Molecular modulating of cobalt phthalocyanines on aminofunctionalized carbon nanotubes for enhanced electrocatalytic CO_(2)conversion  

作　　者：Huajian Xu Huizhu Cai Linxia Cui Limei Yu Rui Gao Chuan Shi 

机构地区：[1]State Key Laboratory of Fine Chemicals,College of Chemical Engineering,Dalian University of Technology,Dalian 116024,China [2]College of Chemistry and Chemical Engineering,Inner Mongolia University,Hohhot 010021,China

出　　处：《Nano Research》2023年第3期3649-3657,共9页纳米研究（英文版）

基　　金：supported by the National Natural Science Foundation of China(Nos.21872014,21932002,21902018,21962013,and 22172083);the National Key Research and Development(R&D)Program of China(No.2017YFA0700103);the Fundamental Research Funds for the Central Universities(No.DUT20ZD205);the Natural Science Foundation of Liaoning Province(No.2019-MS-053);the Liaoning Revitalization Talent Program(No.XLYC2008032).

摘　　要：Metal porphyrins and metal phthalocyanines(Pc)constitute a promising class of metal molecular catalysts(MMCs)for efficient CO_(2)-to-CO electrocatalytic conversion due to their well-defined molecular structures.How to adjust the local coordination and electronic environment of the metal center and enhance the molecular-level dispersion of the active components remains as great challenges for further improving the performance.Herein,a cobalt(II)Pc(CoPc)-COOH/carbon nanotube(CNT)-NH_(2)hybrid catalyst was rationally designed by clicking the CoPc-COOH molecules onto the surface of CNT-NH_(2)through amidation reaction.This novel hybrid catalyst exhibited the enhanced current density of 22.4 mA/cm2 and CO selectivity of 91%at−0.88 V vs.reversible hydrogen electrode(RHE)in the CO_(2)electroreduction,as compared with CoPc-COOH/CNT and CoPc/CNT samples.The superior activity was ascribed to the charge transfer induced by introduction of-COOH and-NH_(2)functional groups to CoPc and CNT,respectively,facilitating the active centers of CoI being generated at lower potentials,and leading to the highest turnover frequency(TOF)being obtained over the CoPc-COOH/CNT-NH_(2)hybrid catalyst.The inherent directivity and saturability of covalent bonds formed via the amidation reaction ensure not only a higher density of Co active centers,but also an improved stability for CO_(2)reduction reaction(CO_(2)RR).The present study represents an effective strategy for improving MMCs performance by molecular modulating of metal phthalocyanines on functionalized carbon substrates directed by click confinement chemistry.

关 键 词：electrocatalytic CO_(2)reduction cobalt tetracarboxylphthalocyanine amino functionalized carbon nanotubes AMIDATION 

分 类 号：O64[理学—物理化学]