交界质子合电子转移的供体依赖动力学
Megan N Jackson1, Yogesh Surendranath1
1Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
Journal of the American Chemical Society
|February 11, 2016
概括
质子供体结构显著影响了电催化的演变. 硬质阻碍的捐赠体减缓了黄金表面的协同质子电子转移 (CPET),影响了能量转换效率.
科学领域:
- 电化学
- 表面科学
- 催化剂
背景情况:
- 在电催化能量转换过程中,相互协调的质子电子转移 (CPET) 是至关重要的.
- 了解影响CPET运动的因素对于设计高效的催化剂至关重要.
研究的目的:
- 研究质子捐赠结构对CPET界面动力学的影响.
- 使用演化反应 (HER) 作为多晶金界面CPET速率的代理.
主要方法:
- 通过使用不同形状但相同的pKa的试基供体,研究了的演化率.
- 在酸和水性电解质中进行了运动研究.
- 分析的转移系数和H/D动态同位素效应.
主要成果:
- 三乙烯 (TEAH+) 的CPET动力比乙烯 (DIPEAH+) 快20倍.
- 在水性电解质中降低了固体效应,表明水的调解作用.
- 与DIPEAH+相比,TEAH+具有更高的转移系数 (β=0. 7) 和潜在依赖的动态同位素效应 (β=0. 4).
结论:
- 质子供体结构对CPET在固体表面的自由能量环境产生了深远的影响.
- 质子捐赠者在电催化能量转换的动力学中起着至关重要的作用.
- 溶剂效应,特别是水,可以减轻界面CPET中的硬质约束.
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