pubmed/30902990 http://dx.doi.org/10.1038/s41467-019-09188-9 |
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author | Hülsey, Max J. Zhang, Bin Ma, Zhirui Asakura, Hiroyuki Do, David A. Chen, Wei Tanaka, Tsunehiro Zhang, Peng Wu, Zili Yan, Ning |
author_facet | Hülsey, Max J. Zhang, Bin Ma, Zhirui Asakura, Hiroyuki Do, David A. Chen, Wei Tanaka, Tsunehiro Zhang, Peng Wu, Zili Yan, Ning |
author_sort | Hülsey, Max J. |
collection | PubMed |
description | Single-atom catalysts have recently been applied in many applications such as CO oxidation. Experimental in situ investigations into this reaction, however, are limited. Hereby, we present a suite of operando/in situ spectroscopic experiments for structurally well-defined atomically dispersed Rh on phosphotungstic acid during CO oxidation. The identification of several key intermediates and the steady-state catalyst structure indicate that the reactions follow an unconventional Mars-van Krevelen mechanism and that the activation of O(2) is rate-limiting. In situ XPS confirms the contribution of the heteropoly acid support while in situ DRIFT spectroscopy consolidates the oxidation state and CO adsorption of Rh. As such, direct observation of three key components, i.e., metal center, support and substrate, is achieved, providing a clearer picture on CO oxidation on atomically dispersed Rh sites. The obtained information are used to engineer structurally similar catalysts that exhibit T(20) values up to 130 °C below the previously reported Rh(1)/NPTA. |
format | Online Article Text |
id | pubmed-6430772 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | Nature Publishing Group UK |
record_format | MEDLINE/PubMed |
spelling | pubmed-64307722019-03-25 In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation Hülsey, Max J. Zhang, Bin Ma, Zhirui Asakura, Hiroyuki Do, David A. Chen, Wei Tanaka, Tsunehiro Zhang, Peng Wu, Zili Yan, Ning Nat Commun Article Single-atom catalysts have recently been applied in many applications such as CO oxidation. Experimental in situ investigations into this reaction, however, are limited. Hereby, we present a suite of operando/in situ spectroscopic experiments for structurally well-defined atomically dispersed Rh on phosphotungstic acid during CO oxidation. The identification of several key intermediates and the steady-state catalyst structure indicate that the reactions follow an unconventional Mars-van Krevelen mechanism and that the activation of O(2) is rate-limiting. In situ XPS confirms the contribution of the heteropoly acid support while in situ DRIFT spectroscopy consolidates the oxidation state and CO adsorption of Rh. As such, direct observation of three key components, i.e., metal center, support and substrate, is achieved, providing a clearer picture on CO oxidation on atomically dispersed Rh sites. The obtained information are used to engineer structurally similar catalysts that exhibit T(20) values up to 130 °C below the previously reported Rh(1)/NPTA. Nature Publishing Group UK 2019-03-22 /pmc/articles/PMC6430772/ /pubmed/30902990 http://dx.doi.org/10.1038/s41467-019-09188-9 Text en © The Author(s) 2019 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/. |
spellingShingle | Article Hülsey, Max J. Zhang, Bin Ma, Zhirui Asakura, Hiroyuki Do, David A. Chen, Wei Tanaka, Tsunehiro Zhang, Peng Wu, Zili Yan, Ning In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation |
title | In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation |
title_full | In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation |
title_fullStr | In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation |
title_full_unstemmed | In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation |
title_short | In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation |
title_sort | in situ spectroscopy-guided engineering of rhodium single-atom catalysts for co oxidation |
topic | Article |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6430772/ https://www.ncbi.nlm.nih.gov/pubmed/30902990 http://dx.doi.org/10.1038/s41467-019-09188-9 |
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