文献类型：期刊文献

英文题名：Electrocatalytic reduction of carbon dioxide in confined microspace utilizing single nickel atom decorated nitrogen-doped carbon nanospheres

作者：Lv, Chunmei[1];Huang, Kai[1];Fan, Yu[1];Xu, Jing[2];Lian, Cheng[1];Jiang, Hongliang[1];Zhang, Yongzheng[1];Ma, Cheng[1,3];Qiao, Wenming[1,3];Wang, Jitong[1,3];Ling, Licheng[1,3]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[2]Guangxi Univ, Sch Chem & Chem Engn, Guangxi Key Lab Petrochem Resource Proc & Proc Int, Nanning 530004, Peoples R China;[3]East China Univ Sci & Technol, Key Lab Specially Funct Polymer Mat & Related Tech, Shanghai 200237, Peoples R China

年份：2023

卷号：111

外文期刊名：NANO ENERGY

收录：;EI(收录号：20231513865734);WOS:【SCI-EXPANDED(收录号:WOS:000972476900001)】；

基金：This work is supported by the National Natural Science Foundation of China (No. U21A2060, No.22178116, No.21978097) , Shanghai Pujiang Program (No.21PJD019) , Natural Science Foundation of Shanghai (No.22ZR1417400) , Fundamental Research Funds for the Central Universities (No.222201817001, No.50321041918013, No. JKA01221601) and the Dean/Opening Project of Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology.

语种：英文

外文关键词：CO 2 RR; Single Ni atom; Nanosphere; Confined microspace

摘要：Carbon dioxide electroreduction reaction (CO2RR), as a rational regulation of CO2 resource utilization, demands effectively selective catalysts for converting CO2 into high-value-added chemicals. Carbon-based nanoreactors featuring rationally designed porous framework structures might provide a unique chemical environment for confining and stabilizing the active metal species, consequently improving the CO2RR activity. Herein, nitrogen -doped porous carbon nanospheres decorated by single Ni atom (Ni-NCN) featuring a Ni-N4 structure were synthesized using the modified sol-gel method for the reduction of CO2 to CO. The synergistic effect of the Ni-N4 active sites homogenously distributed in the interconnected pore structure and the favorable chemical confined microspace of carbon nanospheres endows it with excellent CO2RR activity. In the H-type cell, Ni-NCN displays a CO Faradaic efficiency up to 96.6 % and a CO current density of 9.8 mA cm-2 at -0.83 V (vs. RHE), as well as a high turnover frequency (TOF) of 10658 h-1 at -1.33 V (vs. RHE). In the flow cell, the mass transfer can be further facilitated by the formation of three-phase interface. The Faradaic efficiency and current density of CO2RR catalyzed by Ni-NCN is enhanced to 97.9 % and 102.4 mA cm-2 at -1.13 V (vs. RHE), and the wide potential window ranges from -0.53 V to -1.33 V (vs. RHE) with the Faradaic efficiency more than 95 %. Density functional theory (DFT) calculations reveal that the high selectivity of Ni-N4 sites is mainly ascribed to the high energy barrier that restrains the hydrogen evolution reaction (HER). Meanwhile, the lower CO binding energy on Ni-N4 site helps the escape of CO to increase the TOF of active sites. The in-situ Fourier transform infrared (FTIR) spectroscopy verifies that the intermediate *COOH can be more stable in the confined envi-ronment of Ni-NCN to promote the selectivity of CO2RR. The strategy of constructing confined microspace paves a new path for the rational design of high-efficient single atom catalysts for CO2 reduction.