Author, as appears in the article.: Soriano-López, J; Steuber, FW; Mulahmetovic, M; Besora, M; Clemente-Juan, JM; O'Doherty, M; Zhu, NY; Hill, CL; Coronado, E; Poblet, JM; Schmitt, W
Department: Química Física i Inorgànica
URV's Author/s: Besora Bonet, Maria / Poblet Rius, Josep Maria
Keywords: Exchange interactions oxygen metals hydrogen highly efficient heterogeneous coox energy driven charge-transfer catalysts
Abstract: Water oxidation is a bottleneck reaction for the establishment of solar-to-fuel energy conversion systems. Earth-abundant metal-based polyoxometalates are promising heterogeneous water oxidation catalysts that can operate in a wide pH range. However, detailed structure-reactivity relationships are not yet comprehensively understood, hampering the design and synthesis of more effective polyoxometalate-based oxidation catalysts. Here we report the synthesis of an ordered, mixed-metal cobalt-iron Weakley archetype [CoII2(H2O)2FeIII2(CoIIW9O34)2]14− (Co2Fe2-WS), which unexpectedly highlights the strong influence of the central, coordinatively saturated metal ions on the catalytic water oxidation characteristics. The resulting species exhibits catalytic turnover frequencies which are up to 4× higher than those of the corresponding archetype tetracobalt-oxo species [CoII2(H2O)2CoII2(PW9O34)2]10− (Co4-WS). It is further striking that the system becomes catalytically inactive when one of the central positions is occupied by a WVI ion as demonstrated by [CoII2(H2O)2CoIIWVI(CoIIW9O34)2]12− (Co3W-WS). Importantly, this study demonstrates that coordinatively saturated metal ions in this central position, which at first glance appear insignificant, do not solely have a structural role but also impart a distinctive structural influence on the reactivity of the polyoxometalate. These results provide unique insights into the structure-reactivity relationships of polyoxometalates with improved catalytic performance characteristics.
Thematic Areas: Química Materiais Interdisciplinar General chemistry Farmacia Ciências biológicas iii Ciências biológicas i Chemistry, multidisciplinary Chemistry (miscellaneous) Chemistry (all) Astronomia / física
licence for use: https://creativecommons.org/licenses/by/3.0/es/
Author's mail: maria.besora@urv.cat josepmaria.poblet@urv.cat
Author identifier: 0000-0002-6656-5827 0000-0002-4533-0623
Record's date: 2024-01-29
Papper version: info:eu-repo/semantics/publishedVersion
Link to the original source: https://pubs.rsc.org/en/Content/ArticleLanding/2023/SC/D3SC04002J
Licence document URL: http://repositori.urv.cat/ca/proteccio-de-dades/
Papper original source: Chemical Science. 14 (47): 13722-13733
APA: Soriano-López, J; Steuber, FW; Mulahmetovic, M; Besora, M; Clemente-Juan, JM; O'Doherty, M; Zhu, NY; Hill, CL; Coronado, E; Poblet, JM; Schmitt, W (2023). Accelerating water oxidation - a mixed Co/Fe polyoxometalate with improved turnover characteristics. Chemical Science, 14(47), 13722-13733. DOI: 10.1039/d3sc04002j
Article's DOI: 10.1039/d3sc04002j
Entity: Universitat Rovira i Virgili
Journal publication year: 2023
Publication Type: Journal Publications
Repositori URV