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

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

International Research Centre for Renewable Energy, State Key Laboratory of Multiphase Flow in Power Engineering, Xi'an Jiaotong University, Xi'an 710049, Shaanxi, China

Received Date: 25 September 2017
Revised Date: 29 October 2017

Fund Project: This work was supported by the National Natural Science Foundation of China (51672210, 51323011, 51236007).

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.
- Metal complex,
- BiVO₄,
- Water oxidation,
- Photocatalysis,
- Interfacial kinetics
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Photocatalytic water oxidation over BiVO₄ with interface energetics engineered by Co and Ni-metallated dicyanamides