基于旋转圆盘-原位拉曼光谱联用技术的雌激素界面电催化微观机理研究

Exploring the efficient degradation method of environmental estrogen, one of the most important endocrine disruptors due to its low concentration, wide dispersion, high toxicity and chemical stability, is a vital issue in wastewater treatment. Electrocatalytic technology is widely applied in efficient degradation of estrogen at low concentrations owing to its high catalytic activity and mass transfer efficiency. However, there is a lack of effective method for in-situ investigation of the adsorption and catalysis mechanism for estrogen on the surface of the electrocatalytic materials. Therefore, an "in-situ rotating disk electrode coupled to Raman spectroscopy technology" is established for electrocatalytic process by using TiO2 as the electrocatalytic anode material. Then the in-situ electrochemical signal and Raman spectra during electrocatalytic process was analyzed to confirm effective electron transfer and intermediates. Combining with DFT theoretical calculations, the adsorption and catalysis mechanism of estrogen pollutants on the surface of TiO2 will be investigated. In-situ rotary disk coupled to Raman spectroscopy technology is established for electrocatalytic oxidation of estrogen pollutant. This technology will further guide the design and optimization of highly efficient electrocatalytic system for highly selective and efficient removal of environmental estrogen from wastewater, and has important social and environmental values.

探究环境雌激素这一类浓度低、毒性高、难降解的内分泌干扰素的高效降解方法是环境和化学领域的研究热点。电催化技术，由于其较高催化活性和传质效率，被广泛用于实现低浓度环境雌激素的高效降解。但是，对于雌激素在此催化转化过程的表界面微观机制，尤其是催化材料对雌激素的吸附与催化作用尚缺乏有效的原位监测手段。本项目拟在建立“旋转圆盘电化学-原位拉曼光谱联用技术”的基础上，以模式电催化剂TiO2作为电极材料，同步监测雌激素电催化降解过程中的原位电化学和拉曼光谱信号，分析其降解过程中电催化材料与雌激素间的电子转移机制及中间产物存在形态，并结合DFT理论计算解析雌激素在TiO2表面的微观吸附与催化反应机理，进而构建基于旋转圆盘-原位拉曼光谱联用技术的雌激素表界面电催化微观机理研究体系。该体系的建立将为高效、高选择性电催化去除污水中环境雌激素技术的设计和优化提供理论指导和实验支持，具有重要的学术价值及环境意义。

电催化污染物降解技术作为一种彻底去除废水中的毒性、难生物降解的有效办法，已成为污水处理工艺的一个发展趋势。旋转圆盘电极被广泛地应用于电催化污染物转化中的扩散及电子传递过程的机理研究。然而，精准地原位解析污染物在电催化剂的微观界面吸附催化作用机制不仅是解析污染物催化转化机理和优化电催化剂性能的关键，也是异相催化领域的一个重大挑战。本项目搭建了旋转圆盘电极-拉曼光谱仪联合装置，设计并优化旋转圆盘电电化学拉曼反应池，建立了原位旋转圆盘电化学-拉曼光谱技术，实现了AuAg纳米颗粒表界面4-硝基硫酚转化到4-氨基硫酚的电催化过程的实时监测，解析了该电催化过程中电子转移机制及材料的催化活性位点。其次，利用原位红外光谱微观解析污染物在材料表面的微观吸附作用，结合单颗粒荧光寿命成像的电子进一步解析了催化材料表界面的电子空穴转移机制和活性位点分布。该项目为设计更有效的纳米催化剂和优化电催化体系提供理论参考，同时为原位旋转圆盘电极电化学-拉曼光谱联用分析技术的建立实验和理论基础。