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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.-P. Wang, Y.-T. Cui, Y. Harada, D.-J. Huang, S. Schuppler, C. L. Hill, and F. M. F. de Groot*


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.

Phys. Chem. Chem. Phys. 20 , 4554 (2018)