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Significantly improved electrocatalytic oxygen reduction by an asymmetrical Pacman dinuclear cobalt(ii) porphyrin-porphyrin dyad
文献类型：期刊
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 CoII triphenylporphyrin-tri(pentafluorophenyl)porphyrin 1 and dinuclear CoII 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 CoII tetra(pentafluorophenyl)porphyrin 3 and CoII tetraphenylporphyrin 4 for the four-electron electrocatalytic reduction of ...More
Pacman dinuclear CoII triphenylporphyrin-tri(pentafluorophenyl)porphyrin 1 and dinuclear CoII 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 CoII tetra(pentafluorophenyl)porphyrin 3 and CoII tetraphenylporphyrin 4 for the four-electron electrocatalytic reduction of O2 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 CoIII/CoII 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: CoII-TPFP is likely the O2 binding and reduction site, while CoIII-TPP, which is generated by the oxidation of CoII-TPP on electrodes, may function as a Lewis acid to assist the O2 binding and activation. The positively charged CoIII-TPP will have through-space charge interactions with the negatively charged O2-adduct unit, which will reduce the activation energy barrier for the ORR. This effect of Co-TPP closely resembles that of the CuB site of metalloenzyme cytochrome c oxidase (CcO), which catalyzes the biological reduction of O2. This work represents a rare example of asymmetrical dinuclear metal catalysts, which can catalyze the 4e reduction of O2 with high selectivity and significantly improved activity.This journal is ? The Royal Society of Chemistry 2020. ...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
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