Cho Min, Chung Hyenmi, Choi Wonyong, Yoon Jeyong
School of Chemical Engineering, College of Engineering, Seoul National University, San 56-1, Sillim-dong, Gwanak-gu, Seoul 151-742, South Korea.
Water Res. 2004 Feb;38(4):1069-77. doi: 10.1016/j.watres.2003.10.029.
The biocidal action of the TiO2 photocatalyst has been now well recognized from massive experimental evidences, which demonstrates that the photocatalytic disinfection process could be technically feasible. However, the understanding on the photochemical mechanism of the biocidal action largely remains unclear. In particular, the identity of main acting photooxidants and their roles in the mechanism of killing microorganisms is under active investigation. It is generally accepted that reactive oxygen species (ROS) and OH radicals play the role. The aim of this study is to determine how the OH radical, acting either independently or in collaboration with other ROS, is quantitatively related to the inactivation of E. coli. The steady-state concentrations of OH radicals ([*OH]ss) in UV-illuminated TiO2 suspensions could be quantified from the measured photocatalytic degradation rates of p-chlorobenzoic acid (a probe compound) and its literature bimolecular rate constant with OH radicals. The results demonstrated an excellent linear correlation between [*OH]ss and the rates of E. coli inactivation, which indicates that the OH radical is the primary oxidant species responsible for inactivating E. coli in the UV/TiO2 process. The CT value of OH radical for achieving 2 log E. coli inactivation was initially found to be 0.8x10(-5) mg min/l, as predicted by the delayed Chick-Watson model. Although the primary role of OH radicals in photocatalytic disinfection processes has been frequently assumed, this is the first quantitative demonstration that the concentration of OH radicals and the biocidal activity is linearly correlated.
大量实验证据已充分证实了TiO₂光催化剂的杀菌作用,这表明光催化消毒过程在技术上是可行的。然而,对于杀菌作用的光化学机制的理解在很大程度上仍不明确。特别是,主要起作用的光氧化剂的身份及其在杀灭微生物机制中的作用正在积极研究中。人们普遍认为活性氧(ROS)和OH自由基起作用。本研究的目的是确定OH自由基是如何独立作用或与其他ROS协同作用,与大肠杆菌的失活在数量上相关的。紫外光照射的TiO₂悬浮液中OH自由基的稳态浓度([*OH]ss)可根据对氯苯甲酸(一种探针化合物)的光催化降解速率及其与OH自由基的文献双分子速率常数来定量。结果表明[*OH]ss与大肠杆菌失活速率之间存在极好的线性相关性,这表明OH自由基是负责在紫外/二氧化钛过程中使大肠杆菌失活的主要氧化物种。根据延迟的Chick-Watson模型预测,实现大肠杆菌2个对数级失活的OH自由基的CT值最初为0.8×10⁻⁵毫克·分钟/升。尽管OH自由基在光催化消毒过程中的主要作用经常被假定,但这是首次定量证明OH自由基浓度与杀菌活性呈线性相关。