Issue 47, 2023

Accelerating water oxidation – a mixed Co/Fe polyoxometalate with improved turnover characteristics

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.

Graphical abstract: Accelerating water oxidation – a mixed Co/Fe polyoxometalate with improved turnover characteristics

Supplementary files

Article information

Article type
Edge Article
Submitted
01 Aug. 2023
Accepted
29 Okt. 2023
First published
31 Okt. 2023
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY-NC license

Chem. Sci., 2023,14, 13722-13733

Accelerating water oxidation – a mixed Co/Fe polyoxometalate with improved turnover characteristics

J. Soriano-López, F. W. Steuber, M. Mulahmetović, M. Besora, J. M. Clemente-Juan, M. O'Doherty, N. Zhu, C. L. Hill, E. Coronado, J. M. Poblet and W. Schmitt, Chem. Sci., 2023, 14, 13722 DOI: 10.1039/D3SC04002J

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