Facile Solvent-Free Synthesis of Thin Iron Porphyrin COFs on Carbon Cloth Electrodes for CO2 Reduction

被引：131

作者：

Cheung, Po Ling ^{[1
]}

Lee, Sze Koon ^{[2
,3
]}

Kubiak, Clifford P. ^{[1
]}

机构：

[1] Univ Calif San Diego, Dept Chem & Biochem, 9500 Gilman Dr,Mail Code 0358, La Jolla, CA 92093 USA

[2] Inst Mol Sci, Dept Life & Coordinat Complex Mol Sci, 5-1 Higashiyama, Okazaki, Aichi 4448787, Japan

[3] SOKENDAI Grad Univ Adv Studies, Hayama, Kanagawa 2400193, Japan

来源：

CHEMISTRY OF MATERIALS | 2019年 / 31卷 / 06期

关键词：

COVALENT-ORGANIC FRAMEWORKS; ON-SURFACE SYNTHESIS; ELECTROCHEMICAL REDUCTION; MOLECULAR CATALYSIS; METAL-FREE; NONCOVALENT IMMOBILIZATION; CO2-TO-CO CONVERSION; COBALT PORPHYRINS; OXYGEN REDUCTION; DIOXIDE;

D O I：

10.1021/acs.chemmater.8b04370

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

We demonstrate the solvent-free synthesis of a covalent organic framework (COF) containing 5,10,15,20-tetra-(4-aminophenyl)-porphyrin Fe(III) chloride (FeTAPPCl) and 2,5-dihydroxyterephthalalde-hyde (Dha) for the reduction of CO2 to CO with good turnover frequency (>600 h(-1) mol(-1) of electroactive Fe sites) and reasonable Faradaic efficiency for CO (an average of 80%) at -2.2 V (vs Ag/AgCl) over 3 h in MeCN with 0.5 M trifluoroethanol. Characterization and stability of the COFs were probed by chemical and electrochemical methods. X-ray photoelectron spectroscopy analysis of the COF showed the formation of imine bonds and hemiaminal groups. Cyclic voltammetry of FeDhaTph-COF electrodes revealed three redox couples in MeCN or N,N-dimethylformamide (DMF) systems. The Fe(II/I) and Fe(I/0) redox couples were observed at comparable potentials as FeTAPPCl in solution. Inductively coupled plasma optical emission spectroscopy results suggested that the COF network has retained FeTAPPCl molecules substantially better than simple adsorption in either MeCN or DMF solvent.

引用

页码：1908 / 1919

页数：12

共 94 条

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