Crystalline Carbon Nitride Supported Copper Single Atoms for Photocatalytic CO2 Reduction with Nearly 100% CO Selectivity

被引:533
作者
Li, Yang [1 ,2 ]
Li, Baihai [3 ]
Zhang, Dainan [1 ]
Cheng, Lei [1 ]
Xiang, Quanjun [1 ]
机构
[1] Univ Elect Sci & Technol China, Sch Elect Sci & Engn, State Key Lab Elect Thin Film & Integrated Device, Chengdu 610054, Peoples R China
[2] Huazhong Agr Univ, Coll Resources & Environm, Wuhan 430070, Peoples R China
[3] Univ Elect Sci & Technol China, Sch Mat & Energy, Chengdu 610054, Peoples R China
关键词
crystalline g-C3N4; Cu single atoms; nanorod; photocatalytic CO2 reduction; selective; H-2-PRODUCTION ACTIVITY; HYDROGEN-PRODUCTION; TIO2; H2O; EVOLUTION; WATER; H-2; NANOPARTICLES; PERFORMANCE; CONVERSION;
D O I
10.1021/acsnano.0c04544
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Single metal atom photocatalysts have received widespread attention due to the rational use of metal resources and maximum atom utilization efficiency. In particular, N-rich amorphous g-C3N4 is always used as a support to anchor single metal atoms. However, the enhancement of photocatalytic activity of g-C3N4 by introducing a single atom is limited due to the bulk morphology and the excess defects of amorphous g-C3N4. Here, we report crystalline g-C3N4 nanorod supported copper single atoms by molten salts and the reflux method. The prepared single Cu atoms/crystalline g-C3N4 photocatalyst (Cu-CCN) shows highly selective and efficient photocatalytic reduction of CO2 under the absence of any cocatalyst or sacrificial agent. The introduction of single Cu atoms can be used as the CO2 adsorption site, thus increasing the adsorption capacity of Cu-CCN samples to CO2. Theoretical calculation results show that reducing CO2 to CH4 on Cu-CCN samples is an entropy-increasing process, whereas reducing CO2 to CO is an entropy-decreasing process. As a result, the CuCCN samples exhibited enhanced photocatalytic CO2 reduction with nearly 100% selective photocatalytic CO2 to CO conversion. The mechanism of photocatalytic CO2 reduction over Cu-CCN samples was proposed based on in situ Fourier transform infrared spectra, X-ray absorption spectroscopy, and density functional theory calculation. This work provides an indepth understanding of the design of photocatalysts for enhancing active sites of the reactants.
引用
收藏
页码:10552 / 10561
页数:10
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