TiO2光催化降解PFOA的反应动力学及机制研究

全氟辛酸(PFOA)是一种新的持久性有机污染物,其处置技术是研究的热点.以UV254 nm紫外灯为光源,采用商品TiO2(P25)对PFOA进行光催化降解实验,并考察pH、TiO2用量、初始浓度、反应气氛对降解的影响.结果表明,反应符合准一级动力学方程,pH对反应有重要影响,氧气存在下能提高反应效率.在pH为3,TiO2用量为1.5 g·L-1,通入空气条件下反应7 h实现基本降解,速率常数为0.4206 h-1.投加俘获剂实验表明,空穴(h+)是主要的活性物质,其对反应速率贡献率为66.1%;羟基自由基(·OH)也参与PFOA的降解过程;投加NaF实验表明,PFOA在TiO2上吸附是反应发生的首要条件.UPLC-QTOF/MS分析表明,PFOA光催化降解逐级生成短链全氟羧酸(PFCAs).

Photocatalytic Degradation Kinetics of Perfluorooctanoic Acid (PFOA) in TiO2 Dispersion and Its Mechanism

Decomposition of perfluorooctanoic acid (PFOA) is of prime importance since it is recognized as a persistent organic pollutant and is widespread in the environment. Heterogeneous photocatalytic decomposition of PFOA by TiO₂(P25) was investigated under 254 nm UV light. Experimental conditions including initial pH, TiO₂ content and PFOA concentration, were varied to demonstrate their effects on the decomposition of PFOA. It was observed that the photocatalytic degradation kinetics of PFOA could be fitted to the quasi-first-order equation. The pH played a determinant role in the decomposition of PFOA and the presence of O₂ increased the degradation rate. Optimal conditions for a complete removal were obtained using 1.5 g·L^-1 TiO₂ at pH 3 in air atmosphere, with a rate constant of 0.4206 h^-1. The contribution experiments of various reactive species produced during the photocatalysis were also investigated with the addition of different scavengers and it was found that photogenerated holes (h⁺) was the major reactive species which was responsible for 66.1% of the degradation rate, and the·OH was involved in PFOA degradation as well. In addition, the photocatalytic experiment with the addition of NaF indicated that the adsorption of PFOA was of primary importance for the photocatalytic decomposition. Perfluorocarboxylic acids (PFCAs) with shorter carbon chain length as intermediates and products were identified with UPLC-QTOF/MS, and a possible mechanism for PFOA decomposition was proposed.