Crystal Facet Engineering of TiO2 Nanostructures for Enhancing Photoelectrochemical Water Splitting with BiVO4 Nanodots

Abstract

Highlights

Two types of BiVO4/TiO2 heterostructure photoanodes comprising TiO2 nanorods (NRs) and TiO2 nanoflowers (NFs) with different (001) and (110) crystal facets, respectively, were designed.

The higher photoactivity of BiVO4/TiO2 NFs than BiVO4/TiO2 NRs was attributed to the improvement of charge separation by the TiO2 NFs.

The formation of type II band alignment between BiVO4 nanodots and TiO2 NFs expedited electron transport and reduced charge recombination.

Abstract Although bismuth vanadate (BiVO4) has been promising as photoanode material for photoelectrochemical water splitting, its charge recombination issue by short charge diffusion length has led to various studies about heterostructure photoanodes. As a hole blocking layer of BiVO4, titanium dioxide (TiO2) has been considered unsuitable because of its relatively positive valence band edge and low electrical conductivity. Herein, a crystal facet engineering of TiO2 nanostructures is proposed to control band structures for the hole blocking layer of BiVO4 nanodots. We design two types of TiO2 nanostructures, which are nanorods (NRs) and nanoflowers (NFs) with different (001) and (110) crystal facets, respectively, and fabricate BiVO4/TiO2 heterostructure photoanodes. The BiVO4/TiO2 NFs showed 4.8 times higher photocurrent density than the BiVO4/TiO2 NRs. Transient decay time analysis and time-resolved photoluminescence reveal the enhancement is attributed to the reduced charge recombination, which is originated from the formation of type II band alignment between BiVO4 nanodots and TiO2 NFs. This work provides not only new insights into the interplay between crystal facets and band structures but also important steps for the design of highly efficient photoelectrodes.