State Key Laboratory of Environmental Aquatic Chemistry, Research Center for Eco-Environmental Sciences, Chinese Academy of Sciences, Beijing 100085, China.
J Environ Sci (China). 2009;21(10):1321-8. doi: 10.1016/s1001-0742(08)62421-3.
The anodic oxidation of aqueous solutions containing dimethyl phthalate (DMP) up to 125 mg/L with sodium sulfate (Na2SO4) as supporting electrolyte within the pH range 2.0-10.0 was studied using a one-compartment batch reactor employing a boron-doped diamond (BDD) as anode. Electrolyses were carried out at constant current density (1.5-4.5 mA/cm2). Complete mineralization was always achieved owing to the great concentration of hydroxyl radical (*OH) generated at the BDD surface. The effects of pH, apparent current density and initial DMP concentration on the degradation rate of DMP, the specific charge required for its total mineralization and mineralization current efficiency were investigated systematically. The mineralization rate of DMP was found to be pH-independent and to increase with increasing applied current density. Results indicated that this electrochemical process was subjected, at least partially, to the mass transfer of organics onto the BDD surface. Kinetic analysis of the temporal change of DMP concentration during electrolysis determined by High Performance Liquid Chromatography (HPLC) revealed that DMP decay under all tested conditions followed a pseudo first-order reaction. Aromatic intermediates and generated carboxylic acids were identified by Gas Chromatography-Mass Spectrometry (GC-MS) and a general pathway for the electrochemical incineration of DMP on BDD was proposed.
在 pH 值为 2.0-10.0 范围内,使用一隔间批式反应器,以硼掺杂金刚石 (BDD) 作为阳极,研究了含有邻苯二甲酸二甲酯 (DMP) 达 125mg/L 的水溶液在硫酸钠 (Na2SO4) 作为支持电解质的情况下的阳极氧化。在恒电流密度(1.5-4.5mA/cm2)下进行电解。由于在 BDD 表面生成了大量的羟基自由基 (*OH),因此总是可以实现完全矿化。系统研究了 pH 值、表观电流密度和初始 DMP 浓度对 DMP 降解速率、完全矿化所需的比电荷和矿化电流效率的影响。发现 DMP 的矿化速率与 pH 值无关,并且随着施加电流密度的增加而增加。结果表明,该电化学过程至少部分受到有机物向 BDD 表面的质量转移的影响。通过高效液相色谱法 (HPLC) 确定的电解过程中 DMP 浓度随时间变化的动力学分析表明,在所有测试条件下,DMP 的衰减遵循准一级反应。通过气相色谱-质谱法 (GC-MS) 鉴定了芳香族中间体和生成的羧酸,并提出了在 BDD 上电化学焚烧 DMP 的一般途径。