p-Type BiVO4 for Solar O2 Reduction to H2O2

Seo, Daye; Somjit, Vrindaa; Wi, Dae Han; Galli, Giulia; Choi, Kyoung-Shin

doi:10.1021/jacs.4c13290

Title: p-Type BiVO₄ for Solar O₂ Reduction to H₂O₂

Journal Article · Fri Jan 17 00:00:00 UTC 2025 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.4c13290 · OSTI ID:2574942

Seo, Daye ^[1]; Somjit, Vrindaa ^[2];

^[1];

^[3];

^[1]

Univ. of Wisconsin, Madison, WI (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States)
Argonne National Laboratory (ANL), Argonne, IL (United States); Univ. of Chicago, IL (United States)

Photoelectrochemical cells (PECs) can directly utilize solar energy to drive chemical reactions to produce fuels and chemicals. Oxide-based photoelectrodes in general exhibit enhanced stability against photocorrosion, which is a critical advantage for building a sustainable PEC. However, most oxide-based semiconductors are n-type, and p-type oxides that can be used as photocathodes are limited. In this study, we report the synthesis, characterization, and application of p-type BiVO₄ with a monoclinic scheelite (ms) structure. ms-BiVO₄ is inherently n-type, and it has been investigated only as a photoanode to date. In this study, we prepared p-type ms-BiVO₄ (bandgap of 2.4 eV) via atomic doping of Ca²⁺ at the Bi³⁺ site under an O₂-rich environment and examined its performance as a photocathode. We then demonstrated that the Ca-doped ms-BiVO₄ photocathode can be used for solar O₂ reduction to H₂O₂ when coupled with appropriate catalysts. Our computational investigation using hybrid density functional theory revealed that holes are stable as polarons in ms-BiVO₄ and have a low self-trapping energy, that may lead to free carriers in the valence band at finite temperature. Our calculations also show that Ca is an effective shallow acceptor dopant with low formation energy and thermal ionization energy leading to p-type conductivity. In conclusion, our joint experimental and computational results provide critical insights into the design of p-type ms-BiVO₄, enabling its use as a polaronic oxide photocathode.

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Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Energy Research Scientific Computing Center (NERSC); National Science Foundation (NSF); USDOE Laboratory Directed Research and Development (LDRD) Program; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357; SC0012704; SC0024211

OSTI ID:: 2574942

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 4 Vol. 147; ISSN 0002-7863; ISSN 1520-5126

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Catalysts
Electrodes
O2 reduction
Photonics
Polarons
Redox reactions
electronic structure
oxide
photocathode
point defect

Title: p-Type BiVO4 for Solar O2 Reduction to H2O2

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Title: p-Type BiVO₄ for Solar O₂ Reduction to H₂O₂