Spatially Separated C–C Coupling and Protonation on Cl‐Bridged Ti–Ag Dual‐Site Catalysts for Efficient Photocatalytic CO 2 Reduction to C 2 H 4
Year: 2025
Type: article
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 .
Authors: Haoran Du, Yangjie Fu, Rou Shi, Zhiyang Cao, Shao Zhang, Kaihong Liu, Jiaqi Wang, Bo Jiang, Hexing Li
Institutions: East China University of Science and Technology, Shanghai Normal University, International Joint Laboratory of Resource Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Fujian Institute of Research on the Structure of Matter, State Key Laboratory of Structural Chemistry, Shanghai Research Institute of Chemical Industry
Language: English
Field: Energy
Domain: Physical Sciences
Open Access status: bronze
OpenAlex ID: W4416453601