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Tuning Intrinsic Electronic Properties via Size-Controlled Hydrothermal Crystalline Transformation from Tetragonal BiVO4 Spheroids to Monoclinic Plates

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    Tuning Intrinsic Electronic Properties via Size-Controlled Hydrothermal Crystalline Transformation from Tetragonal BiVO4 Spheroids to Monoclinic Plates
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    • Miquel Torras*
      Miquel Torras
      Univ. Bordeaux, CNRS, LOMA, UMR 5798, 351 Cours de la Libération, Talence Cedex F-33400, France
      Univ. Bordeaux, CNRS, Bordeaux INP, ICMCB, UMR 5026, 87 Avenue du Dr. A. Schweitzer, Pessac Cedex F-33608, France
      Groupe Chimie Moléculaire et Matériaux (C2M), Univ. Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, 351 Cours de la Libération, Talence Cedex F-33400, France
      *Email: [email protected]
      More by Miquel Torras
    • Marie-Anne Dourges
      Marie-Anne Dourges
      Groupe Chimie Moléculaire et Matériaux (C2M), Univ. Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, 351 Cours de la Libération, Talence Cedex F-33400, France
      More by Marie-Anne Dourges
    • Justine Quinet
      Justine Quinet
      Institut de Chimie et Procédés pour l′Energie, l′Environnement et la Santé, (ICPEES UMR7515) - CNRS - Université de Strasbourg, 25 rue Becquerel, Strasbourg 67087, France
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    • Anaëlle Demange
      Anaëlle Demange
      Institut de Chimie et Procédés pour l′Energie, l′Environnement et la Santé, (ICPEES UMR7515) - CNRS - Université de Strasbourg, 25 rue Becquerel, Strasbourg 67087, France
      More by Anaëlle Demange
    • Thomas Cottineau
      Thomas Cottineau
      Institut de Chimie et Procédés pour l′Energie, l′Environnement et la Santé, (ICPEES UMR7515) - CNRS - Université de Strasbourg, 25 rue Becquerel, Strasbourg 67087, France
      More by Thomas Cottineau
      Orcidhttps://orcid.org/0000-0001-8058-4824
    • Jean-Pierre Delville
      Jean-Pierre Delville
      Univ. Bordeaux, CNRS, LOMA, UMR 5798, 351 Cours de la Libération, Talence Cedex F-33400, France
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    • Marie-Helène Delville
      Marie-Helène Delville
      Univ. Bordeaux, CNRS, Bordeaux INP, ICMCB, UMR 5026, 87 Avenue du Dr. A. Schweitzer, Pessac Cedex F-33608, France
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    • Thierry Toupance*
      Thierry Toupance
      Groupe Chimie Moléculaire et Matériaux (C2M), Univ. Bordeaux, CNRS, Bordeaux INP, ISM, UMR 5255, 351 Cours de la Libération, Talence Cedex F-33400, France
      *Email: [email protected]
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      Orcidhttps://orcid.org/0000-0001-8234-7064
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    ACS Applied Energy Materials

    Cite this: ACS Appl. Energy Mater. 2025, 8, 6, 3929–3941
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    https://doi.org/10.1021/acsaem.5c00215
    Published March 12, 2025
    Copyright © 2025 The Authors. Published by American Chemical Society
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    Abstract

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    This study reports the synthesis of monoclinic clinobisvanite BiVO4 crystals with well-defined {010} and {110} facets and nanometer sizes through controlled reactant addition and hydrothermal treatment. By adjustment of the Bi3+ precursor addition rate, nanoplates with significantly reduced edge length and thickness were obtained compared to conventional microplates. The formation process involves the nucleation of surfactant-coated tetragonal zircon BiVO4 nanocrystals, which aggregate into spheroids before being transformed into monoclinic clinobisvanite plates. A proposed model explains this size-tuning mechanism through partial dissolution, phase transformation, and facet-selective growth. Reducing the size of tetragonal zircon BiVO4 spheroids enhanced photocatalytic water oxidation, while for monoclinic clinobisvanite BiVO4 plates, size reduction had the opposite effect. Photoelectrochemical analysis revealed a shift from n-type behavior in microplates to p-type behavior in nanoplates under negative bias. These findings highlight the need to integrate size control with surface chemistry, bulk doping, and defect engineering to optimize BiVO4 for catalytic and electronic applications.

    Copyright © 2025 The Authors. Published by American Chemical Society

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    • Detailed experimental procedures, Raman and FTIR spectra, complementary XRD and XPS data and HR-TEM images, TG-DTG curves, N2 sorption isotherms, particle size histograms, and raw photocatalysis data (PDF)

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    ACS Applied Energy Materials

    Cite this: ACS Appl. Energy Mater. 2025, 8, 6, 3929–3941
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsaem.5c00215
    Published March 12, 2025
    Copyright © 2025 The Authors. Published by American Chemical Society
    Request reuse permissions

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