4.8 Article

Tuneable Phase, Morphology, and Performance of Bismuth Oxyhalide Photocatalysts via Microwave-Assisted Synthesis

Journal

ACS APPLIED MATERIALS & INTERFACES
Volume 14, Issue 20, Pages 23496-23506

Publisher

AMER CHEMICAL SOC
DOI: 10.1021/acsami.2c03837

Keywords

photocatalysis; bismuth oxyhalides; pH-dependence; pair distribution function analysis; Rietveld refinements; benzylamine oxidation

Funding

  1. Independent Research Fund Denmark [8021-00349B]
  2. Center for Integrated Materials Research (iMAT) at Aarhus University
  3. Sino-Danish Center (SDC) for Education and Research
  4. Carlsberg Foundation [CF14-0506, CF17-0937, CF18-0840]
  5. Danish National Research Foundation (Carbon Dioxide Activation Center) [DNRF 118]
  6. Danscatt

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In this study, a series of bismuth oxyhalide photocatalysts were synthesized using a facile microwave-assisted approach with controlled synthesis pH. The materials exhibited different morphologies, facet dominance, and phases depending on the pH value. The photocatalytic performance of the materials was evaluated, with factors such as surface area, facet dominance, amorphous content, and band gap found to significantly impact the photocatalytic yield.
In this study, a facile microwave-assisted synthesis approach was used to produce a series of bismuth oxyhalide photocatalysts, with systematic changes in synthesis pH between 1 and 14 allowing control over a broad range of material properties and characteristics. Detailed structural and morphological investigations with powder X-ray diffraction (PXRD), Rietveld refinements, pair distribution function (PDF) analysis, and scanning electron microscopy (SEM) show that thin particles of BiOCl, BiOBr, Bi24O31Cl10, and Bi24O31Br10 were selectively produced, with progressive changes in morphology, facet dominance, and phase as a function of pH. The impact of these changes on photocatalytic performance was evaluated by studying the aerobic oxidation of benzylamine to N-benzylidenebenzylamine, with all materials exhibiting photocatalytic abilities under UV or blue light. While a combination of material properties and characteristics influenced the photocatalytic performance, certain factors such as surface area, facet dominance, amorphous content, and band gap were found to have a larger impact on the photocatalytic yield. Overall, this study demonstrates the possibilities of phase, morphology, and performance of bismuth oxyhalide photocatalysts over the entire pH range, produced using a fast and facile microwave-assisted synthesis technique as an alternative to the more widely applied hydrothermal synthesis approach. Additionally, the detailed structural and morphological investigations of the materials contribute to a greater understanding of bismuth oxyhalide photocatalysts in general, while also highlighting some of the most desirable properties for improved photocatalytic performance of these materials.

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