Boosting solar water oxidation activity and stability of BiVO4 photoanode through the Co-catalytic effect of CuCoO2

• Published in: Electrochimica acta 2019-05, Vol.304, p.301-311
• Main Authors: Zhong, Xiaohui, He, Huichao, Du, Jinyan, Ren, Qin, Huang, Ji, Tang, Yi, Wang, Jun, Yang, Long, Dong, Faqin, Bian, Liang, Zhou, Yong
• Format: Article
• Language: English
• Subjects: Bismuth oxides; Catalysis; Charge efficiency; Charge separation and transfer; Charge transfer; Copper; CuCoO2/BiVO4; Heterojunctions; Oxidation; P-n junctions; Photoanodes; Photoelectric effect; Photoelectric emission; Photoelectrochemical water oxidation; Reaction kinetics; Separation; Stability; Surface charge; Synergistic effect; Vanadates; Water oxidation kinetics
• ISSN: 0013-4686; 1873-3859
• DOI: 10.1016/j.electacta.2019.02.101

The poor surface charge separation and transfer properties as well as sluggish water oxidation kinetics jointly limit the performance of BiVO4 photoanode for water oxidation. In this work, p-type CuCoO2 with high-spin Co3+(Oh) was investigated as co-catalyst to synergistically improve the surface charge separation and transfer efficiencies as well as reaction kinetics of BiVO4 film for photoelectrochemical water oxidation. In comparison with the photocurrent on BiVO4 photoanode for water oxidation (1.21 mA/cm2 at 1.23 V vs. RHE), the CuCoO2-coupled BiVO4 (CuCoO2/BiVO4) photoanode exhibits a higher photocurrent density of 3.32 mA/cm2 at 1.23 V vs. RHE under AM 1.5G illumination. In addition, a significant improvement on the reaction stability is achieved on the CuCoO2/BiVO4 photoanode, about ∼79% water oxidation activity is retained on the CuCoO2/BiVO4 photoanode after operating at 0.8 V vs. RHE for 5 h, while only ∼9% activity is retained on the BiVO4 photoanode. The boosted water oxidation activity and stability on CuCoO2/BiVO4 photoanode could be attributed the synergistic effect that originated from CuCoO2-electrocatalysis and BiVO4-photocatalysis in thermodynamics and kinetics. Specifically, p-n heterojunctions are formed in the coupling interface between CuCoO2 (p-type) and BiVO4 (n-type), which thermodynamically improve the surface charge separation and transfer efficiencies of BiVO4 photoanode during water oxidation. Simultaneously, the high-spin Co3+(Oh) of CuCoO2 could act as active sites to accelerate the water oxidation of CuCoO2/BiVO4 photoanode in kinetics. In addition, Cu2+ active sites are formed for water oxidation through the oxidation reaction of photogenerated holes with the Cu+ of CuCoO2. The CuCoO2-coupled BiVO4 film is of enhanced photoelectrochemical water oxidation activity and stability, which is originated from the synergistic effect between CuCoO2-electrocatalysis and BiVO4-photocatalysis in thermodynamics and kinetics. [Display omitted] •CuCoO2/BiVO4 film is of higher PEC water oxidation performance than BiVO4 film.•CuCoO2-coupling improves the charge separation and transfer of BiVO4 thermodynamically.•CuCoO2-coupling accelerates the water oxidation in kinetics.