TY - JOUR
T1 - Influence of Composition and Structure on the Optoelectronic Properties of Photocatalytic Bi4NbO8Cl-Bi2GdO4Cl Intergrowths
AU - Christudas Beena, Nayana
AU - Magnard, Nicolas P.L.
AU - Puggioni, Danilo
AU - dos Reis, Roberto
AU - Chatterjee, Kaustav
AU - Zhan, Xun
AU - Dravid, Vinayak P.
AU - Rondinelli, James M.
AU - Jensen, Kirsten M.Ø.
AU - Skrabalak, Sara E.
N1 - Publisher Copyright:
© 2024 American Chemical Society.
PY - 2024/5/6
Y1 - 2024/5/6
N2 - 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.
AB - 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.
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U2 - 10.1021/acs.inorgchem.4c00306
DO - 10.1021/acs.inorgchem.4c00306
M3 - Article
C2 - 38639743
AN - SCOPUS:85191386637
SN - 0020-1669
VL - 63
SP - 8131
EP - 8141
JO - Inorganic chemistry
JF - Inorganic chemistry
IS - 18
ER -