在非缓冲溶液中解表面联质子电子转移:向通用电压计pH电极
Journal of the American Chemical Society
|December 12, 2018
概括
这项研究研究了未缓冲溶液中添加钻石电极的电化学. 一种脉冲电量测量技术可以实现普适的两电子/两质子纳尔斯蒂安通路用于pH传感.
科学领域:
- 电化学
- 表面科学
- 分析化学
背景情况:
- 在缓冲溶液中,昆的质子合电子转移 (PCET) 已被很好地理解.
- 在非缓冲解决方案中的行为是复杂的,限制了通用应用.
- 开发基于子的电压pH电极需要了解PCET在不同的环境中.
研究的目的:
- 调查表面结合的金在添加钻石 (BDD) 电极上的电压反应.
- 在缓冲和非缓冲溶液中实现通用两电子/两质子 (2e-/2H+) 纳尔斯蒂安通路的pH传感.
- 探索局部pH变化对低表面覆盖面的氧还原电化学的影响.
主要方法:
- 使用激光切除将子集成到BDD电极上.
- 在缓冲和非缓冲条件下进行电压测量分析.
- 拉维伦分析以确定电子转移 (ET) 速率常数.
- 使用脉冲电压测量来减轻局部pH的影响.
主要成果:
- 在所有pH值的缓冲条件下观察到单波和2e-/2H+通路.
- 由于局部pH值的变化,在没有缓冲的条件下,在中性pH值范围 (6-8) 中观察到偏离缓冲的行为.
- 减少表面覆盖率可以最大限度地减少,但不能消除局部pH影响.
- 在低表面覆盖率的非缓冲溶液中,脉冲电压测量成功产生了Nernstian 2e-/2H+反应.
结论:
- 局部pH变化对未缓冲溶液中的氧还原电化学有显著影响,即使表面覆盖率很低.
- 脉冲电压测量是一种可行的技术,可以克服这些局限性,并实现通用pH传感响应.
- 开发的方法有望为各种应用制造强大的基电压pH电极.
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