A molecular cobalt hydrogen evolution catalyst showing high activity and outstanding tolerance to CO and O2
A molecular cobalt hydrogen evolution catalyst showing high activity and outstanding tolerance to CO and O2
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一种分子钴析氢催化剂，具有高活性和对 CO 和 O2 的出色耐受性
DOI：
10.1002/anie.201904578
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发表时间：
2019
期刊：
影响因子：
--
通讯作者：
Sakai Ken
中科院分区：
文献类型：
--
作者：
Wang Jia-Wei;Yamauchi Kosei;Huang Hai-Hua;Sun Jia-Kai;Luo Zhi-Mei;Zhong Di-Chang;Lu Tong-Bu;Sakai Ken
需要开发促进析氢反应（HER）的分子催化剂，其具有高催化速率和对各种抑制剂（例如CO和O2）的高耐受性。在本文中，我们报道了具有五齿大环配体（1-Co）的钴催化剂，其在pH 7.0的磷酸盐缓冲水溶液中表现出快速的催化速率（TOF=2210 s−1），其中来自磷酸二氢阴离子（H2 PO 4 −）的质子转移在催化增强中起关键作用。 该电催化剂对缓蚀剂具有很高的耐受性，在CO或空气气氛下，其活性保持率均超过90%。其对CO的高耐受性被认为是由于配体造成的几何挫折导致的不期望的CO结合物质的动力学不稳定特性引起的，这阻止了理想的三角双锥的建立。
There is a demand to develop molecular catalysts promoting the hydrogen evolution reaction (HER) with a high catalytic rate and a high tolerance to various inhibitors, such as CO and O2. Herein we report a cobalt catalyst with a penta‐dentate macrocyclic ligand (1‐Co), which exhibits a fast catalytic rate (TOF=2210 s−1) in aqueous pH 7.0 phosphate buffer solution, in which proton transfer from a dihydrogen phosphate anion (H2PO4−) plays a key role in catalytic enhancement. The electrocatalyst exhibits a high tolerance to inhibitors, displaying over 90 % retention of its activity under either CO or air atmosphere. Its high tolerance to CO is concluded to arise from the kinetically labile character of undesirable CO‐bound species due to the geometrical frustration posed by the ligand, which prevents an ideal trigonal bipyramid being established.