Bisulfate as a redox-active ligand in vanadium-based electrocatalysis for CH 4 functionalization
Bisulfate as a redox-active ligand in vanadium-based electrocatalysis for CH 4 functionalization
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硫酸氢盐作为钒基电催化 CH 4 功能化的氧化还原活性配体
DOI：
10.1039/d1cc06596c
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发表时间：
2022
影响因子：
4.9
通讯作者：
Liu, Chong
中科院分区：
文献类型：
--
作者：
Xiang, Danlei;Lin, Sheng-Chih;Deng, Jiao;Chen, Hao Ming;Liu, Chong
尽管有计算预测，但不可饶恕的硫酸溶剂在分子催化剂活化CH4中的作用还没有得到很好的实验说明。在这里，我们提供了由H_2SO_4溶剂引入的金属结合硫酸配体在最近发现的钒基电催化CH4活化中具有氧化还原活性的实验证据。在前催化剂钒(V)-氧二聚体中，用氧化还原惰性磷酸二氢盐取代两个末端硫酸氢配体中的一个，可以完全熄灭其对CH4的活性，这可能会激发出环境友好的催化反应，而最少使用H_2SO_4。
The roles of unforgiving H2SO4 solvent in CH4 activation with molecular catalysts have not been experimentally well-illustrated despite computational predictions. Here, we provide experimental evidence that metal-bound bisulfate ligand introduced by H2SO4 solvent is redox-active in vanadium-based electrocatalytic CH4 activation discovered recently. Replacing one of the two terminal bisulfate ligands with redox-inert dihydrogen phosphate in the pre-catalyst vanadium (V)-oxo dimer completely quenches its activity towards CH4, which may inspire environmentally benign catalysis with minimal use of H2SO4.