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Understanding the Impact of Defects on Catalytic CO Oxidation of LaFeO(3)-Supported Rh, Pd, and Pt Single-Atom Catalysts
[Image: see text] Understanding the intrinsic catalytic properties of perovskite materials can accelerate the development of highly active and abundant complex oxide catalysts. Here, we performed a first-principles density functional theory study combined with a microkinetics analysis to comprehensi...
Autores principales: | , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American Chemical
Society
2019
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6443215/ https://www.ncbi.nlm.nih.gov/pubmed/30949277 http://dx.doi.org/10.1021/acs.jpcc.9b01520 |
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author | Zhang, Long Filot, Ivo A. W. Su, Ya-Qiong Liu, Jin-Xun Hensen, Emiel J. M. |
author_facet | Zhang, Long Filot, Ivo A. W. Su, Ya-Qiong Liu, Jin-Xun Hensen, Emiel J. M. |
author_sort | Zhang, Long |
collection | PubMed |
description | [Image: see text] Understanding the intrinsic catalytic properties of perovskite materials can accelerate the development of highly active and abundant complex oxide catalysts. Here, we performed a first-principles density functional theory study combined with a microkinetics analysis to comprehensively investigate the influence of defects on catalytic CO oxidation of LaFeO(3) catalysts containing single atoms of Rh, Pd, and Pt. La defects and subsurface O vacancies considerably affect the local electronic structure of these single atoms adsorbed at the surface or replacing Fe in the surface of the perovskite. As a consequence, not only the stability of the introduced single atoms is enhanced but also the CO and O(2) adsorption energies are modified. This also affects the barriers for CO oxidation. Uniquely, we find that the presence of La defects results in a much higher CO oxidation rate for the doped perovskite surface. A linear correlation between the activation barrier for CO oxidation and the surface O vacancy formation energy for these models is identified. Additionally, the presence of subsurface O vacancies only slightly promotes CO oxidation on the LaFeO(3) surface with an adsorbed Rh atom. Our findings suggest that the introduction of La defects in LaFeO(3)-based environmental catalysts could be a promising strategy toward improved oxidation performance. The insights revealed herein guide the design of the perovskite-based three-way catalyst through compositional variation. |
format | Online Article Text |
id | pubmed-6443215 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | American Chemical
Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-64432152019-04-02 Understanding the Impact of Defects on Catalytic CO Oxidation of LaFeO(3)-Supported Rh, Pd, and Pt Single-Atom Catalysts Zhang, Long Filot, Ivo A. W. Su, Ya-Qiong Liu, Jin-Xun Hensen, Emiel J. M. J Phys Chem C Nanomater Interfaces [Image: see text] Understanding the intrinsic catalytic properties of perovskite materials can accelerate the development of highly active and abundant complex oxide catalysts. Here, we performed a first-principles density functional theory study combined with a microkinetics analysis to comprehensively investigate the influence of defects on catalytic CO oxidation of LaFeO(3) catalysts containing single atoms of Rh, Pd, and Pt. La defects and subsurface O vacancies considerably affect the local electronic structure of these single atoms adsorbed at the surface or replacing Fe in the surface of the perovskite. As a consequence, not only the stability of the introduced single atoms is enhanced but also the CO and O(2) adsorption energies are modified. This also affects the barriers for CO oxidation. Uniquely, we find that the presence of La defects results in a much higher CO oxidation rate for the doped perovskite surface. A linear correlation between the activation barrier for CO oxidation and the surface O vacancy formation energy for these models is identified. Additionally, the presence of subsurface O vacancies only slightly promotes CO oxidation on the LaFeO(3) surface with an adsorbed Rh atom. Our findings suggest that the introduction of La defects in LaFeO(3)-based environmental catalysts could be a promising strategy toward improved oxidation performance. The insights revealed herein guide the design of the perovskite-based three-way catalyst through compositional variation. American Chemical Society 2019-03-06 2019-03-28 /pmc/articles/PMC6443215/ /pubmed/30949277 http://dx.doi.org/10.1021/acs.jpcc.9b01520 Text en Copyright © 2019 American Chemical Society This is an open access article published under a Creative Commons Non-Commercial No Derivative Works (CC-BY-NC-ND) Attribution License (http://pubs.acs.org/page/policy/authorchoice_ccbyncnd_termsofuse.html) , which permits copying and redistribution of the article, and creation of adaptations, all for non-commercial purposes. |
spellingShingle | Zhang, Long Filot, Ivo A. W. Su, Ya-Qiong Liu, Jin-Xun Hensen, Emiel J. M. Understanding the Impact of Defects on Catalytic CO Oxidation of LaFeO(3)-Supported Rh, Pd, and Pt Single-Atom Catalysts |
title | Understanding the Impact of Defects on Catalytic CO
Oxidation of LaFeO(3)-Supported Rh, Pd, and Pt Single-Atom
Catalysts |
title_full | Understanding the Impact of Defects on Catalytic CO
Oxidation of LaFeO(3)-Supported Rh, Pd, and Pt Single-Atom
Catalysts |
title_fullStr | Understanding the Impact of Defects on Catalytic CO
Oxidation of LaFeO(3)-Supported Rh, Pd, and Pt Single-Atom
Catalysts |
title_full_unstemmed | Understanding the Impact of Defects on Catalytic CO
Oxidation of LaFeO(3)-Supported Rh, Pd, and Pt Single-Atom
Catalysts |
title_short | Understanding the Impact of Defects on Catalytic CO
Oxidation of LaFeO(3)-Supported Rh, Pd, and Pt Single-Atom
Catalysts |
title_sort | understanding the impact of defects on catalytic co
oxidation of lafeo(3)-supported rh, pd, and pt single-atom
catalysts |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6443215/ https://www.ncbi.nlm.nih.gov/pubmed/30949277 http://dx.doi.org/10.1021/acs.jpcc.9b01520 |
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