Unitat de Química Industrial, Escola Universitària d'Enginyeria Tècnica Industrial de Barcelona, Universitat Politècnica de Catalunya, Comte d'Urgell 187, 08036 Barcelona, Spain.
J Phys Chem A. 2010 Jun 24;114(24):6613-21. doi: 10.1021/jp1035647.
Solutions of 30 mg L(-1) of the herbicide atrazine have been degraded by environmentally friendly electrochemical advanced oxidation processes (EAOPs) such as anodic oxidation (AO), electro-Fenton (EF), and photoelectro-Fenton (PEF) using a small open and cylindrical cell with a boron-doped diamond (BDD) anode. AO has been carried out either with a stainless steel cathode or an O(2) diffusion cathode able to generate H(2)O(2). Hydroxyl radicals (()OH) formed at the BDD surface in all EAOPs and in the bulk from Fenton's reaction between added Fe(2+) and electrogenerated H(2)O(2) in EF and PEF are the main oxidants. All treatments yielded almost overall mineralization, although the rate for total organic carbon (TOC) removal is limited by the oxidation of persistent byproducts with ()OH at the BDD surface. In AO, TOC abatement is enhanced by parallel electrochemical reduction of organics at the stainless steel cathode, while in PEF, it also increases from additional photolysis of intermediates by UVA light under the synergistic action of ()OH in the bulk. The effect of current and pH on the degradative behavior of EAOPs has been examined to determine their optimum values. Atrazine decay always follows a pseudo-first-order reaction, being more rapidly destroyed from ()OH in the bulk than at the BDD surface. Aromatic intermediates such as desethylatrazine, desethyldesisopropylatrazine, and cyanuric acid and short linear carboxylic acids such as formic, oxalic, and oxamic have been identified and quantified by reversed-phase and ion-exclusion HPLC, respectively. Released inorganic ions such as Cl(-), NO(3)(-), and NH(4)(+) have been followed by ionic chromatography.
已使用带有掺硼金刚石(BDD)阳极的小型敞开式圆柱形电池,通过环境友好型电化学高级氧化工艺(EAOPs),如阳极氧化(AO)、电芬顿(EF)和光电芬顿(PEF),对 30mg/L 的除草剂莠去津溶液进行了降解。AO 可以使用不锈钢阴极或 O(2)扩散阴极进行,后者能够生成 H(2)O(2)。在所有的 EAOPs 中以及在 EF 和 PEF 中 Fenton 反应之间添加的 Fe(2+)和电生成的 H(2)O(2)在 bulk 中生成的羟基自由基(()OH)在 BDD 表面形成,是主要的氧化剂。所有处理都几乎实现了完全矿化,尽管总有机碳(TOC)的去除率受到 ()OH 在 BDD 表面氧化持久性副产物的限制。在 AO 中,TOC 的去除率通过不锈钢阴极上有机物的平行电化学还原得到增强,而在 PEF 中,在 bulk 中 ()OH 的协同作用下,通过 UVA 光对中间产物的额外光解,TOC 的去除率也会增加。研究了电流和 pH 值对 EAOPs 降解行为的影响,以确定其最佳值。莠去津的降解始终遵循准一级反应,在 bulk 中比在 BDD 表面更快地被 ()OH 破坏。通过反相和离子排斥 HPLC 分别鉴定和定量了芳香族中间体,如去乙基莠去津、去乙基二异丙基莠去津和氰尿酸以及短线性羧酸,如甲酸、草酸和草酰胺。通过离子色谱法跟踪释放的无机离子,如 Cl(-)、NO(3)(-)和 NH(4)(+)。