P-functionalized carbon nanotubes promote highly stable electrocatalysts based on Fe-phthalocyanines for oxygen reduction: Experimental and computational studies  

作　　者：Beatriz Martinez-Sanchez Diego Cazorla-Amors Emilia Morallon 

机构地区：[1]Departamento de Quimica Fisica and Instituto Universitario de Materiales de Alicante(IUMA)University of Alicante,Ap.99.03080 Alicante,Spain [2]Departamento de Quimica Inorganica and Instituto Universitario de Materiales de Alicante(IUMA),University of Alicante,Ap.99,03080 Alicante,Spain

出　　处：《Journal of Energy Chemistry》2022年第9期276-290,I0008,共16页能源化学（英文版）

基　　金：the Ministry of Science,Innovation and Universities of Spain for the FPU grant(FPU18/05127);MCI/AEI and FEDER,UE(PID2019-105923RB-I00,RTI2018-095291-B-I00 projects)for the financial support。

摘　　要：Iron(Ⅱ) phthalocyanines(FePc) supported on functionalized nanostructured carbon materials have been studied as electrocatalysts for the oxygen reduction reaction(ORR) in an alkaline medium. Herein, two types of carbon nanotubes(CNTs) have been explored as support, Single-Walled Carbon Nanotubes and Herringbone Carbon Nanotubes(SWCNTs and h CNTs, respectively), both electrochemically modified with ortho-aminophenylphosphonic acid(2APPA), which provides phosphate axial coordinating ligands for the immobilization of FePc molecules. All the catalysts were prepared via a facile incipient wetness impregnation method. Comprehensive experimental analysis together with density functional theory(DFT) calculations has demonstrated both the importance of the five-coordinated Fe macrocycles that favor the interaction between the FePc and the carbon support, as well as the effect of the CNT structure in the ORR. FePc axial coordination provides a better dispersion, leading to higher stability and a favorable electron redistribution that also tunes the ORR performance by lowering the stability of the reaction intermediates. Interestingly, such improvement occurs with a very low content of metal(~1 wt% Fe),which is especially remarkable when h CNT support is employed. This work provides a novel strategy for the development of Fe-containing complexes as precious metal-free catalysts towards the ORR.

关 键 词：Carbon nanotubes Iron phthalocyanine Oxygen reduction ELECTROCATALYSIS Axial ligand 

分 类 号：X382[环境科学与工程—环境工程] TQ426[化学工程]