Synergistic Effect between CO<sub>2</sub> Chemisorption Using Amino-Modified Carbon Nitride and Epoxide Activation by High-Energy Electrons for Plasmon-Assisted Synthesis of Cyclic Carbonates
Xueqin Gong, Yujia Zhang, Yayang Xu, Guangyao Zhai, Xiaolei Liu, Xiaolei Bao, Zeyan Wang, Yuanyuan Liu, Peng Wang, Hefeng Cheng, Yu‐Chen Fan, Ying Dai, Zhaoke Zheng, Baibiao Huang
Abstract
Photocatalytic CO 2 cycloaddition is a promising approach for CO 2 value-added processes. However, the efficiency of plasmon-assisted CO 2 cycloaddition still needs to be improved and the reaction mechanism is unclear. Herein, g-C 3 N 4 /Ag (ACN–Ag) hybrids exhibited superior activity of CO 2 cycloaddition by coupling a semiconductor into the plasmonic system, in which the ACN grafting amino group by the formation of carbon vacancies can enhance CO 2 chemisorption; meanwhile, photo-generated electrons from ACN transfer to Ag to form high-energy electrons, which can activate propylene oxide, accelerating the ring-opening step. Importantly, photo-generated electron injection from ACN to Ag and the interaction between Ag nanoparticles and ACN were confirmed by single-particle photoluminescence spectroscopy. The wavelength-dependent activity demonstrated that the plasmon excitation is crucial for the reaction. Moreover, in situ single-particle PL quenching caused by propylene oxide and in situ electron paramagnetic resonance verified the activation of propylene oxide by ACN–Ag. This work is conducive to an in-depth understanding of the mechanism of CO 2 cycloaddition at the single-particle level and provides guidance for the organic synthesis.