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Photoelectrochemical solar energy conversion offers a way to directly store light into energy-rich chemicals. Photoanodes based on the WO 3 /BiVO 4 heterojunction are most effective mainly thanks to the efficient separation of photogenerated charges. The WO 3 /BiVO 4 interfacial space region in the heterojunction is investigated here with the increasing thickness of the BiVO 4 layer over a WO 3 scaffold. On the basis of X-ray diffraction analysis results, density functional theory simulations show a BiVO 4 growth over the WO 3 layer along the BiVO 4 {010} face, driven by the formation of a stable interface with new covalent bonds, with a favorable band alignment and band bending between the two oxides. This crystal facet phase matching allows a smooth transition between the electronic states of the two oxides and may be a key factor ensuring the high efficiency attained with this heterojunction. The photoelectrochemical activity of the WO 3 /BiVO 4 photoanodes depends on both the irradiation wavelength and the thickness of the visible-light-absorbing BiVO 4 layer, a 75 nm thick BiVO 4 layer on WO 3 being best performing.

WO3/BiVO4 Photoanodes: Facets Matching at the Heterojunction and BiVO4 Layer Thickness Effects

WO₃/BiVO₄ Photoanodes: Facets Matching at the Heterojunction and BiVO₄ Layer Thickness Effects