Identification of the activity source of CO2 electroreduction by strategic catalytic site distributi

• 作 者: Sheng-Nan Sun Ning Li Jiang Liu Wen-Xin Ji Long-Zhang Dong Yi-Rong Wang Ya-Qian Lan
• 机 构: Jiangsu Collaborative Innovation Centre of Biomedical Functional Materials,Jiangsu Key Laboratory of
• 出 处: 国家科学评论（英文版）
• 发表日期: 2021年3期
• 关键词: strategic catalytic site distribution supramolecular structure system active sou

Identification of the real catalytic site in CO2 reduction reaction(CO2RR)is critical for the rational design of catalysts and the understanding of reactive mechanisms.In this study,the catalytic activity of pyridine-containing materials was for the first time structurally demonstrated in CO2RRby crystalline supramolecular coordination compounds model system.The system consists of three stable supramolecular coordination compounds(Ni-TPYP,Ni-TPYP-1 and Ni-TPP)with different numbers(4,2 and 0)of active pyridine groups(i.e.uncoordinated pyridine nitrogen atoms).The electrocatalytic test results show that with the decrease of the number of active pyridine groups,the CO2RR performance is gradually reduced,mainly showing the reduction of highest FEco(99.8％,83.7％and 25.6％,respectively).The crystallographic,experimental and theoretical evidences prove that the CO2RR activity is more likely derived from uncoordinated pyridine nitrogen than the electrocatalytic inert metal nickel in porphyrin center.This work serves as an important case study for the identification of electrocatalytic activity of pyridine-containing materials in CO2RR by simple supramolecular model system.