Mechanically and photoelectrochemically stable WO₃|BiVO₄|NiFeOOH photoanodes synthesised by a scalable chemical vapour deposition method
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Author(s)
Type
Journal Article
Abstract
The development of scalable, stable and high performance photoelectrodes remains the major bottleneck in up-scaling photoelectrochemical (PEC) water splitting systems. A photoanode structure of particular promise is WO3|BiVO4, where the formation of staggered heterojunction between nanostructured WO3 and a thin layer of BiVO4 mitigates charge carrier mobility limitations present for BiVO4 alone and suppresses recombination. Although these electrodes remain prone to photo-corrosion, this effect can be mitigated through the application of water oxidation surface co-catalysts. An additional challenge that has rarely been addressed in the literature to date is the need for strong adhesion to the substrate and mechanical stability of these photoelectrodes, so that they can withstand flow-induced shear stress exerted by the electrolyte in continuous flow under operational conditions. Herein, we propose a scalable route to synthesising WO3|BiVO4|NiFeOOH photoanodes entirely by aerosol-assisted chemical vapour deposition (AA-CVD). The mechanical stability of the WO3|BiVO4 heterojunction was optimised by tuning the morphology of the WO3 underlayer and improving its adhesion to the FTO transparent substrate. To address BiVO4 dissolution at the electrode|electrolyte interface, we fabricated a NiFeOOH co-catalyst by a novel AA-CVD method. This suppressed BiVO4 dissolution and enhanced the water oxidation performance of the photoanode, characterised by linear sweep voltammetry (LSV), photoelectrochemical impedance spectroscopy (PEIS) and chopped chronoamperometry. The photoanode materials were physically characterised by X-ray diffraction (XRD), UV-Vis spectroscopy, scanning electron microscopy (SEM), high resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS), Raman spectroscopy and time-of-flight secondary ion mass spectrometry (ToF-SIMS). Our optimised photoanodes with 1 cm2 photoactive area delivered a stable photocurrent density of 1.75 mA cm−2 (at 1 simulated sun irradiance and 1.23 VRHE) during 24 hours testing in a continuous PEC flow reactor (operated at 0.5 cm s−1). Our method for growing WO3|BiVO4|NiFeOOH photoanodes is up-scalable, and therefore suitable for producing large-area demonstration devices, providing a pathway to commercial photoelectrochemical hydrogen production.
Date Issued
2025-04-26
Date Acceptance
2025-03-15
Citation
Journal of Materials Chemistry A, 2025, 13 (16), pp.11585-11604
ISSN
2050-7488
Publisher
Royal Society of Chemistry (RSC)
Start Page
11585
End Page
11604
Journal / Book Title
Journal of Materials Chemistry A
Volume
13
Issue
16
Copyright Statement
© The Royal Society of Chemistry 2025 Open Access Article. This article is licensed under a Creative Commons Attribution 3.0 Unported Licence.
License URL
Identifier
https://pubs.rsc.org/en/content/articlelanding/2025/ta/d5ta00440c
Publication Status
Published
Date Publish Online
2025-03-17