Modeling Mechanochemical Reaction Mechanisms
Modeling Mechanochemical Reaction Mechanisms
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DOI：
10.1021/acsami.7b05440
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发表时间：
2017-08-09
影响因子：
9.5
通讯作者：
Tysoe, Wilfred T.
中科院分区：
文献类型：
--
作者：
Adams, Heather;Miller, Brendan P.;Tysoe, Wilfred T.
在超高真空条件下，研究了铜与二甲基二硫醚的机械力化学反应。通过快速S-S键断裂引发反应以形成吸附的甲基硫醇盐物种，并且通过两个随后的基本机械化学反应步骤再现反应动力学，即甲基硫醇盐的机械化学分解以在表面上存款硫并形成小的气相烃，以及通过硫再生空反应位点的滑动诱导的铜氧化。稳态反应动力学监测原位从摩擦力的变化，作为反应的进行和建模使用的基本步骤的反应速率常数发现单层吸附。的分析产生极好的协议之间的实验和动力学模型，以及正确预测的总金额使用俄歇能谱测量的膜和硫的深度分布角分辨X射线光电子能谱测量的次表面硫。
The mechanochemical reaction between copper and dimethyl disulfide is studied under well-controlled conditions in ultrahigh vacuum (UHV). Reaction is initiated by fast S-S bond scission to form adsorbed methyl thiolate species, and the reaction kinetics are reproduced by two subsequent elementary mechanochemical reaction steps, namely a mechanochemical decomposition of methyl thiolate to deposit sulfur on the surface and evolve small, gas-phase hydrocarbons, and sliding-induced oxidation of the copper by sulfur that regenerates vacant reaction sites. The steady-state reaction kinetics are monitored in situ from the variation in the friction force as the reaction proceeds and modeled using the elementary-step reaction rate constants found for monolayer adsorbates. The analysis yields excellent agreement between the experiment and the kinetic model, as well as correctly predicting the total amount of subsurface sulfur in the film measured using Auger spectroscopy and the sulfur depth distribution measured by angle-resolved X-ray photoelectron spectroscopy.