Liu Zhiguo, Wu Shiqun, Li Mingyang, Zhang Jinlong
Shanghai Engineering Research Center for Multi-Media Environmental Catalysis and Resource Utilization, Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, Frontiers Science Center for Materiobiology and Dynamic Chemistry, School of Chemistry and Molecular Engineering, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, P. R. China.
School of Chemistry & Chemical Engineering, Yancheng Institute of Technology, Yancheng 224051, China.
ACS Appl Mater Interfaces. 2022 Jun 8;14(22):25417-25426. doi: 10.1021/acsami.2c03913. Epub 2022 May 30.
Realizing the high selectivity of CH from the photocatalytic CO reduction reaction (CO RR) remains a great challenge owing to the lower efficiency of multi-electron transfer and the similar thermodynamic properties of CH and CO. Herein, nitrogen-deficient carbon nitride two-dimensional (2D) nanosheets were prepared via the high-temperature crystalline phase transformation process. Optimizing crystallinity enhances the in-plane polarization along the -axis. Owing to the increased electron density of the N defect, the kinetic possibilities of CH production have increased. Furthermore, the potential energy of the mid-gap states introduced by the N defect favors the thermodynamics of CH production. The selectivity values of CH based on yield and electrons are 87.1 and 96.4%. This work unravels the mechanism to selectively produce CH from CO photoreduction through the crystalline phase and defect regulation and provides significant guidance for the rational design of CO reduction photocatalysts for selective CH production.
由于多电子转移效率较低以及CH和CO相似的热力学性质，实现光催化CO还原反应（CO RR）中CH的高选择性仍然是一个巨大的挑战。在此，通过高温晶相转变过程制备了缺氮的二维（2D）氮化碳纳米片。优化结晶度可增强沿轴的面内极化。由于N缺陷处电子密度增加，生成CH的动力学可能性增加。此外，N缺陷引入的带隙中间态的势能有利于CH生成的热力学。基于产率和电子的CH选择性值分别为87.1%和96.4%。这项工作揭示了通过晶相和缺陷调控从CO光还原中选择性生成CH的机制，并为选择性生成CH的CO还原光催化剂的合理设计提供了重要指导。
