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.

Highlights

  • Produced in a one-step reaction from commercially available starting materials

  • BiVO4 has been utilized in state-of-the-art tandem photoelecoxidation, with photocurrent densities >1 mA cm−2 at 1.23 V vs reversible hydrogen electrode (RHE)

  • Trochemical devices, sometimes referred to as “artificial leaves,”[4] with monoclinic scheelite BiVO4 established as the most effective polymorph for photoanodes.[2c,d] Doping,[5] nanostructuring,[4b,6] heterojunction formation,[7] and the addition of oxygen evolution catalysts (OECs)[6,8] are Converting solar energy into hydrogen by the splitting of water employed to remediate the low carrier diffusion lengths associor the conversion of anthropogenic CO2 into fuels coupled to ated with BiVO4,[9] which reduce efficiency due to accumulation water oxidation are attractive solutions to energy production and recombination of charge carriers.[10]

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Summary

Introduction

Produced in a one-step reaction from commercially available starting materials. Simple annealing of the molecular precursor produces nanocrystalline BiVO4 films. The SSPs decompose to form two separate phases (a type III SSP),[17a,21], e.g., BiVO4 and V2O5 (Figure 2a–e).[20] Scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS) conducted before the washing process indicated the presence of large rods amongst smaller particles, with the rods composed mainly of V and O (Figures S26 and S27, Supporting Information).

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