Contactless measurement of the photovoltage in BiVO4 photoelectrodes

Daemi, Sahar; Kundmann, Anna; Becker, Kathleen; Cendula, Peter; Osterloh, Frank E.

doi:10.1039/d3ee02087h

Title: Contactless measurement of the photovoltage in BiVO₄ photoelectrodes

Journal Article · 31 August 2023 · Energy & Environmental Science

DOI: https://doi.org/10.1039/d3ee02087h · OSTI ID:2000436

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University of California, Davis, CA (United States); UC Davis
University of California, Davis, CA (United States)
University of Žilina, Liptovsky Mikulas (Slovakia)

The power output of photoelectrochemical devices for solar energy-to-fuel conversion is determined by the photovoltage of the junction under illumination. In the presence of fast redox couples, the photovoltage can be obtained directly from current–voltage measurements of the device. However, for slow redox couples (H⁺/H₂, O₂/H₂O) used in solar fuel photoelectrodes, photovoltage measurements are not straightforward, due to the kinetic overpotentials during charge transfer. Here we show that the photovoltage of BiVO₄ electrodes in contact with fast electron donors KI, Na₂SO₃ or H₂O₂ or K₄Fe(CN)₆ can be measured in a contactless way with vibrating Kelvin probe surface photovoltage (SPV) spectroscopy. The photovoltage varies with illumination wavelength and intensity and matches the open circuit potential of the electrodes, obtained separately from electrochemical measurements. Plots of the photovoltage versus irradiance can be used to predict the oxidizing power of each electrode under zero applied bias. Except for K₄Fe(CN)₆, which causes shunting in the BiVO₄ electrode, photovoltage values correlate well with the built-in potential of each junction. Furthermore, the ability to obtain photovoltage information through contactless SPV measurements will be useful in the search for solid–liquid junctions with superior energy conversion properties.

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Research Organization:: University of California, Davis, CA (United States)

Sponsoring Organization:: Slovak Research and Development Agency; USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0015329

OSTI ID:: 2000436

Journal Information:: Energy & Environmental Science, Journal Name: Energy & Environmental Science Journal Issue: 10 Vol. 16; ISSN 1754-5692

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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