Dual Heterojunctions and Nanobowl Morphology Engineered BiVO₄ Photoanodes for Enhanced Solar Water Splitting

Photoelectrochemical (PEC) water splitting represents an attractive strategy to realize the conversion from solar energy to hydrogen energy, but severe charge recombination in photoanodes significantly limits the conversion efficiency. Herein, a unique BiVO₄ (BVO) nanobowl (NB) heterojunction photoanode, which consists of [001]-oriented BiOCl underlayer and BVO nanobowls containing embedded BiOCl nanocrystals, is fabricated by nanosphere lithography followed by in situ transformation. Experimental characterizations and theoretical simulation prove that nanobowl morphology can effectively enhance light absorption while reducing carrier diffusion path. Density functional theory (DFT) calculations show the tendency of electron transfer from BVO to BiOCl. The [001]-oriented BiOCl underlayer forms a compact type II heterojunction with the BVO, favoring electron transfer from BVO through BiOCl to the substrate. Furthermore, the embedded BiOCl nanoparticles form a bulk heterojunction to facilitate bulk electron transfer. Consequently, the dual heterojunctions engineered BVO/BiOCl NB photoanode exhibits attractive PEC performance toward water oxidation with an excellent bulk charge separation efficiency of 95.5%, and a remarkable photocurrent density of 3.38 mA cm^-2 at 1.23 V versus reversible hydrogen electrode, a fourfold enhancement compared to the flat BVO counterpart. This work highlights the great potential of integrating dual heterojunctions engineering and morphology engineering in fabricating high-performance photoelectrodes toward efficient solar conversion.