Bi12O17Cl2 with a Sextuple BiO Layer Composed of Rock-Salt and Fluorite Units and its Structural Conversion through Fluorination to Enhance Photocatalytic Activity
Kirsanova, Maria A.
Brown, Craig M.
Gorelik, Tatiana E.
Abakumov, Artem M.
KAUST DepartmentChemical Science Program KAUST Catalysis Center Division of Physical Science and Engineering King Abdullah University of Science and Technology (KAUST) Thuwal 23955-6900 Saudi Arabia
Physical Science and Engineering (PSE) Division
Chemical Science Program
KAUST Catalysis Center (KCC)
Embargo End Date2023-08-02
Permanent link to this recordhttp://hdl.handle.net/10754/680132
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AbstractLayered bismuth oxyhalides with bilayered (Bi2O2) fluorite (FL) slabs are promising visible-light photocatalysts because of their excellent stability and the ability to adjust band levels depending on the layers combined. It is interesting to manipulate the Bi2O2 slab itself, but only trilayered FL blocks (e.g., Bi3O4) are reported so far. Here, a structurally uncharacterized Bi12O17Cl2, which is extensively studied as a photocatalyst for a variety of reactions, has a sextuple Bi6O8.5 block separated by Cl is shown. Unlike double and triple layered cases, the inner region of the Bi6O8.5 block contains 1D rock-salt (RS) units in the FL matrix along the a-axis, causing in-plane corrugation. A topochemical reaction involving anion-exchange gives Bi12O17–0.5xFxCl2 (x ≤ 6) with alternate FL and RS slabs along the c-axis. The elimination of the structural corrugation increases higher photo-conductivity and improves photocatalytic activity against acetic acid decomposition under visible light irradiation. This study paves new opportunities of controlling the properties of layered bismuth oxyhalides by the thickness of Bi–O block, FL/RS configuration, and structural modulation.
CitationKato, D., Tomita, O., Nelson, R., Kirsanova, M. A., Dronskowski, R., Suzuki, H., Zhong, C., Tassel, C., Ishida, K., Matsuzaki, Y., Brown, C. M., Fujita, K., Fujii, K., Yashima, M., Kobayashi, Y., Saeki, A., Oikawa, I., Takamura, H., Abe, R., … Abakumov, A. M. (2022). Bi 12 O 17 Cl 2 with a Sextuple BiO Layer Composed of Rock-Salt and Fluorite Units and its Structural Conversion through Fluorination to Enhance Photocatalytic Activity. Advanced Functional Materials, 2204112. Portico. https://doi.org/10.1002/adfm.202204112
SponsorsThe authors are grateful to Egbert Keller (Freiburg, Germany) for Bi12O17Cl2 crystals for electron diffraction analysis and fruitful discussions on the crystallographic part. TEG was supported by German Science Foundation, project CRC1279. This work was supported by JST PRESTO (JPMJPR21A5), JSPS Core-to-Core Program (A) Advanced Research Networks (JPJSCCA20200004), the Grant-in-Aid for Scientific Research on Innovative Areas “Mixed Anion” project (16H06438 and 16H06439), CREST (JPMJCR1421), JSPS KAKENHI (JP21K20556, JP20H00398, and JP22H04914). The research leading to these results has received funding from the European Union Seventh Framework Programme under Grant Agreement 312483 – ESTEEM2 (Integrated Infrastructure Initiative–I3). The authors acknowledge the support of the National Institute of Standards and Technology, U. S. Department of Commerce, in providing the neutron research facilities used in this work. The SXPD and TOF neutron-diffraction experiments were performed at the BL02B2 of SPring-8 (Proposal no. 2022A1081 and 2020A1669) and at iMATERIA of J-PARC (Proposal nos. 2020A0085 and 2020PM2002). Certain commercial equipment, instruments, or materials are identified in this document. Such identification does not imply recommendation or endorsement by the National Institute of Standards and Technology, nor does it imply that the products identified are necessarily the best available for the purpose.
JournalAdvanced Functional Materials