New visible-light-driven Bi2MoO6/Cs3Sb2Br9 heterostructure for selective photocatalytic oxidation of toluene to benzaldehyde

Sujitra Wongthep; Prayoonsak Pluengphon; Doldet Tantraviwat; Waraporn Panchan; Sadanan Boochakiat; Kasornkamol Jarusuphakornkul; Qilong Wu; Jun Chen; Burapat Inceesungvorn

doi:10.1016/j.jcis.2023.10.148

New visible-light-driven Bi₂MoO₆/Cs₃Sb₂Br₉ heterostructure for selective photocatalytic oxidation of toluene to benzaldehyde

J Colloid Interface Sci. 2024 Feb:655:32-42. doi: 10.1016/j.jcis.2023.10.148. Epub 2023 Oct 30.

Authors

Sujitra Wongthep¹, Prayoonsak Pluengphon², Doldet Tantraviwat³, Waraporn Panchan⁴, Sadanan Boochakiat⁵, Kasornkamol Jarusuphakornkul¹, Qilong Wu⁶, Jun Chen⁶, Burapat Inceesungvorn⁷

Affiliations

¹ Department of Chemistry, Center of Excellence for Innovation in Chemistry (PERCH-CIC), and Center of Excellence in Materials Science and Technology, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand.
² Division of Physical Science, Faculty of Science and Technology, Huachiew Chalermprakiet University, Samutprakarn 10540, Thailand.
³ Department of Electrical Engineering, Faculty of Engineering, Chiang Mai University, Chiang Mai 50200, Thailand.
⁴ National Metal and Materials Technology Center (MTEC), National Science and Technology Development Agency (NSTDA), 114 Thailand Science Park, Phahonyothin Road, Khlong Luang, Pathum Thani 12120, Thailand.
⁵ Department of Chemistry, Center of Excellence for Innovation in Chemistry (PERCH-CIC), and Center of Excellence in Materials Science and Technology, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand; Intelligent Polymer Research Institute, ARC Centre of Excellence for Electromaterials Science, Australian Institute for Innovative Materials, Innovation Campus, University of Wollongong, North Wollongong, NSW 2500, Australia.
⁶ Intelligent Polymer Research Institute, ARC Centre of Excellence for Electromaterials Science, Australian Institute for Innovative Materials, Innovation Campus, University of Wollongong, North Wollongong, NSW 2500, Australia.
⁷ Department of Chemistry, Center of Excellence for Innovation in Chemistry (PERCH-CIC), and Center of Excellence in Materials Science and Technology, Faculty of Science, Chiang Mai University, Chiang Mai 50200, Thailand. Electronic address: burapat.i@cmu.ac.th.

PMID: 37924589
DOI: 10.1016/j.jcis.2023.10.148

Abstract

Herein, new Bi₂MoO₆/Cs₃Sb₂Br₉ heterostructure (BiMo/CSB) was investigated for the first time as a visible-light-driven photocatalyst for C(sp³)-H bond activation using molecular oxygen as a green oxidant and toluene as a model substrate. The optimized BiMo/CSB photocatalyst exhibited enhanced toluene oxidation activity (2,346 μmol g^-1h^-1), which was almost two- and five-fold that of pristine CSB (1,165 μmol g^-1h^-1) and BiMo (482 μmol g^-1h^-1), respectively. The improved photocatalytic performance was essentially attributed to the formation of staggered band energy lineup in the BiMo/CSB hybrid, which promoted S-scheme charge transfer across the BiMo/CSB heterointerface as supported by ultraviolet photoelectron spectroscopy (UPS), density functional theoretical (DFT), time-resolve photoluminescence (TRPL), and photoelectrochemical studies. Spin-trapping electron paramagnetic resonance (EPR) and radical scavenging studies revealed that photoinduced hole, molecular oxygen, and superoxide radical are key active species in this photocatalytic system. The developed BiMo/CSB catalyst provided good selectivity toward benzaldehyde product (94-98 %), presumably due to the inhibiting effect of benzyl alcohol on benzaldehyde oxidation. No significant change in structure and morphology was observed for the spent catalyst, however small negative shift of Sb 3d and Bi 4f binding energy was found suggesting partial reduction of Sb³⁺ and Bi³⁺. This work not only provides a new visible-light-driven photocatalyst for C(sp³)-H bond activation but also opens the doors for exploitation of the conversion and functionalization of this inert bond toward the production of high value-added organic chemicals.

Keywords: Bi(2)MoO(6); C(sp(3))–H activation; Cs(3)Sb(2)Br(9); Photocatalyst; Toluene; Visible light.