Spatially Separated C–C Coupling and Protonation on Cl‐Bridged Ti–Ag Dual‐Site Catalysts for Efficient Photocatalytic CO <sub>2</sub> Reduction to C <sub>2</sub> H <sub>4</sub>
Abstract
Abstract Solar‐driven selective reduction of CO 2 to C 2 H 4 conversion is bottlenecked by the concurrent demands for intermediate protonation and C–C coupling. Herein, we constructed a chlorine (Cl)‐bridged Ti–Ag dual‐site catalysts to overcome above issues. The introduction of Cl on Ti‐Ag dual sites spatially separates C–C coupling and intermediate protonation, making *CO dimerization thermodynamically more favorable than *CO hydrogenation. In situ characterization and DFT calculations reveal that the Cl enables the Ti sites within the Ti─Cl─Ag configuration act as active center for CO 2 activation and C–C coupling, thereby increasing the *CO intermediate concentration and lowering the C–C coupling energy barrier. Concurrently, Ag sites preferentially catalyze H 2 O dissociation, providing active hydrogen for the subsequent protonation of *OCCO intermediates, thus increasing the overall C 2 H 4 formation rate. The optimized Ti─Cl─Ag catalysts achieve high C 2 H 4 production rate of 244 µmol·g −1 ·h −1 with 64.3% selectivity, outperforming O‐bridged Ti–Ag catalysts which mainly favor *CO deep hydrogenation. This work establishes spatially separated Ti–Ag dual sites that orchestrates site‐specific C–C coupling and active hydrogen feeding, providing a rational design concept of photocatalysts for selective reduction of CO 2 to C 2 H 4 .
Article Details
Authors (9)
Haoran Du
Yangjie Fu
University of Chinese Academy of Sciences Beijing P. R. China
Rou Shi
The Education Ministry Key Lab of Resource Chemistry, Joint International Research Laboratory of Resource Chemistry Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Frontiers Science Center of Biomimetic Catalysis, College of Chemistry and Materials Science Shanghai Normal University Shanghai 200234 P.R. China
Zhiyang Cao
The Education Ministry Key Lab of Resource Chemistry, Joint International Research Laboratory of Resource Chemistry Shanghai Key Laboratory of Rare Earth Functional Materials, Shanghai Frontiers Science Center of Biomimetic Catalysis, College of Chemistry and Materials Science Shanghai Normal University Shanghai 200234 P.R. China
Shao Zhang
Kaihong Liu
Chinese Education Ministry Key Lab and Joint International Research Lab of Resource Chemistry, Shanghai Frontiers Science Center of Biomimetic Catalysis, College of Chemistry and Materials Science
Jiaqi Wang
Bo Jiang
Chinese Education Ministry Key Lab and Joint International Research Lab of Resource Chemistry, Shanghai Frontiers Science Center of Biomimetic Catalysis, College of Chemistry and Materials Science
Hexing Li
Chinese Education Ministry Key Lab and Joint International Research Lab of Resource Chemistry, Shanghai Frontiers Science Center of Biomimetic Catalysis, College of Chemistry and Materials Science