文献类型：期刊文献

英文题名：Building a stable cationic molecule/electrode interface for highly efficient and durable CO2 reduction at an industrially relevant current

作者：Su, Jianjun[1];Zhang, Jun-Jie[2,3];Chen, Jiacheng[4];Song, Yun[1];Huang, Libei[1];Zhu, Minghui[4];Yakobson, Boris I.[2,3];Tang, Ben Zhong[5,6,7,8];Ye, Ruquan[1,9]

机构：[1]City Univ Hong Kong, Dept Chem, State Key Lab Marine Pollut, Hong Kong 999077, Peoples R China;[2]Rice Univ, Dept Mat Sci & Nano Engn, 6100 Main St, Houston, TX 77005 USA;[3]Rice Univ, Dept Chem, 6100 Main St, Houston, TX 77005 USA;[4]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China;[5]Hong Kong Univ Sci & Technol, Chinese Natl Engn Res Ctr Tissue Restorat & Recon, Hong Kong Branch, Dept Chem,Kowloon, Clear Water Bay, Hong Kong 999077, Peoples R China;[6]Hong Kong Univ Sci & Technol, Inst Adv Study, SCUT HKUST Joint Res Inst, Kowloon, Clear Water Bay, Hong Kong 999077, Peoples R China;[7]HKUST Shenzhen Res Inst, 9 Yuexing 1st Rd,Hitech Pk, Shenzhen 518057, Peoples R China;[8]South China Univ Technol, Ctr Aggregat Induced Emiss, State Key Lab Luminescent Mat & Devices, Guangzhou 510640, Peoples R China;[9]City Univ Hong Kong, Shenzhen Res Inst, Shenzhen 518057, Guangdong, Peoples R China

年份：2021

卷号：14

期号：1

起止页码：483

外文期刊名：ENERGY & ENVIRONMENTAL SCIENCE

收录：;EI(收录号：20210709906821);WOS:【SCI-EXPANDED(收录号:WOS:000611850000026)】；

基金：This work was supported by the Hong Kong Research Grant Council under Early Career Scheme (Project No. 21300620), Young Scientists Fund of the National Natural Science Foundation of China (Project No. 21905240), and the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning and Shanghai Sailing Program (19YF1410600). Work at Rice (J. Z. and B. I. Y.) was supported by the National Science Foundation (CBET-1605848).

语种：英文

外文关键词：Catalysts - Leaching - Cobalt compounds - Grafting (chemical) - Alkylation - Current density - Molecules - Reaction intermediates - Yarn

摘要：Aggregation and leaching are two major obstacles to the synthesis of efficient and durable heterogeneous molecular catalysts. These problems are even more severe for charged molecules, not only resulting in unsatisfactory performance, but also leading to misleading evaluation of charged functionalities. In this work, methylation of cobalt(ii) tetraamino phthalocyanine (CoTAPc) transforms its electron-donating amino groups into electron-withdrawing quaternary ammonium cations, which favor the formation of *COOH intermediate and the desorption of *CO; this is conducive to a 130% increase of the current density for the CO2 reduction reaction (CO2RR). However, the catalysts leach severely; consequently, the current density decays rapidly. To resolve this dilemma, we developed an in situ functionalization strategy by first covalently grafting CoTAPc onto carbon nanotubes via a diazo-reaction, followed by a complete methylation reaction. This is conducive to a 700% increase in CO partial current density compared to that of a physically mixed sample at -0.72 V vs. RHE with highly stable currents. In a flow cell, this covalently immobilized structure delivers an industrially relevant current density of 239 mA cm(-2), CO selectivity of 95.6% at 590 mV overpotential and very low molecular loading of 0.069 mg cm(-2). This work provides mechanistic insight and a design strategy for charged molecular catalysts for high-performance and stable heterogeneous electrolysis.