Single‐Source Bismuth (Transition Metal) Polyoxovanadate Precursors for the Scalable Synthesis of Doped BiVO₄ Photoanodes

Abstract

Single-source precursors are used to produce nanostructured BiVO₄ photoanodes for water oxidation in a straightforward and scalable drop-casting synthetic process. Polyoxometallate precursors, which contain both Bi and V, are produced in a one-step reaction from commercially available starting materials. Simple annealing of the molecular precursor produces nanocrystalline BiVO₄ films. The precursor can be designed to incorporate a third metal (Co, Ni, Cu, or Zn), enabling the direct formation of doped BiVO₄ films. In particular, the Co- and Zn-doped photoanodes show promise for photoelectrochemical water oxidation, with photocurrent densities >1 mA cm^-2 at 1.23 V vs reversible hydrogen electrode (RHE). Using this simple synthetic process, a 300 cm² Co-BiVO₄ photoanode is produced, which generates a photocurrent of up to 67 mA at 1.23 V vs RHE and demonstrates the scalability of this approach.