Highly efficient electroreduction of CO_(2) by defect single-atomic Ni-N_(3) sites anchored on ordered micro-macroporous carbons

作     者：Qiu-Xia Li Duan-Hui Si Wan Lin Yao-Bing Wang Hong-Jing Zhu Yuan-Biao Huang Rong Cao 

作者机构：State Key Laboratory of Structural ChemistryFujian Institute of Research on the Structure of MatterChinese Academy of SciencesFuzhou 350002China College of ChemistryFuzhou UniversityFuzhou 350108China University of the Chinese Academy of SciencesBeijing 100049China Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of ChinaFuzhou 350108China 

出 版 物：《Science China Chemistry》 (中国科学（化学英文版）)

年 卷 期：2022年第65卷第8期

页      面：1584-1593页

核心收录：

学科分类：083002[工学-环境工程] 0830[工学-环境科学与工程（可授工学、理学、农学学位）] 081705[工学-工业催化] 08[工学] 0817[工学-化学工程与技术] 0805[工学-材料科学与工程（可授工学、理学学位）] 080502[工学-材料学] 0703[理学-化学] 0702[理学-物理学] 

基　　金：supported by the National Key Research and Development Program of China(2018YFA0208600,2018YFA0704502) the National Science Foundation of China(21871263,22071245,22033008) the Youth Innovation Promotion Association,CAS(Y201850) Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(2021ZZ103) 

主　　题：metal-organic framework hierarchically ordered porous carbon Ni single atom CO_(2)electrocatalysis CO 

摘      要：Microporous supports typically fail to fully expose active sites for electrolytes and CO_(2) molecules,and this usually results in low current density for the electrocatalytic CO_(2) reduction reaction(CO_(2)RR).To overcome the biggest obstacle and facilitate commercial applications,defective single-atomic Ni-N_(3) sites anchored to ordered micro-macroporous N-doped carbon(Ni-N/OMC)have been prepared by the pyrolysis of the Ni-ZIF-8@PS(ZIF=zeolitic imidazolate framework)and are intended to provide enhanced CO_(2)RR with a current density at an industrial *** Ni-ZIF-8@PS is constructed of nickel-based ZIF-8 embedded in the three-dimensional(3D)highly ordered polystyrene spheres(PS).The 3D ordered micro-macroporous architecture of Ni-N/OMC could facilitate the mass transfer of substrates to the accessible defective single-atomic Ni-N_(3) sites through micropores(0.6 nm)and macropores(~200 nm)interconnected by 50 nm *** a flow cell,Ni-N/OMC exhibits almost 100.0%CO Faraday efficiency(FECO)between−0.2 and−1.1 V *** and an industrial level CO partial current density of 208 mA cm^(−2).It has a turnover frequency of 1.5×10^(5) h^(−1) at−1.1 V *** in 1 M KOH electrolyte,which exceeds that of most reported nickel-based *** excellent CO_(2)RR performance for Ni-N/OMC makes it a state-of-the-art electrocatalyst for CO_(2)*** calculations show that the defective Ni-N_(3) site can lower the energy of*COOH formation compared with that of the Ni-N4 site,thereby accelerating CO_(2)***-N/OMC can also be utilized as a cathodic catalyst in Zn-CO_(2) battery,exhibiting high CO selectivity in the discharge process and excellent *** work paves a pathway to rational design of highly efficient electrocatalysts with 3D hierarchically ordered micro-macroporous architecture for CO_(2)RR towards industrial production and commercial applications.