Photocatalytic water oxidation over BiVO4 with interface energetics engineered by Co and Ni-metallated dicyanamides

doi:10.1016/S1872-2067(17)62943-7

Abstract

Abstract:

Photocatalytic water oxidation based on semiconductors usually suffers from poor charge transfer from the bulk to the interface, which is necessary for oxygen generation. Here, we construct a hybrid artificial photosynthesis system for photocatalytic water oxidation. The system consists of BiVO₄ as the light harvester, a transitional metal complex (M(dca)₂, M=Co, Ni, dca:dicyanamide) as the water oxidation catalyst, and S₂O₈^2- as a sacrificial electron acceptor. The system exhibits enhanced oxygen evolution activity when M(dca)₂ is introduced. The BiVO₄/Co(dca)₂ and BiVO₄/Ni(dca)₂ systems exhibit excellent oxygen evolution rates of 508.1 and 297.7 μmol/(h·g) compared to the pure BiVO₄ which shows a photocatalytic oxygen evolution rate of 252.2 μmol/(h·g) during 6 h of photocatalytic reaction. Co(dca)₂ is found to be more effective than Ni(dca)₂ as a water oxidation catalyst. The enhanced photocatalytic performance is ascribed to the M(dca)₂-engineered BiVO₄/electrolyte interface energetics, and to the M(dca)₂-catalyzed surface water oxidation. These two factors lead to a decrease in the energy barrier for hole transfer from the bulk to the surface of BiVO₄, which promotes the water oxidation kinetics.

Key words: Metal complex, BiVO₄, Water oxidation, Photocatalysis, Interfacial kinetics

Yi Shang, Fujun Niu, Shaohua Shen. Photocatalytic water oxidation over BiVO₄ with interface energetics engineered by Co and Ni-metallated dicyanamides[J]. Chinese Journal of Catalysis, 2018, 39(3): 502-509.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(17)62943-7

https://www.cjcatal.com/EN/Y2018/V39/I3/502

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Photocatalytic water oxidation over BiVO₄ with interface energetics engineered by Co and Ni-metallated dicyanamides

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