New Insights in the Catalytic Activity of Cobalt Orthophosphate Co3 (PO4)2 from Charge Density Analysis

2019 | journal article. A publication with affiliation to the University of Göttingen.

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​New Insights in the Catalytic Activity of Cobalt Orthophosphate Co3 (PO4)2 from Charge Density Analysis​
Keil, H.; Hellström, M.; Stückl, C.; Herbst‐Irmer, R.; Behler, J. & Stalke, D.​ (2019) 
Chemistry – A European Journal25(25) pp. 15786​-15794​.​ DOI: https://doi.org/10.1002/chem.201902303 

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Authors
Keil, Helena; Hellström, Matti; Stückl, Claudia; Herbst‐Irmer, Regine; Behler, Jörg; Stalke, Dietmar
Abstract
An extensive characterization of Co3 (PO4 )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.
Issue Date
2019
Journal
Chemistry – A European Journal 
Organization
Fakultät für Chemie 
ISSN
1521-3765; 0947-6539
eISSN
1521-3765
Language
English
Sponsor
DFG http://dx.doi.org/10.13039/501100001659
Danish National Research Foundation http://dx.doi.org/10.13039/501100001732
European Union’s Horizon 2020 research and innovation programme under grant agreement No. 798129

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