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Interplay of Electronic and Steric Effects to Yield Low‐Temperature CO Oxidation at Metal Single Sites in Defect‐Engineered HKUST‐1
In contrast to catalytically active metal single atoms deposited on oxide nanoparticles, the crystalline nature of metal‐organic frameworks (MOFs) allows for a thorough characterization of reaction mechanisms. Using defect‐free HKUST‐1 MOF thin films, we demonstrate that Cu(+)/Cu(2+) dimer defects,...
Autores principales: | , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2020
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7318571/ https://www.ncbi.nlm.nih.gov/pubmed/32196128 http://dx.doi.org/10.1002/anie.202000385 |
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author | Wang, Weijia Sharapa, Dmitry I. Chandresh, Abhinav Nefedov, Alexei Heißler, Stefan Heinke, Lars Studt, Felix Wang, Yuemin Wöll, Christof |
author_facet | Wang, Weijia Sharapa, Dmitry I. Chandresh, Abhinav Nefedov, Alexei Heißler, Stefan Heinke, Lars Studt, Felix Wang, Yuemin Wöll, Christof |
author_sort | Wang, Weijia |
collection | PubMed |
description | In contrast to catalytically active metal single atoms deposited on oxide nanoparticles, the crystalline nature of metal‐organic frameworks (MOFs) allows for a thorough characterization of reaction mechanisms. Using defect‐free HKUST‐1 MOF thin films, we demonstrate that Cu(+)/Cu(2+) dimer defects, created in a controlled fashion by reducing the pristine Cu(2+)/Cu(2+) pairs of the intact framework, account for the high catalytic activity in low‐temperature CO oxidation. Combining advanced IR spectroscopy and density functional theory we propose a new reaction mechanism where the key intermediate is an uncharged O(2) species, weakly bound to Cu(+)/Cu(2+). Our results reveal a complex interplay between electronic and steric effects at defect sites in MOFs and provide important guidelines for tailoring and exploiting the catalytic activity of single metal atom sites. |
format | Online Article Text |
id | pubmed-7318571 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2020 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-73185712020-06-29 Interplay of Electronic and Steric Effects to Yield Low‐Temperature CO Oxidation at Metal Single Sites in Defect‐Engineered HKUST‐1 Wang, Weijia Sharapa, Dmitry I. Chandresh, Abhinav Nefedov, Alexei Heißler, Stefan Heinke, Lars Studt, Felix Wang, Yuemin Wöll, Christof Angew Chem Int Ed Engl Communications In contrast to catalytically active metal single atoms deposited on oxide nanoparticles, the crystalline nature of metal‐organic frameworks (MOFs) allows for a thorough characterization of reaction mechanisms. Using defect‐free HKUST‐1 MOF thin films, we demonstrate that Cu(+)/Cu(2+) dimer defects, created in a controlled fashion by reducing the pristine Cu(2+)/Cu(2+) pairs of the intact framework, account for the high catalytic activity in low‐temperature CO oxidation. Combining advanced IR spectroscopy and density functional theory we propose a new reaction mechanism where the key intermediate is an uncharged O(2) species, weakly bound to Cu(+)/Cu(2+). Our results reveal a complex interplay between electronic and steric effects at defect sites in MOFs and provide important guidelines for tailoring and exploiting the catalytic activity of single metal atom sites. John Wiley and Sons Inc. 2020-04-17 2020-06-22 /pmc/articles/PMC7318571/ /pubmed/32196128 http://dx.doi.org/10.1002/anie.202000385 Text en © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA. This is an open access article under the terms of the http://creativecommons.org/licenses/by/4.0/ License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. |
spellingShingle | Communications Wang, Weijia Sharapa, Dmitry I. Chandresh, Abhinav Nefedov, Alexei Heißler, Stefan Heinke, Lars Studt, Felix Wang, Yuemin Wöll, Christof Interplay of Electronic and Steric Effects to Yield Low‐Temperature CO Oxidation at Metal Single Sites in Defect‐Engineered HKUST‐1 |
title | Interplay of Electronic and Steric Effects to Yield Low‐Temperature CO Oxidation at Metal Single Sites in Defect‐Engineered HKUST‐1 |
title_full | Interplay of Electronic and Steric Effects to Yield Low‐Temperature CO Oxidation at Metal Single Sites in Defect‐Engineered HKUST‐1 |
title_fullStr | Interplay of Electronic and Steric Effects to Yield Low‐Temperature CO Oxidation at Metal Single Sites in Defect‐Engineered HKUST‐1 |
title_full_unstemmed | Interplay of Electronic and Steric Effects to Yield Low‐Temperature CO Oxidation at Metal Single Sites in Defect‐Engineered HKUST‐1 |
title_short | Interplay of Electronic and Steric Effects to Yield Low‐Temperature CO Oxidation at Metal Single Sites in Defect‐Engineered HKUST‐1 |
title_sort | interplay of electronic and steric effects to yield low‐temperature co oxidation at metal single sites in defect‐engineered hkust‐1 |
topic | Communications |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC7318571/ https://www.ncbi.nlm.nih.gov/pubmed/32196128 http://dx.doi.org/10.1002/anie.202000385 |
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