Selective CO<sub>2</sub> Photoreduction into CH<sub>4</sub> Triggered by the Synergy between Oxygen Vacancy and Ru Substitution under Near‐Infrared Light Irradiation
Jun Li, Xinglong Liu, Xi Wu, Zhongyi Liu, Zaiwang Zhao, Yi‐Feng Liu, Shi Xue Dou, Yao Xiao
Abstract
Abstract Near‐infrared (NIR) light powdered CO 2 photoreduction reaction is generally restricted to the separation efficiency of photogenerated carriers and the supply of active hydrogen (*H). Herein, the study reports a retrofitting hydrogenated MoO 3‐x (H‐MoO 3‐x ) nanosheet photocatalysts with Ru single atom substitution (Ru@H‐MoO 3‐x ) fabricated by one‐step solvothermal method. Experiments together with theoretical calculations demonstrate that the synergistic effect of Ru substitution and oxygen vacancy can not only inhibit the recombination of photogenerated carriers, but also facilitate the CO 2 adsorption/activation as well as the supply of *H. Compared with H‐MoO 3‐x , the Ru@H‐MoO 3‐x exhibit more favorable formation of *CHO in the process of *CO conversion due to the fast *H generation on electron‐rich Ru sites and transfer to *CO intermediates, leading to the preferential photoreduction of CO 2 to CH 4 with high selectivity. The optimized Ru@H‐MoO 3‐x exhibits a superior CO 2 photoreduction activity with CH 4 evolution rate of 111.6 and 39.0 µmol g catalyst −1 under full spectrum and NIR light irradiation, respectively, which is 8.8 and 15.0 times much higher than that of H‐MoO 3‐x . This work provides an in‐depth understanding at the atomic level on the design of NIR responsive photocatalyst for achieving the goal of carbon neutrality.