建模潜在依赖的电化学激活障碍:回顾性进化反应
Jiang Li1,2, Joakim Halldin Stenlid1,2, Thomas Ludwig1,2
1SUNCAT Center for Interface Science and Catalysis, Department of Chemical Engineering, Stanford University, Stanford, California 94305, United States.
Journal of the American Chemical Society
|November 9, 2021
概括
我们开发了一种新的分析方法, 精确模拟电化学激活障碍, 这种方法解释了溶剂的波动,显著提高了当前的演化反应 (HER) 预测.
科学领域:
- 计算化学
- 电催化
- 表面科学
背景情况:
- 精确模拟电化学激活障碍对于催化剂设计至关重要.
- 像DFT这样的现有方法面临着不断的潜力,时间尺度和溶剂波动的挑战.
- 计算成本和可疑的结果阻碍了对接口的潜在依赖障碍的建模.
研究的目的:
- 开发一种可计算的分析方法来模拟潜在依赖激活障碍.
- 在电极-溶剂接口上明确包括溶剂的热波动.
- 准确地建模电催化反应的微动力学,使用演化反应 (HER) 作为基准.
主要方法:
- 开发了基于电荷保存和脱的潜在能量表面的分析方法.
- 模拟不同电位的电化学过程,包括溶剂的热波动.
- 模拟Pt催化性HER,考虑金属表面和溶剂层之间的空间波动.
主要成果:
- 该方法可以在不同的电位下模拟电化学过程,并包括溶剂波动.
- 水与金属之间的距离波动对电荷转移障碍产生重大影响.
- 与静态溶剂模型相比,统计波动增加了预测的HER电流数个数量级.
- 模拟了HER机制的趋势,并获得了与实验数据质量一致的理论I-V曲线.
结论:
- 开发的分析方法提供了电化学激活障碍的精确理论模拟.
- 这种方法成功地模拟了电触媒中的电位依赖性障碍和溶剂效应.
- 这项工作为设计先进的电催化剂提供了更可靠,更高效的计算工具.
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