Insight into the key restriction of BiVO${}_4$ photoanodes prepared by pyrolysis method for scalable preparation

Bismuth Vanadate (BiVO${}_4$) photoanode has been popularly investigated for promising solar water oxidation, but its intrinsic performance has been greatly retarded by the direct pyrolysis method. Here we insight the key restriction of BiVO${}_4$ prepared by metal-organic decomposition (MOD) method. It is found that the evaporation of vanadium during the pyrolysis tends to cause a substantial phase impurity, and the unexpected few tetragonal phase inhibits the charge separation evidently. Consequently, suitably excessive vanadium precursor was adopted to eliminate the phase impurity, based on which the obtained intrinsic BiVO${}_4$ photoanode could exhibit photocurrent density of 4.2 mA cm${}^{-2}$ at 1.23 V${}_{RHE}$ under AM 1.5 G irradiation, as comparable to the one fabricated by the currently popular two-step electrodeposition method. Furthermore, the excellent performance can be maintained on the enlarged photoanode (25 cm${}^2$), demonstrating the advantage of MOD method in scalable preparation. Our work provides new insight and highlights the glorious future of MOD method for the design of scale-up efficient BiVO${}_4$ photoanode. (© 2023 Wiley‐VCH GmbH)