文献详情
Significantly improved electrocatalytic oxygen reduction by an asymmetrical Pacman dinuclear cobalt(ii) porphyrin-porphyrin dyad
文献类型：期刊
通讯作者：Cao, R (reprint author), Shaanxi Normal Univ, Key Lab Appl Surface & Colloid Chem, Minist Educ, Sch Chem & Chem Engn, Xian 710119, Shaanxi, Peoples R China.
期刊名称：CHEMICAL SCIENCE影响因子和分区
年：2020
卷：11
期：1
页码：87-96
ISSN：2041-6520
所属部门：化学系
摘要：Pacman dinuclear Co-II triphenylporphyrin-tri(pentafluorophenyl)porphyrin 1 and dinuclear Co-II bis-tri(pentafluorophenyl)porphyrin 2, anchored at the two meso-positions of a benzene linker, are synthesized and examined as electrocatalysts for the oxygen reduction reaction (ORR). Both dinuclear Co bisporphyrins are more efficient and selective than corresponding mononuclear Co-II tetra(pentafluorophenyl)porphyrin 3 and Co-II tetraphenylporphyrin 4 for the four-electron electrocatalytic reduction ...More
Pacman dinuclear Co-II triphenylporphyrin-tri(pentafluorophenyl)porphyrin 1 and dinuclear Co-II bis-tri(pentafluorophenyl)porphyrin 2, anchored at the two meso-positions of a benzene linker, are synthesized and examined as electrocatalysts for the oxygen reduction reaction (ORR). Both dinuclear Co bisporphyrins are more efficient and selective than corresponding mononuclear Co-II tetra(pentafluorophenyl)porphyrin 3 and Co-II tetraphenylporphyrin 4 for the four-electron electrocatalytic reduction of O-2 to water. Significantly, although the ORR selectivities of the two dinuclear Co bisporphyrins are similar to each other, 1 outperforms 2, in terms of larger catalytic ORR currents and lower overpotentials. Electrochemical studies showed different redox behaviors of the two Co sites of 1: the Co-III/Co-II reduction of the Co-TPP (TPP = triphenylporphyrin) site is well-behind that of the Co-TPFP (TPFP = tri(pentafluorophenyl)porphyrin) site by 440 mV. This difference indicated their different roles in the ORR: Co-II-TPFP is likely the O-2 binding and reduction site, while Co-III-TPP, which is generated by the oxidation of Co-II-TPP on electrodes, may function as a Lewis acid to assist the O-2 binding and activation. The positively charged Co-III-TPP will have through-space charge interactions with the negatively charged O-2-adduct unit, which will reduce the activation energy barrier for the ORR. This effect of Co-TPP closely resembles that of the Cu-B site of metalloenzyme cytochrome c oxidase (CcO), which catalyzes the biological reduction of O-2. This work represents a rare example of asymmetrical dinuclear metal catalysts, which can catalyze the 4e reduction of O-2 with high selectivity and significantly improved activity. ...Hide

DOI：10.1039/c9sc05041h
百度学术：Significantly improved electrocatalytic oxygen reduction by an asymmetrical Pacman dinuclear cobalt(ii) porphyrin-porphyrin dyad
语言：外文
人气指数：1
浏览次数：1
基金："Thousand Talents Program" of China; Fok Ying-Tong Education Foundation for Outstanding Young Teachers in University; National Natural Science Foundation of ChinaNational Natural Science Foundation of China [21101170, 21573139, 21773146]; Fundamental Research Funds for the Central UniversitiesFundamental Research Funds for the Central Universities; Shaanxi Normal University
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