文献类型：期刊文献

英文题名：Molecular Assembled Electrocatalyst for Highly Selective CO2 Fixation to C2+Products

作者：Wang, Peng[1];Li, Tan[1];Wu, Qiqi[1];Du, Ruian[1];Zhang, Qinghua[2];Huang, Wei-Hsiang[3,4];Chen, Chi-Liang[3,4];Fan, Yan[5];Chen, Haonan[5];Jia, Yanyan[6,7];Dai, Sheng[6,7];Qiu, Yongcai[1];Yan, Keyou[1];Meng, Yuanyuan[8];Waterhouse, Geoffrey I. N.[9];Gu, Lin[2];Zhao, Yun[1];Zhao, Wei-Wei[10];Chen, Guangxu[1]

机构：[1]South China Univ Technol, Sch Environm & Energy, State Key Lab Luminescent Mat & Devices, Guangdong Prov Key Lab Atmospher Environm & Pollut, Guangzhou 510006, Peoples R China;[2]Chinese Acad Sci, Inst Phys, Beijing 100190, Peoples R China;[3]Natl Synchrotron Radiat Res Ctr, Hsinchu 30076, Taiwan;[4]Natl Taiwan Univ Sci & Technol NTUST, Grad Inst Appl Sci & Technol, Taipei 10607, Taiwan;[5]South China Univ Technol, Med Device Res & Testing Ctr, Guangzhou 510006, Peoples R China;[6]East China Univ Sci & Technol, Inst Fine Chem, Sch Chem & Mol Engn, Key Lab Adv Mat, Shanghai 200237, Peoples R China;[7]East China Univ Sci & Technol, Inst Fine Chem, Frontiers Sci Ctr Materiobiol & Dynam Chem, Feringa Nobel Prize Scientist Joint Res Ctr,Sch Ch, Shanghai 200237, Peoples R China;[8]Taiyuan Univ Technol, Coll Chem & Chem Engn, Taiyuan 030002, Peoples R China;[9]Univ Auckland, Sch Chem Sci, Auckland 1142, New Zealand;[10]Nanjing Univ, Sch Chem & Chem Engn, State Key Lab Analyt Chem Life Sci, Nanjing 210023, Peoples R China

年份：2022

卷号：16

期号：10

起止页码：17021

外文期刊名：ACS NANO

收录：;EI(收录号：20224212969247);WOS:【SCI-EXPANDED(收录号:WOS:000879330300001)】；

基金：This work was supported by the National Natural Science Foundation of China (21971070, 22106048), Natural Science Foundation of Guangdong Province (2021A1515010091), Guangdong Innovative and Entrepreneurial Research Team Program (2019ZT08L075), Guangdong Pearl River Talent Program (2019QN01L159), Science and Technology Program of Guangzhou (202103040002, 202102020306), and China Postdoctoral Science Foundation (2020M682714) and the National Key R & D Program of China (2021YFA1501900) for financial support. G.I.N.W. acknowledges funding support from the MacDiarmid Institute for Advanced Materials and Nanotechnology, the Energy Education Trust of New Zealand, and the Royal Society Te Aparangi (for the award of a James Cook Research Fellowship). The authors would like to thank G. C. Deng and N. F. Zheng from Xiamen University for the measurement and analysis of single crystal of CuPPh. The authors also thank Y. J. Zhang, G. Fu, and J. F. Li from Xiamen University for the helpful discussions. X-ray absorption spectroscopy studies were carried out at the beamline 17C1 of the National Synchrotron Radiation Research Center (NSRRC) in Taiwan and the BL14W1 beamline in the Shanghai Synchrotron Radiation Facility (SSRF). In situ XAS was performed at the beamline 17C1 of the NSRRC in Taiwan. The authors also thank R. X. Q from Xiamen University for the help of EXAFS simulation.

语种：英文

外文关键词：bimetal center; CO2 reduction mechanism; CO2 fixation; electrocatalysis; molecular assembly

摘要：In certain metalloenzymes, multimetal centers with appropriate primary/secondary coordination environments allow carbon-carbon coupling reactions to occur efficiently and with high selectivity. This same function is seldom realized in molecular electrocatalysts. Herein we synthesized rod-shaped nanocatalysts with multiple copper centers through the molecular assembly of a triphenylphosphine copper complex (CuPPh). The assembled molecular CuPPh catalyst demonstrated excellent electrochemical CO2 fixation performance in aqueous solution, yielding high-value C2+ hydrocarbons (ethene) and oxygenates (ethanol) as the main products. Using density functional theory (DFT) calculations, in situ X-ray absorption spectroscopy (XAS) and quasi -in situ X-ray photoelectron spectroscopy (XPS), and reaction intermediate capture, we established that the excellent catalytic performance originated from the large number of double copper centers in the rod-shaped assemblies. Cu-Cu distances in the absence of CO2 were as long as 7.9 angstrom, decreasing substantially after binding CO2 molecules indicating dynamic and cooperative function. The double copper centers were shown to promote carbon-carbon coupling via a CO2 transfer-coupling mechanism involving an oxalate (OOC-COO) intermediate, allowing the efficient production of C2+ products. The assembled CuPPh nanorods showed high activity, excellent stability, and a high Faradaic efficiency (FE) to C2+ products (65.4%), with performance comparable to state-of-the-art copper oxide-based catalysts. To our knowledge, our findings demonstrate that harnessing metalloenzyme-like properties in molecularly assembled catalysts can greatly improve the selectivity of CO2RR, promoting the rational design of improved CO2 reduction catalysts.