文献类型：期刊文献

英文题名：Axial Ligand Coordination Tuning of the Electrocatalytic Activity of Iron Porphyrin Electrografted onto Carbon Nanotubes for the Oxygen Reduction Reaction

作者：Zhou, Xin-You[1];Xu, Chao[1];Guo, Peng-Peng[1];Sun, Wei-Li[1];Wei, Ping-Jie[1];Liu, Jin-Gang[1]

机构：[1]East China Univ Sci & Technol, Key Lab Adv Mat, Sch Chem & Mol Engn, Shanghai 200237, Peoples R China

年份：2021

卷号：27

期号：38

起止页码：9898

外文期刊名：CHEMISTRY-A EUROPEAN JOURNAL

收录：;EI(收录号：20212210416519);WOS:【SCI-EXPANDED(收录号:WOS:000654458900001)】；

基金：This study was financially supported by the National Nature Science Foundation of China (grants no. 21571062, 21271072 to J.G.L.) and the Program for Professor of Special Appointment (Eastern Scholar) at the Shanghai Institutions of Higher Learning (to J.G.L.), and the Fundamental Research Funds for the Central Universities (No. 222201717003)

语种：英文

外文关键词：covalent immobilization; electrochemistry; energy conversion; iron porphyrin; oxygen reduction reaction

摘要：The oxygen reduction reaction (ORR) is essential in many life processes and energy conversion systems. It is desirable to design transition metal molecular catalysts inspired by enzymatic oxygen activation/reduction processes as an alternative to noble-metal-Pt-based ORR electrocatalysts, especially in view point of fuel cell commercialization. We have fabricated bio-inspired molecular catalysts electrografted onto multiwalled carbon nanotubes (MWCNTs) in which 5,10,15,20-tetra(pentafluorophenyl) iron porphyrin (iron porphyrin FeF20TPP) is coordinated with covalently electrografted axial ligands varying from thiophene to imidazole on the MWCNTs' surface. The catalysts' electrocatalytic activity varied with the axial coordination environment (i. e., S-thiophene, N-imidazole, and O-carboxylate); the imidazole-coordinated catalyst MWCNTs-Im-FeF20TPP exhibited the highest ORR activity among the prepared catalysts. When MWCNT-Im-FeF20TPP was loaded onto the cathode of a zinc-air battery, an open-cell voltage (OCV) of 1.35 V and a maximum power density (P-max) of 110 mW cm(-2) were achieved; this was higher than those of MWCNTs-Thi-FeF20TPP (OCV=1.30 V, P-max=100 mW cm(-2)) and MWCNTs-Ox-FeF20TPP (OCV=1.28 V, P-max=86 mW cm(-2)) and comparable with a commercial Pt/C catalyst (OCV=1.45 V, P-max=120 mW cm(-2)) under similar experimental conditions. This study provides a time-saving method to prepare covalently immobilized molecular electrocatalysts on carbon-based materials with structure-performance correlation that is also applicable to the design of other electrografted catalysts for energy conversion.