Bioinspired iron porphyrins with appended poly-pyridine/amine units for boosted electrocatalytic CO_(2) reduction reaction  

作　　者：Jinxiu Han Ni Wang Xialiang Li Haitao Lei Yabo Wang Hongbo Guo Xiaotong Jin Qingxin Zhang Xinyang Peng Xue-Peng Zhang Wei Zhang Ulf-Peter Apfel Rui Cao 

机构地区：[1]Key Laboratory of Applied Surface and Colloid Chemistry,Ministry of Education,School of Chemistry and Chemical Engineering,Shaanxi Normal University,Xi'an,710119,China [2]Ruhr-Universität Bochum,Fakultät für Chemie und Biochemie,Anorganische Chemie I Universitätsstrasse 150,44801,Bochum,Germany [3]Fraunhofer UMSICHT,Department for Electrosynthesis,46047,Oberhausen,Germany

出　　处：《eScience》2022年第6期623-631,共9页电化学与能源科学（英文）

基　　金：We are grateful for support from National Natural Science Foundation of China(21773146,22003036 and 22171176);Fok Ying-Tong Education Foundation for Outstanding Young Teachers in University,Fundamental Research Funds for the Central Universities(GK202103045 and GK202103033);Research Funds of Shaanxi Normal University,and the open fund of State Key Laboratory of Structural Chemistry.U.-P.A.thanks for the support by the Fraunhofer Internal Programs under Grant No.Attract 097-602175 and the DFG under Germany's Excellence Strategy-EXC-2033-Projektnummer 390677874“RESOLV”.

摘　　要：Developing highly efficient electrocatalysts for the CO_(2) reduction reaction(CO_(2)RR)has attracted increasing interest in the past decade.Herein,we report on the design and synthesis of Fe porphyrin 1 with an appended N,N-di(2-picolyl)ethylenediamine(DPEN)unit that boosts electrocatalytic activity for CO_(2)-to-CO conversion in acetonitrile with water as the proton source.By mimicking carbon monoxide dehydrogenase(CODH),1 has poly-pyridine/amine units located at the active site to form hydrogen-bonded water-containing networks that enable fast proton transfer.The protonated and positively charged DPEN unit can also stabilize CO_(2) reduction intermediates through electrostatic and hydrogen-bonding interactions.These factors make 1 a highly active electrocatalyst for the CO_(2)RR by achieving a TOFmax of 5.0×10^(4)s^(−1) with water providing the protons.These critical roles of the DPEN unit in the CO_(2)RR are further supported by theoretical studies.This work is significant to highlight the benefits of using molecular catalysts to elucidate structural effects.

关 键 词：CO_(2)reduction reaction Fe porphyrin Molecular electrocatalysis Structural effect Water network 

分 类 号：O643.3[理学—物理化学]