Constructing an Active Sulfur-Vacancy-Rich Surface for Selective *CH 3 -CH 3 Coupling in CO 2 -to-C 2 H 6 Conversion With 92% Selectivity.

Autor: Yang X; School of Materials Science and Engineering, and the Key Laboratory of Structure & Functional Regulation of Hybrid Materials, Ministry of Education, Anhui University, Hefei, 230601, P. R. China., Ren L; School of Physics and Electronics, Henan University, Kaifeng, 475004, P. R. China., Chen Z; School of Materials Science and Engineering, and the Key Laboratory of Structure & Functional Regulation of Hybrid Materials, Ministry of Education, Anhui University, Hefei, 230601, P. R. China., Li H; Anhui Provincial Key Laboratory of Green Carbon Chemistry, Fuyang Normal University, Fuyang, 236037, P. R. China., Yuan Y; School of Materials Science and Engineering, and the Key Laboratory of Structure & Functional Regulation of Hybrid Materials, Ministry of Education, Anhui University, Hefei, 230601, P. R. China.
Jazyk: angličtina
Zdroj: Advanced materials (Deerfield Beach, Fla.) [Adv Mater] 2024 Nov 06, pp. e2412299. Date of Electronic Publication: 2024 Nov 06.
DOI: 10.1002/adma.202412299
Abstrakt: To achieve high selectivity in photocatalytic CO 2 reduction to C 2+ products, increasing the number of CO 2 adsorption sites and lowering the energy barriers for key intermediates are critical. A ZnIn 2 S 4 (ZIS)/MoO 3-x (Z-M) photocatalyst is presented, in which plasmonic MoO 3-x generates hot electrons, creating a multielectron environment in ZIS that facilitates efficient C─C coupling reactions. Density functional theory (DFT) calculations reveal that MoO 3-x reduces the formation energy of sulfur vacancies (S V ) in ZIS, thereby enhancing CO 2 adsorption and activation. The S V -rich surface lowers the energy barrier for forming HCOO * to -0.33 eV whereas the energy barrier for forming * COOH is 0.77 eV. Successive hydrogenation of HCOO * leads to * CH 2 , which converts to * CH 3 with an energy barrier of -0.63 eV. The energy barrier for * CH 3 -CH 3 coupling is 0.54 eV, which is lower than the 0.73 eV for * CH 2 -CH 2 coupling to form * C 2 H 4 . Thus, Z-M preferentially produces C 2 H 6 over C 2 H 4 . Under visible light, Z-M achieves a CO 2 -to-C 2 H 6 conversion rate of 467.3 µmol g -1 h -1 with 92.0% selectivity. This work highlights the dual role of plasmonic photocatalysts in enhancing CO 2 adsorption and improving C 2+ production in CO 2 reduction.
(© 2024 Wiley‐VCH GmbH.)
Databáze: MEDLINE
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