不对称“吃豆人”双核钴(II)卟啉-卟啉二元体显著改善电催化氧还原性能

Significantly improved electrocatalytic oxygen reduction by an asymmetrical Pacman dinuclear cobalt(ii) porphyrin-porphyrin dyad.

作者信息

Liu Yanju, Zhou Guojun, Zhang Zongyao, Lei Haitao, Yao Zhen, Li Jianfeng, Lin Jun, Cao Rui

机构信息

Key Laboratory of Applied Surface and Colloid Chemistry , Ministry of Education , School of Chemistry and Chemical Engineering , Shaanxi Normal University , Xi'an 710119 , China . Email:

Department of Chemistry , Renmin University of China , Beijing 100872 , China.

出版信息

Chem Sci. 2019 Nov 4;11(1):87-96. doi: 10.1039/c9sc05041h. eCollection 2020 Jan 7.

Abstract

Pacman dinuclear Co triphenylporphyrin-tri(pentafluorophenyl)porphyrin and dinuclear Co bis-tri(pentafluorophenyl)porphyrin , anchored at the two -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 tetra(pentafluorophenyl)porphyrin and Co tetraphenylporphyrin for the four-electron electrocatalytic reduction of O to water. Significantly, although the ORR selectivities of the two dinuclear Co bisporphyrins are similar to each other, outperforms , in terms of larger catalytic ORR currents and lower overpotentials. Electrochemical studies showed different redox behaviors of the two Co sites of : the Co/Co 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-TPFP is likely the O binding and reduction site, while Co-TPP, which is generated by the oxidation of Co-TPP on electrodes, may function as a Lewis acid to assist the O binding and activation. The positively charged Co-TPP will have through-space charge interactions with the negatively charged O-adduct unit, which will reduce the activation energy barrier for the ORR. This effect of Co-TPP closely resembles that of the Cu site of metalloenzyme cytochrome oxidase (CO), which catalyzes the biological reduction of O. This work represents a rare example of asymmetrical dinuclear metal catalysts, which can catalyze the 4e reduction of O with high selectivity and significantly improved activity.

摘要

合成了固定在苯连接体两个位置上的“吃豆人”双核钴三苯基卟啉 - 三(五氟苯基)卟啉和双核钴双 - 三(五氟苯基)卟啉,并将其作为氧还原反应(ORR)的电催化剂进行了研究。对于将O四电子电催化还原为水,这两种双核钴双卟啉都比相应的单核钴四(五氟苯基)卟啉和钴四苯基卟啉更高效、更具选择性。值得注意的是,尽管这两种双核钴双卟啉的ORR选择性彼此相似,但在更大的催化ORR电流和更低的过电位方面,[具体物质]优于[另一物质]。电化学研究表明[具体物质]的两个钴位点具有不同的氧化还原行为:钴 - TPP(TPP = 三苯基卟啉)位点的Co/Co还原比钴 - TPFP(TPFP = 三(五氟苯基)卟啉)位点落后440 mV。这种差异表明它们在ORR中具有不同的作用:钴 - TPFP可能是O结合和还原位点,而电极上钴 - TPP氧化产生的钴 - TPP可能作为路易斯酸来辅助O的结合和活化。带正电荷的钴 - TPP将与带负电荷的O - 加合物单元产生空间电荷相互作用,这将降低ORR的活化能垒。钴 - TPP的这种效应与金属酶细胞色素c氧化酶(CO)的铜位点的效应非常相似,后者催化O的生物还原。这项工作代表了不对称双核金属催化剂的一个罕见例子,其可以高选择性地催化O的4e还原并显著提高活性。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/b881/7012046/a56310217a2f/c9sc05041h-s1.jpg

文献AI研究员

20分钟写一篇综述,助力文献阅读效率提升50倍

立即体验

用中文搜PubMed

大模型驱动的PubMed中文搜索引擎

马上搜索