Explicating the Role of Metal Centers in Porphyrin-Based MOFs of PCN-222(M) for Electrochemical Reduction of CO_(2)  

作　　者：Mengjie Liu Mengting Peng Baoxia Dong Yunlei Teng Ligang Feng Qiang Xu 

机构地区：[1]School of Chemistry and Chemical Engineering,Yangzhou University,Yangzhou,Jiangsu 225002,China

出　　处：《Chinese Journal of Structural Chemistry》2022年第7期46-52,共7页结构化学（英文）

基　　金：financially supported by the NNSFC (No. 21671169);the Foundation from the Priority Academic Program Development of Jiangsu Higher Education Institutions。

摘　　要：The porphyrin-based MOFs formed by combining Zrclusters and porphyrin carboxylic acids with clear M-Nactive centers show unique advantages in electrocatalytic reduction of CO(CORR). However, its conductivity is still the bottleneck that limits its catalytic activity due to the electrical insulation of the Zr cluster. Therefore, the porphyrin-based MOFs of PCN-222(M)(M = Mn, Co, Ni, Zn) with explicit M-Ncoordination were combined with the highly conductive material carbon nanotube(CNT) for discussing the influence of metal centers on the CORR performance based on theoretical calculations and experimental observations. The results show that the PCN-222(Mn)/CNT, PCN-222(Co)/CNT, and PCN-222(Zn)/CNT all exhibit high selectivity to CO(FECO > 80%) in the range of-0.60 to-0.70 V vs. RHE. The FECOmax of PCN-222(Mn)/CNT(-0.60 V vs. RHE), PCN-222(Co)/CNT(-0.65 V vs. RHE), and PCN-222(Zn)/CNT(-0.70 V vs.RHE) are 88.5%, 89.3% and 92.5%, respectively. The high catalytic activity of PCN-222(Mn)/CNT and PCN-222(Co)/CNT comes from the excellent electron mobility of their porphyrin rings and their low ΔG*COOH(0.87 and 0.58 eV). It reveals that the strength of backbonding π of the transition metal and its influence on the electron mobility in the porphyrin ring can affect its CORR activity.

关 键 词：PCN-222 electrochemical reduction of CO_(2) DFT calculation MOFS 

分 类 号：O643.36[理学—物理化学]