文献类型：期刊文献

英文题名：Constructing asymmetric unsaturated copper coordination in Zinc(II)/Copper(I, II)-based metal-organic framework toward productive CO2-to-methanol photocatalytic conversion from CO2-capturing solution

作者：Wu, Kongguo[1];Liu, Chuanlei[1];Chen, Yuxiang[1];Jiang, Hao[1];Peng, Qilong[1];Chen, Yu[1];Fang, Diyi[1];Shen, Benxian[1,2];Wu, Qiumin[1,2];Zhan, Liang[1];Sun, Weizhen[1];Wu, Di[3,4,5,6];Sun, Hui[1,2]

机构：[1]East China Univ Sci & Technol, Sch Chem Engn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Int Joint Res Ctr Green Energy Chem Engn, Shanghai 200237, Peoples R China;[3]Washington State Univ, Alexandra Navrotsky Inst Expt Thermodynam, Pullman, WA 99163 USA;[4]Washington State Univ, Gene & Linda Voiland Sch Chem Engn & Bioengn, Pullman, WA 99163 USA;[5]Washington State Univ, Mat Sci & Engn, Pullman, WA 99163 USA;[6]Washington State Univ, Dept Chem, Pullman, WA 99163 USA

年份：2023

卷号：650

外文期刊名：APPLIED CATALYSIS A-GENERAL

收录：;EI(收录号：20224813199284);WOS:【SCI-EXPANDED(收录号:WOS:000904383100004)】；

基金：This work is supported by the National Natural Science Foundation of China (Grant 21878097 and 22178109) and the Natural Science Foundation of Shanghai (Grant 21ZR1417700) . D.W. acknowledges the institutional funds from the Gene and Linda Voiland School of Chemical Engineering and Bioengineering, and the Alexandra Navrotsky Institute for Experimental Thermodynamics at Washington State University. We thank Dr. Weizhong Zheng for the helpful discussion.

语种：英文

外文关键词：Copper coordination; Metal-organic framework; CO2 reduction; Photocatalysis; Methanol

摘要：Copper-based catalysts show potential advantages with respect to applications in CO2 photoreduction into valuable chemicals. However, there remain great challenges to reduce band gap energy and inhibit recombination of photogenerated electron-hole pairs. Herein, we report a metal-organic framework, Zn(II)/Cu(I, II)-BTC synthesized via facile one-pot solvothermal method. Asymmetric unsaturated tetrahedral copper coordination was verified by multiple characterizations including extended X-ray absorption fine structure and electron paramagnetic resonance analyses coupled with DFT calculations. Promoted separation and transfer of photogenerated electrons and largely inhibited recombination of electron-hole pairs contribute to a productive methanol yield of 4470 mu mol center dot g(-1)center dot h(-1), which is 107% higher than that over the parent Cu-BTC. In situ diffuse reflectance infrared Fourier transform spectroscopy measurement and DFT calculation were combined to elucidate the underlying mechanism. This study provides insights into effectively tuning separation and transfer of charge within copper-based photocatalysts and highlights the role of copper coordination in valence engineering.