Influence of Composition and Structure on the Optoelectronic Properties of Photocatalytic Bi4NbO8Cl-Bi2GdO4Cl Intergrowths

Nayana Christudas Beena, Nicolas P.L. Magnard, Danilo Puggioni, Roberto dos Reis, Kaustav Chatterjee, Xun Zhan, Vinayak P. Dravid, James M. Rondinelli, Kirsten M.Ø. Jensen, Sara E. Skrabalak*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

Abstract

Mixed metal oxyhalides are an exciting class of photocatalysts, capable of the sustainable generation of fuels and remediation of pollutants with solar energy. Bismuth oxyhalides of the types Bi4MO8X (M = Nb and Ta; X = Cl and Br) and Bi2AO4X (A = most lanthanides; X = Cl, Br, and I) have an electronic structure that imparts photostability, as their valence band maxima (VBM) are composed of O 2p orbitals rather than X np orbitals that typify many other bismuth oxyhalides. Here, flux-based synthesis of intergrowth Bi4NbO8Cl-Bi2GdO4Cl is reported, testing the hypothesis that both intergrowth stoichiometry and M identity serve as levers toward tunable optoelectronic properties. X-ray scattering and atomically resolved electron microscopy verify intergrowth formation. Facile manipulation of the Bi4NbO8Cl-to-Bi2GdO4Cl ratio is achieved with the specific ratio influencing both the crystal and electronic structures of the intergrowths. This compositional flexibility and crystal structure engineering can be leveraged for photocatalytic applications, with comparisons to the previously reported Bi4TaO8Cl-Bi2GdO4Cl intergrowth revealing how subtle structural and compositional features can impact photocatalytic materials.

Original languageEnglish (US)
Pages (from-to)8131-8141
Number of pages11
JournalInorganic chemistry
Volume63
Issue number18
DOIs
StatePublished - May 6 2024

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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