期刊
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 136, 期 39, 页码 13727-13734出版社
AMER CHEMICAL SOC
DOI: 10.1021/ja505845t
关键词
-
Molecular catalysis of H-2 production from the electrochemical reduction of acids by transition-metal complexes is one of the key issues of modern energy challenges. The question of whether it proceeds heterolytically (through reaction of an initially formed metal hydride with the acid) or homolytically (through symmetrical coupling of two molecules of hydride) has to date received inconclusive answers for a quite simple reason: the theoretical bases for criteria allowing the distinction between homolytic and heterolytic pathways in nondestructive methods such as cyclic voltammetry have been lacking heretofore. They are provided here, allowing the distinction between the two pathways. The theoretical predictions and the diagnosing strategy are illustrated by catalysis of the reduction of phenol, acetic acid, and protonated triethylamine by electrogenerated iron(0) tetraphenylporphyrin. Rather than being an intrinsic property of the catalytic system, the occurrence of either a heterolytic or a homolytic pathway results from their competition as a function of the concentrations of acid and catalyst and the rate constants for hydride formation and H-2 evolution by hydride protonation or dimerization.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据