University of Science and Technology of Hanoi, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet, Hanoi, Vietnam.
Institute of Materials Science, Vietnam Academy of Science and Technology, 18 Hoang Quoc Viet, Hanoi, Vietnam.
Chemistry. 2019 Oct 28;25(60):13676-13682. doi: 10.1002/chem.201903098. Epub 2019 Sep 30.
Amorphous molybdenum sulfide is an attractive electrode material for Li/Mg batteries and an efficient Pt-free catalyst for the hydrogen evolution reaction in water. By using the electrochemical quartz crystal microbalance (EQCM) analysis, new insights were gained into the electrochemical polymerization of the [Mo S ] cluster, which generates amorphous molybdenum sulfide thin films. In this work, it is shown that, at the anodic potential, a two-electron oxidative elimination of the terminal disulfide ligand within the [Mo S ] cluster induces the polymerization. A reductive elimination of the terminal disulfide ligand also occurs at the cathodic potential, inducing the polymerization. However, in sharp contrast to the anodic polymerization, according to which the film growth is rapid, the cathodic polymerization competes with the electrochemical reductive corrosion of the readily grown film, therefore occurring at a significant lower growth rate.
无定形硫化钼是 Li/Mg 电池中极具吸引力的电极材料，也是水析氢反应中高效的无铂催化剂。通过电化学石英晶体微天平（EQCM）分析，我们对 [Mo S ] 簇的电化学聚合有了新的认识，该聚合会生成无定形硫化钼薄膜。在这项工作中，我们表明在阳极电势下，[Mo S ] 簇中末端二硫配体的双电子氧化消除会引发聚合。末端二硫配体也会在阴极电势下发生还原消除，从而引发聚合。然而，与阳极聚合形成鲜明对比的是，根据阳极聚合，薄膜生长迅速，阴极聚合与容易生长的薄膜的电化学还原腐蚀竞争，因此生长速度明显较慢。
