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New Insights into the Catalytic Activity of Cobalt Orthophosphate Co(3)(PO(4))(2) from Charge Density Analysis
An extensive characterization of Co(3)(PO(4))(2) was performed by topological analysis according to Bader‘s Quantum Theory of Atoms in Molecules from the experimentally and theoretically determined electron density. This study sheds light on the reactivity of cobalt orthophosphate as a solid‐state h...
Autores principales: | , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
John Wiley and Sons Inc.
2019
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Materias: | |
Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6916324/ https://www.ncbi.nlm.nih.gov/pubmed/31361370 http://dx.doi.org/10.1002/chem.201902303 |
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author | Keil, Helena Hellström, Matti Stückl, Claudia Herbst‐Irmer, Regine Behler, Jörg Stalke, Dietmar |
author_facet | Keil, Helena Hellström, Matti Stückl, Claudia Herbst‐Irmer, Regine Behler, Jörg Stalke, Dietmar |
author_sort | Keil, Helena |
collection | PubMed |
description | An extensive characterization of Co(3)(PO(4))(2) was performed by topological analysis according to Bader‘s Quantum Theory of Atoms in Molecules from the experimentally and theoretically determined electron density. This study sheds light on the reactivity of cobalt orthophosphate as a solid‐state heterogeneous oxidative‐dehydration and ‐dehydrogenation catalyst. Various faces of the bulk catalyst were identified as possible reactive sites given their topological properties. The charge accumulations and depletions around the two independent five‐ and sixfold‐coordinated cobalt atoms, found in the topological analysis, are correlated to the orientation and population of the d‐orbitals. It is shown that the (011) face has the best structural features for catalysis. Fivefold‐coordinated ions in close proximity to advantageously oriented vacant coordination sites and electron depletions suit the oxygen lone pairs of the reactant, mainly for chemisorption. This is confirmed both from the multipole refinement as well as from density functional theory calculations. Nearby basic phosphate ions are readily available for C−H activation. |
format | Online Article Text |
id | pubmed-6916324 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2019 |
publisher | John Wiley and Sons Inc. |
record_format | MEDLINE/PubMed |
spelling | pubmed-69163242019-12-17 New Insights into the Catalytic Activity of Cobalt Orthophosphate Co(3)(PO(4))(2) from Charge Density Analysis Keil, Helena Hellström, Matti Stückl, Claudia Herbst‐Irmer, Regine Behler, Jörg Stalke, Dietmar Chemistry Full Papers An extensive characterization of Co(3)(PO(4))(2) was performed by topological analysis according to Bader‘s Quantum Theory of Atoms in Molecules from the experimentally and theoretically determined electron density. This study sheds light on the reactivity of cobalt orthophosphate as a solid‐state heterogeneous oxidative‐dehydration and ‐dehydrogenation catalyst. Various faces of the bulk catalyst were identified as possible reactive sites given their topological properties. The charge accumulations and depletions around the two independent five‐ and sixfold‐coordinated cobalt atoms, found in the topological analysis, are correlated to the orientation and population of the d‐orbitals. It is shown that the (011) face has the best structural features for catalysis. Fivefold‐coordinated ions in close proximity to advantageously oriented vacant coordination sites and electron depletions suit the oxygen lone pairs of the reactant, mainly for chemisorption. This is confirmed both from the multipole refinement as well as from density functional theory calculations. Nearby basic phosphate ions are readily available for C−H activation. John Wiley and Sons Inc. 2019-11-08 2019-12-10 /pmc/articles/PMC6916324/ /pubmed/31361370 http://dx.doi.org/10.1002/chem.201902303 Text en © 2019 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 | Full Papers Keil, Helena Hellström, Matti Stückl, Claudia Herbst‐Irmer, Regine Behler, Jörg Stalke, Dietmar New Insights into the Catalytic Activity of Cobalt Orthophosphate Co(3)(PO(4))(2) from Charge Density Analysis |
title | New Insights into the Catalytic Activity of Cobalt Orthophosphate Co(3)(PO(4))(2) from Charge Density Analysis |
title_full | New Insights into the Catalytic Activity of Cobalt Orthophosphate Co(3)(PO(4))(2) from Charge Density Analysis |
title_fullStr | New Insights into the Catalytic Activity of Cobalt Orthophosphate Co(3)(PO(4))(2) from Charge Density Analysis |
title_full_unstemmed | New Insights into the Catalytic Activity of Cobalt Orthophosphate Co(3)(PO(4))(2) from Charge Density Analysis |
title_short | New Insights into the Catalytic Activity of Cobalt Orthophosphate Co(3)(PO(4))(2) from Charge Density Analysis |
title_sort | new insights into the catalytic activity of cobalt orthophosphate co(3)(po(4))(2) from charge density analysis |
topic | Full Papers |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC6916324/ https://www.ncbi.nlm.nih.gov/pubmed/31361370 http://dx.doi.org/10.1002/chem.201902303 |
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