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Improving the Photo-Oxidative Performance of Bi2MoO6 by Harnessing the Synergy between Spatial Charge Separation and Rational Co-Catalyst Deposition

Wu, Xuelian, Hart, Judy N., Wen, Xiaoming, Wang, Liang, Du, Yi, Dou, Shi Xue, Ng, Yun Hau, Amal, Rose, Scott, Jason
ACS applied materials & interfaces 2018 v.10 no.11 pp. 9342-9352
bismuth, electrons, energy, gold, manganese oxides, materials science, molybdates, oxygen production, photocatalysis, photocatalysts, photooxidation, platinum, semiconductors, silver
It has been reported that photogenerated electrons and holes can be directed toward specific crystal facets of a semiconductor particle, which is believed to arise from the differences in their surface electronic structures, suggesting that different facets can act as either photoreduction or photo-oxidation sites. This study examines the propensity for this effect to occur in faceted, plate-like bismuth molybdate (Bi₂MoO₆), which is a useful photocatalyst for water oxidation. Photoexcited electrons and holes are shown to be spatially separated toward the {100} and {001}/{010} facets of Bi₂MoO₆, respectively, by facet-dependent photodeposition of noble metals (Pt, Au, and Ag) and metal oxides (PbO₂, MnOₓ, and CoOₓ). Theoretical calculations revealed that differences in energy levels between the conduction bands and valence bands of the {100} and {001}/{010} facets can contribute to electrons and holes being drawn to different surfaces of the plate-like Bi₂MoO₆. Utilizing this knowledge, the photo-oxidative capability of Bi₂MoO₆ was improved by adding an efficient water oxidation co-catalyst, CoOₓ, to the system, whereby the extent of enhancement was shown to be governed by the co-catalyst location. A greater oxygen evolution occurred when CoOₓ was selectively deposited on the hole-rich {001}/{010} facets of Bi₂MoO₆ compared to when CoOₓ was randomly located across all of the facets. The elevated performance exhibited for the selectively loaded CoOₓ/Bi₂MoO₆ was ascribed to the greater opportunity for hole trapping by the co-catalyst being accentuated over other potentially detrimental effects, such as the co-catalyst acting as a recombination medium and/or covering reactive sites. The results indicate that harnessing the synergy between the spatial charge separation and the co-catalyst location on the appropriate facets of plate-like Bi₂MoO₆ can promote its photocatalytic activity.