Lee Katherine J, McCarthy Brian D, Rountree Eric S, Dempsey Jillian L
Department of Chemistry, University of North Carolina , Chapel Hill, North Carolina 27599-3290, United States.
Inorg Chem. 2017 Feb 20;56(4):1988-1998. doi: 10.1021/acs.inorgchem.6b02586. Epub 2017 Feb 6.
Analysis of a cobalt bis(dithiolate) complex reported to mediate hydrogen evolution under electrocatalytic conditions in acetonitrile revealed that the cobalt complex transforms into an electrode-adsorbed film upon addition of acid prior to application of a potential. Subsequent application of a reducing potential to the film results in desorption of the film and regeneration of the molecular cobalt complex in solution, suggesting that the adsorbed species is an intermediate in catalytic H evolution. The electroanalytical techniques used to examine the pathway by which H is generated, as well as the methods used to probe the electrode-adsorbed species, are discussed. Tentative mechanisms for catalytic H evolution via an electrode-adsorbed intermediate are proposed.
对一种据报道在乙腈中电催化条件下介导析氢反应的双（二硫醇盐）钴配合物的分析表明，在施加电势之前加入酸后，钴配合物会转化为电极吸附膜。随后对该膜施加还原电势会导致膜解吸并使溶液中的分子钴配合物再生，这表明吸附物种是催化析氢反应的中间体。讨论了用于研究氢气生成途径的电分析技术以及用于探测电极吸附物种的方法。提出了通过电极吸附中间体进行催化析氢反应的初步机理。
