Phase transition-induced band edge engineering of BiVO4 to split pure water under visible light.

Jo, Won Jun; Kang, Hyun Joon; Kong, Ki-Jeong; Lee, Yun Seog; Park, Hunmin; Lee, Younghye; Buonassisi, Tonio; Gleason, Karen K et al. · Proc Natl Acad Sci U S A · 2015

basic_science · Level V

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Abstract

Through phase transition-induced band edge engineering by dual doping with In and Mo, a new greenish BiVO4 (Bi1-XInXV1-XMoXO4) is developed that has a larger band gap energy than the usual yellow scheelite monoclinic BiVO4 as well as a higher (more negative) conduction band than H(+)/H2 potential [0 VRHE (reversible hydrogen electrode) at pH 7]. Hence, it can extract H2 from pure water by visible light-driven overall water splitting without using any sacrificial reagents. The density functional theory calculation indicates that In(3+)/Mo(6+) dual doping triggers partial phase transformation from pure monoclinic BiVO4 to a mixture of monoclinic BiVO4 and tetragonal BiVO4, which sequentially leads to unit cell volume growth, compressive lattice strain increase, conduction band edge uplift, and band gap widening.