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Black TiO2 with/without noble metal has been proposed for visiblephotocatalyst, still leaving poor catalyst efficiency. Alternatively,phase-mixed TiO2 such as anatase and rutile has been commonly used for visiblecatalysts with the inevitable inclusion of noble metal. Here, we perform anoble metal-free visible photocatalyst blue TiO2 with type-II band-alignedordered anatase/disordered rutile structure, via phase-selective reduction withalkali metals. The changed band alignment in this heterostructure wasidentified by absorption and ultraviolet photoemission spectroscopy, which wasfurther confirmed by transient charge separation. The band alignment of type-Iand type-II was clearly restructured by converting from ordered to disorderedphase with a prolonged reduction period and as followed light absorbanceenhancement also observed. Initiated type-I in a pristine sample, the type-IIwas organized from disordered rutile phase in 3-day Li-reduction. The type-IIdisordered rutile TiO2 heterostructure exhibits a remarkable photocatalyticperformance by 55 times higher than conventional P25 TiO2 in solar-light drivenhydrogen evolution reaction owing to an efficient electron and hole separationof type-II heterojunction. Furthermore, this restructured heterojunctiontype-II TiO2 demanded 10 times less Pt amount as a co-catalyst for thecomparable photocatalytic performance, compared to Pt decorated type-I pristineanatase/rutile phase-mixed TiO2.

Band restructuring of ordered/disordered blue TiO2 for visible photocatalyst