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水溶液中双酚A与铁氧化物和草酸盐的非均相光降解

Heterogeneous photodegradation of bisphenol A with iron oxides and oxalate in aqueous solution.

作者信息

Li F B, Li X Z, Li X M, Liu T X, Dong J

机构信息

Department of Civil and Structural Engineering, The Hong Kong Polytechnic University, Hong Kong, China.

出版信息

J Colloid Interface Sci. 2007 Jul 15;311(2):481-90. doi: 10.1016/j.jcis.2007.03.067. Epub 2007 Apr 4.

Abstract

To understand the degradation of endocrine disrupting chemicals (EDCs) with existence of iron oxides and polycarboxylic acids in the natural environment, the photodegradation of bisphenol A (BPA) at the interface of iron oxides under UV illumination was conducted. Four iron oxides were prepared by a hydrothermal process and then sintered at different temperatures of 65, 280, 310, and 420 degrees C named "IO-65," "IO-280," "IO-310," and "IO-420," respectively. The prepared iron oxides were characterized by X-ray diffraction (XRD) and Brunauer-Emmett-Teller (BET) methods. The XRD pattern of IO-65 showed a crystal structure of lepidocrocite (gamma-FeOOH) and that of IO-420 demonstrated a crystal structure of hematite (alpha-Fe(2)O(3)), while IO-280 and IO-310 have the mixed crystal structures of maghemite (gamma-Fe(2)O(3)) and hematite. The BET results revealed that the specific surface areas decreased with the increase of sintering temperature. The results demonstrated that the photodegradation of BPA depends strongly on the properties of iron oxides and oxalate, and pH. The properties of iron oxides influenced strongly the dependence of the BPA degradation on the oxalate concentration. The optimal initial concentrations of oxalate for BPA degradation under UV illumination were determined to be 2.0, 2.0, 2.4, and 2.0 mM for IO-65, IO-280, IO-310, and IO-420, respectively. The first-order kinetic constants k for BPA degradation under UV illumination in the presence of oxalate with the optimal initial concentration are ranked as IO-280>IO-310>IO-65>IO-420. The experiments demonstrated that the optimal pH value should be in the range of 3-4. Furthermore, the dependence of BPA degradation should be also attributable to the formation of the dissolved Fe-oxalate in the solution and the adsorbed Fe-oxalate on the surface of iron oxides, and also the formation of hydrogen peroxide.

摘要

为了解天然环境中存在铁氧化物和多元羧酸时内分泌干扰化学物质(EDCs)的降解情况,开展了紫外光照下双酚A(BPA)在铁氧化物界面的光降解研究。通过水热法制备了四种铁氧化物,然后分别在65、280、310和420摄氏度的不同温度下烧结,命名为“IO - 65”、“IO - 280”、“IO - 310”和“IO - 420”。采用X射线衍射(XRD)和布鲁诺尔 - 埃米特 - 泰勒(BET)方法对制备的铁氧化物进行表征。IO - 65的XRD图谱显示出纤铁矿(γ - FeOOH)的晶体结构,IO - 420的XRD图谱显示出赤铁矿(α - Fe₂O₃)的晶体结构,而IO - 280和IO - 310具有磁赤铁矿(γ - Fe₂O₃)和赤铁矿的混合晶体结构。BET结果表明,比表面积随烧结温度的升高而降低。结果表明,BPA的光降解强烈依赖于铁氧化物和草酸盐的性质以及pH值。铁氧化物的性质强烈影响BPA降解对草酸盐浓度的依赖性。对于IO - 65、IO - 280、IO - 310和IO - 420,紫外光照下BPA降解的草酸盐最佳初始浓度分别确定为2.0、2.0、2.4和2.0 mM。在存在最佳初始浓度草酸盐的情况下,紫外光照下BPA降解的一级动力学常数k的排序为IO - 280>IO - 310>IO - 65>IO - 420。实验表明,最佳pH值应在3 - 4范围内。此外,BPA降解的依赖性还应归因于溶液中溶解的铁 - 草酸盐和铁氧化物表面吸附的铁 - 草酸盐的形成,以及过氧化氢的形成。

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