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Polyoxothiometalate-Derivatized Silicon Photocathodes for Sunlight-Driven Hydrogen Evolution Reaction.

ABSTRACT: Silicon photocathodes coated with drop-casted {Mo₃S₄}-based polyoxothiometalate assemblies are demonstrated to be effective for sunlight-driven hydrogen evolution reaction (HER) in acid conditions. These photocathodes are catalytically more efficient than that coated with the parent thiomolybdate incorporating an organic ligand, as supported by a higher onset potential and a lower overvoltage at 10 mA cm^-2. At pH 7.3, the trend is inversed and the beneficial effect of the polyoxometalate for the HER is not observed. Moreover, the polyoxothiometalate-modified photocathode is found to be also more stable under acid conditions and can be operated at the light-limited catalytic current for more than 40 h. Furthermore, X-ray photoelectron spectroscopy and atomic force microscopy measurements indicate that the cathodic polarization of both photocathodes leads to the release of a large amount of the deposited material into the electrolyte solution concomitantly with the formation of mixed valence species {Mo(IV)_3-x Mo(III) _x O_4-n S _n }^(4-x)+ resulting from the replacement of S^2- sulfido ligands in the cluster by oxo O^2- groups; these combined effects are shown to be beneficial for the photoelectrocatalysis.

SUBMITTER: Fu D

PROVIDER: S-EPMC6645094 | biostudies-literature |

REPOSITORIES: biostudies-literature

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