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Role of Alkali Metal in BiVO4 Crystal Structure for Enhancing Charge Separation and Diffusion Length for Photoelectrochemical Water Splitting

Cite this: ACS Appl. Mater. Interfaces 2020, 12, 47, 52808–52818
Publication Date (Web):November 13, 2020
Copyright © 2020 American Chemical Society
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Alkali metal (Na or K) doping in BiVO4 was examined systematically for enhancing bulk charge separation and transport in addition to improving charge transfer from the surface. The alkali metal-doped BiVO4 thin film photoanodes having nanostructured porous grain surface morphology exhibited better photocurrent density than pristine BiVO4. In particular, Na:BiVO4/Fe:Ni/Co–Pi photoanode showed a significantly improved photocurrent of 3.2 ± 0.15 mA·cm–2 in 0.1 M K2HPO4 electrolyte at 1.23 VRHE under 1 sun illumination. The depth-dependent Doppler broadening spectroscopy measurements confirmed the significant reduction in Bi- and V-based defect density with Na metal doping, and this led to a higher bulk diffusion length of charge pairs (four times that of the pristine one). Na doping led to reduced surface defects resulting in improved surface charge transfer based on cyclic voltammetry experiments. The density functional theory calculations confirmed the improved performance in Na-doped BiVO4 photoanodes achieved through interband formation and reduction in the band gap.

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  • Additional information including photoelectrochemical and Mott–Schottky measurement details, calculation process of theoretical photocurrent, charge transport, IPCE, APCE, integrated current, LHE, and absorption efficiency evaluation; various analysis including Mott–Schottky, EDX, XPS, UV–vis, ECSA, and DFT calculation details; and tables including lattice parameters, XPS, calculated parameters, formation energies, and spd-orbital site projections for the three interbands (PDF)

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This article is cited by 5 publications.

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  5. Basanth S. Kalanoor, Hyungtak Seo, Shankara S. Kalanur. Multiple ion doping in BiVO4 as an effective strategy of enhancing photoelectrochemical water splitting: A review. Materials Science for Energy Technologies 2021, 4 , 317-328.