The photo-decomposition and self-restructuring dynamic equilibrium mechanism of Cu_(2)(OH)_(2)CO_(3)for stable photocatalytic CO_(2)reduction  

作　　者：Yaqing Zhi Haoning Mao Guangxing Yang Qiao Zhang Zhiting Liu Yonghai Cao Siyuan Yang Feng Peng 

机构地区：[1]School of Chemistry and Chemical Engineering,Guangzhou University,Guangzhou 510006,Guangdong,China [2]College of Materials and Energy,South China Agricultural University,Guangzhou 510642,Guangdong,China [3]School of Chemistry and Chemical Engineering,South China University and Technology,Gangzhou 510640,Guangdong,China

出　　处：《Journal of Energy Chemistry》2024年第5期104-112,共9页能源化学（英文版）

基　　金：financial support from the National Natural Science Foundation of China(No.22272038);the Science and Technology Planning Project of Guangzhou City(No.2023A03J0026)。

摘　　要：Developing suitable photocatalysts and understanding their intrinsic catalytic mechanism remain key challenges in the pursuit of highly active,good selective,and long-term stable photocatalytic CO_(2)reduction(PCO_(2)R)systems.Herein,monoclinic Cu_(2)(OH)_(2)CO_(3)is firstly proven to be a new class of photocatalyst,which has excellent catalytic stability and selectivity for PCO_(2)R in the absence of any sacrificial agent and cocatalysts.Based on a Cu_(2)(OH)_(2)^(13)CO_(3)photocatalyst and 13CO_(2)two-sided^(13)C isotopic tracer strategy,and combined with in situ diffused reflectance infrared Fourier transform spectroscopy(DRIFTS)analysis and density functional theory(DFT)calculations,two main CO_(2)transformation routes,and the photo-decomposition and self-restructuring dynamic equilibrium mechanism of Cu_(2)(OH)_(2)CO_(3)are definitely revealed.The PCO_(2)R activity of Cu_(2)(OH)_(2)CO_(3)is comparable to some of state-of-the-art novel photocatalysts.Significantly,the PCO_(2)R properties can be further greatly enhanced by simply combining Cu_(2)(OH)_(2)CO_(3)with typical TiO_(2)to construct composites photocatalyst.The highest CO_(2)and CH_(4)production rates by 7.5 wt%Cu_(2)(OH)_(2)CO_(3)-TiO_(2)reach 16.4μmol g^(-1)h^(-1)and 116.0μmol g^(-1)h^(-1),respectively,which are even higher than that of some of PCO_(2)R systems containing sacrificial agents or precious metals modified photocatalysts.This work provides a better understanding for the PCO_(2)R mechanism at the atomic levels,and also indicates that basic carbonate photocatalysts have broad application potential in the future.

关 键 词：CO_(2)photocatalytic reduction PHOTOCATALYSIS Basic copper carbonate SELF-RECONSTRUCTION PHOTOCATALYST 

分 类 号：O643.36[理学—物理化学] O644.1[理学—化学] X701[环境科学与工程—环境工程]