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在电化学模型中,温度效应是经常被忽略的重要参量.本文采用最近发展的经典分子动力学和第一性原理杂化方法研究了室温下Pt(111)电极在0.77 mol/L NaClO_4电解质溶液中的零电荷电极电势(PZC).分子动力学结果表明,ClO_4~-弱吸附于Pt(111)表面,而Na~+则分布在整个溶液中.基于分子动力学的轨迹,第一性原理计算得到的平均PZC相对于标准氢电极为0.57 V.相较于无限稀溶液,该值正移了0.33 V.这一结果归结于ClO_4~-的弱吸附,并且趋势和实验测量值一致.计算结果同时表明,暂态PZC呈标准方差为0.60 V的准正态分布.电解质和溶剂的热运动是引起这一分布的原因.本文中的理论结果有助于深入了解双电层结构以及电催化剂的设计.
In the electrochemical model, the temperature effect is an important parameter that is often neglected.In this paper, we use the recent development of classical molecular dynamics and first-principles hybridization to study the electrochemical behavior of Pt (111) electrode in a 0.77 mol / L NaClO_4 electrolyte solution (PZC). The molecular dynamics results show that ClO 4 ~ - weakly adsorbs on the surface of Pt (111) and Na ~ + distributes in the solution. Based on the molecular dynamics trajectories, the first principle The calculated mean PZC is 0.57 V relative to the standard hydrogen electrode, which is shifted by 0.33 V compared to the infinity dilute solution. This result is due to the weak adsorption of ClO 4 - and the trend is in agreement with the experimental measurements. The results also show that the transient PZC has a standard deviation of 0.60 V quasi-normal distribution.The thermal motions of electrolytes and solvents are responsible for this distribution.The theoretical results in this paper will help to understand the electrical double layer structure and the electrocatalyst the design of.