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电化学增强太阳能光催化:Ti/TiO2 薄膜上内分泌干扰物双酚 A 的降解。

Electrochemical enhancement of solar photocatalysis: degradation of endocrine disruptor bisphenol-A on Ti/TiO2 films.

机构信息

Department of Environmental Engineering, Technical University of Crete, Polytechneioupolis, Chania, Greece.

出版信息

Water Res. 2011 Apr;45(9):2996-3004. doi: 10.1016/j.watres.2011.03.030. Epub 2011 Mar 21.

Abstract

The photoelectrocatalytic oxidation over immobilized Ti/TiO(2) films in the presence of simulated solar light was investigated for the degradation of bisphenol-A (BPA) in water. The catalyst, consisting of 75:25 anatase:rutile, was prepared by a sol-gel method and characterized by cyclic voltammetry, X-ray diffraction and scanning electron microscopy. Experiments were conducted to assess the effect of applied current (0.02-0.32 mA/cm(2)), TiO(2) loading (1.3-9.2 mg), BPA concentration (120-820 μg/L), initial solution pH (1 and 7.5) and the aqueous matrix (pure water and treated effluent) on BPA photoelectrocatalytic degradation which was monitored by high performance liquid chromatography equipped with a fluorescence detector. The reaction was favored at anodic currents up to 0.04 mA/cm(2) and lower substrate concentrations, but it was hindered by the presence of residual organic matter and radical scavengers (e.g. bicarbonates) in treated effluents. Moreover, a pseudo-first order kinetic model could fit the experimental data well with the apparent reaction constant taking values between 2.9 and 32.4 10(-3)/min. The degradation of BPA by pure photocatalysis or electrochemical oxidation alone was also studied leading to partial substrate removal. In all cases, the contribution of applied potential to photocatalytic degradation was synergistic with the photocatalytic efficiency increasing between 24% and 97% possibly due to a more efficient separation and utilization of the photogenerated charge carriers. The effect of photoelectrocatalysis on the ecotoxic and estrogenic properties of BPA was also evaluated measuring the bioluminescence inhibition of Vibrio fischeri and performing the yeast estrogen screening assay, respectively.

摘要

采用溶胶-凝胶法制备了 75:25 锐钛矿-金红石的 TiO2 负载型 Ti/TiO2 光电极,通过循环伏安法、X 射线衍射和扫描电子显微镜对催化剂进行了表征。在模拟太阳光照射下,考察了固定化 TiO2 薄膜光电催化氧化降解水中双酚 A(BPA)的性能。实验评估了电流密度(0.02-0.32 mA/cm2)、TiO2 负载量(1.3-9.2 mg)、BPA 初始浓度(120-820 μg/L)、初始溶液 pH 值(1 和 7.5)和水基质(纯水和处理后的废水)对 BPA 光电催化降解的影响,采用高效液相色谱法(荧光检测器)监测 BPA 的光降解。结果表明,在阳极电流 0.04 mA/cm2 以下和较低的底物浓度下,反应更有利,但处理后的废水中存在残余有机物和自由基清除剂(如碳酸氢盐)会阻碍反应。此外,准一级动力学模型能够很好地拟合实验数据,表观反应常数在 2.9-32.4×10(-3)/min 之间。单独进行光催化或电化学氧化也可以降解 BPA,但仅部分去除了 BPA。在所有情况下,施加电位对光催化降解的贡献与光催化效率呈协同关系,光催化效率提高了 24%-97%,这可能是由于光生载流子的分离和利用效率更高。还评估了光电催化对 BPA 的生态毒性和雌激素效应的影响,分别采用发光菌毒性试验和酵母雌激素筛选试验进行了测定。

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