Sulfur defect induced Cd0.3Zn0.7S in-situ anchoring on metal organic framework for enhanced photothermal catalytic CO2 reduction to prepare proportionally adjustable syngas

Hongbin He; Xuan Jian; Tianxu Zen; Bingbing Feng; Yanan Hu; Zhongqiang Yuan; Zizhen Zhao; Xiaoming Gao; Lei Lv; Zhenheng Cao

doi:10.1016/j.jcis.2023.09.103

Sulfur defect induced Cd_0.3Zn_0.7S in-situ anchoring on metal organic framework for enhanced photothermal catalytic CO₂ reduction to prepare proportionally adjustable syngas

J Colloid Interface Sci. 2024 Jan;653(Pt A):687-696. doi: 10.1016/j.jcis.2023.09.103. Epub 2023 Sep 18.

Authors

Affiliations

¹ Department of Chemistry and Chemical Engineering, Clean Utilization of Low Rank Coal of Shaanxi Collaborative Innovation Center, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan'an University, Yan'an 716000, PR China.
² Department of Chemistry and Chemical Engineering, Clean Utilization of Low Rank Coal of Shaanxi Collaborative Innovation Center, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan'an University, Yan'an 716000, PR China. Electronic address: ydgaoxm@126.com.

PMID: 37741176
DOI: 10.1016/j.jcis.2023.09.103

Abstract

The rapid recombination of interfacial charges is considered to be the main obstacle limiting the photocatalytic CO₂ reduction. Thus, it is a challenge to research an accurate and stable charge transfer control strategy. MIL-53 (Al)-S/Cd_0.3Zn_0.7S (MAS/CZS-0.3) photocatalysts with chemically bonded interfaces were constructed by in-situ electrostatic assembly of sulfur defect Cd_0.3Zn_0.7S (CZS-0.3) on the surface of MIL-53 (Al) (MAW), which enhanced interfacial coupling and accelerated electron transfer efficiency. An adjustable proportion of syngas (H₂/CO) was prepared by photothermal catalytic CO₂ reduction at micro-interface. and the optimal yield of CO (66.10 μmol∙g^-1∙h^-1) and H₂ (71.0 μmol∙g^-1∙h^-1) was realized by the MAS/CZS-0.3 photocatalyst. The improved activity was due to the photogenerated electrons migrated from CZS-0.3 to the adsorption active sites of MAS, which strengthened the adsorption and activation of CO₂ on MAS. The photothermal catalytic CO₂ reduction to CO follows the pathway of CO₂→*COOH → CO and CO₂→*HCO₃^-→CO. This work provided a reference for the research, characterization, and application of in-situ anchoring of metal organic frameworks in photothermal catalytic CO₂ reduction, and provided a green path for the supply of Syngas in industry.

Keywords: CO(2) reduction; Gas solid interfacial catalysis; Interfacial chemical bonds; Photothermal catalysis; S-vacancy.