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Issue 6, 2018
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Cobalt-to-vanadium charge transfer in polyoxometalate water oxidation catalysts revealed by 2p3d resonant inelastic X-ray scattering

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Abstract

Two isostructural cobalt containing polyoxometalate water oxidation catalysts, [Co4(H2O)2(α-PW9O34)2]10− (Co4P2) and [Co4(H2O)2(α-VW9O34)2]10− (Co4V2), exhibit large differences in their catalytic performance. The substitution of phosphorus centers in Co4P2 with redox-active vanadium centers in Co4V2 leads to electronic structure modifications. Evidence for the significance of the vanadium centers to catalysis, predicted by theory, was found from soft X-ray absorption (XAS) and resonant inelastic X-ray scattering (RIXS). The XAS and RIXS spectra determine the electronic structure of the cobalt and vanadium sites in the pre-reaction state of both Co4V2 and Co4P2. High-energy resolution RIXS results reveal that Co4V2 possesses a smaller ligand field within the tetra-cobalt core and a cobalt-to-vanadium charge transfer band. The differences in electronic structures offer insights into the enhanced catalysis of Co4V2.

Graphical abstract: Cobalt-to-vanadium charge transfer in polyoxometalate water oxidation catalysts revealed by 2p3d resonant inelastic X-ray scattering

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Publication details

The article was received on 04 Oct 2017, accepted on 22 Jan 2018 and first published on 23 Jan 2018


Article type: Paper
DOI: 10.1039/C7CP06786K
Citation: Phys. Chem. Chem. Phys., 2018,20, 4554-4562

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    Cobalt-to-vanadium charge transfer in polyoxometalate water oxidation catalysts revealed by 2p3d resonant inelastic X-ray scattering

    B. Liu, E. N. Glass, R. Wang, Y. Cui, Y. Harada, D. Huang, S. Schuppler, C. L. Hill and F. M. F. de Groot, Phys. Chem. Chem. Phys., 2018, 20, 4554
    DOI: 10.1039/C7CP06786K

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