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取决于pH的Fe (III) 规化和协同的质子电子转移机制加速S (IV) 在空气水界面的氧化
Xiaomeng Zhang1,2,3, Jiarong Liu4, Hao Li2,3
1State Key Laboratory of Advanced Environmental Technology, Institute of Urban Environment, Chinese Academy of Sciences, Xiamen 361021, China.
Journal of the American Chemical Society
|February 13, 2026
概括
由于界面效应,硫酸盐 (S(IV)) 的铁催化氧化在微滴中更快. 较低的pH值通过特定的铁物种化和协调的质子电子转移机制增强了这种反应.
科学领域:
- 大气化学 大气化学
- 化学动力学 化学动力学
- 环境科学 环境科学
背景情况:
- (III) 催化氧化 (IV) 对于硫循环和大气气溶形成至关重要.
- 微滴表面的机制和加速动力学尚不清楚.
研究的目的:
- 阐明Fe (III) 催化S (IV) 氧化在微滴中的反应机制和界面加速度.
- 调查pH和铁物种化在这个过程中的作用.
主要方法:
- 波恩-奥本海默分子动力学 (BOMD) 模拟的集成.
- 电子偏磁共振 (EPR) 光谱学实验.电子偏磁共振 (EPR) 光谱学实验.
主要成果:
- 与溶液阶段相比,在空气-水界面的SO3·-基生成中观察到数量级的增强.
- 界面加速度随着pH值的下降而增加,这是由自由能量计算和EPR信号强度所支持的.
- 确定了在低pH下高度反应性的Fe(III) 变异是主要的驱动因素,而不是Fe(III) 溶解度.
- 建立了一个新的协同质子电子转移 (CPET) 机制.
结论:
- 在微滴中Fe (III) 催化S (IV) 氧化的高效率是由界面效应和在低pH下特定的Fe (III) 变异驱动的.
- CPET机制解释了加速的动力学.
- 过渡金属离子的pH依赖性物种化是大气硫酸盐气溶形成和硫循环的关键,低估的因素.
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