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β-受体阻滞剂的电化学降解。单组份和多组份合成水溶液的研究。

Electrochemical degradation of beta-blockers. Studies on single and multicomponent synthetic aqueous solutions.

机构信息

Université Paris-Est, Laboratoire Géomatériaux et Géologie de l'Ingénieur, 5 Bd Descartes, 77454 Marne-la-Vallée Cedex 2, France.

出版信息

Water Res. 2010 May;44(10):3109-20. doi: 10.1016/j.watres.2010.03.005. Epub 2010 Mar 6.

Abstract

As far as we know, this is the first study reporting the electrochemical decontamination of solutions containing beta-blockers, which are pharmaceutical pollutants with a high occurrence in natural waters. The oxidation ability of two pre-eminent, eco-friendly electrochemical advanced oxidation processes (EAOPs), namely anodic oxidation (AO) and electro-Fenton (EF), has been compared at lab-scale by carrying out bulk electrolyses at pH 3.0 at constant current using a carbon-felt cathode able to electrogenerate H(2)O(2) in situ. The studies of single component aqueous solutions were focused on atenolol as a model beta-blocker. The AO process was proven much more effective using a large surface area boron-doped diamond (BDD) anode than a Pt one, which was explained by the great amount of active hydroxyl radicals (BDD(OH)) and the minimization of their parasitic reactions. The EF process with a Pt anode and 0.2 mmol l(-1) Fe(2+) showed even higher performance, with fast destruction of atenolol following pseudo-first order kinetics and fast mineralization because the oxidation process in the bulk allows overcoming the mass transport limitations. The time course of the concentration of the aromatic and short-chain carboxylic acid intermediates demonstrated the progressive detoxification of the solutions. Almost 100% of the initial N content was accumulated as NH(4)(+). Multicomponent solutions containing atenolol, metoprolol, and propranolol, which usually occur together in the aquatic environment, were treated by EF using the Pt/carbon felt cell. A high mineralization rate was observed up to the overall total organic carbon (TOC) removal, which allowed reducing the energy consumption. The absolute rate constant for the reaction of each beta-blocker with OH was determined and the reactivity was found to increase in the order: atenolol (1.42 x 10(9) l mol(-1) s(-1)) < metoprolol (2.07 x 10(9) l mol(-1) s(-1)) < propranolol (3.36 x 10(9) l mol(-1) s(-1)).

摘要

据我们所知,这是首例研究报告电化学净化含有β受体阻滞剂的溶液,β受体阻滞剂是在天然水中高频率出现的药物污染物。在 pH 值为 3.0 的条件下,使用能够原位电生成 H2O2 的碳纤维阴极,在恒定电流下进行批量电解,在实验室规模下比较了两种卓越的环保电化学高级氧化工艺(EAOPs)——阳极氧化(AO)和电芬顿(EF)的氧化能力。在单一成分水溶液的研究中,以阿替洛尔作为模型β受体阻滞剂。与 Pt 电极相比,使用大面积掺硼金刚石(BDD)阳极的 AO 过程更为有效,这可以解释为大量的活性羟基自由基(BDD(OH))和最小化它们的寄生反应。EF 过程使用 Pt 阳极和 0.2 mmol l(-1) Fe(2+) 表现出更高的性能,阿替洛尔的快速破坏遵循准一级动力学,并且快速矿化,因为在体相中的氧化过程允许克服质量传递限制。芳香族和短链羧酸中间产物浓度的时间进程证明了溶液的逐渐解毒。初始 N 含量的近 100%被积累为 NH(4)(+)。在水环境中通常同时存在的含有阿替洛尔、美托洛尔和普萘洛尔的多组分溶液通过 EF 使用 Pt/碳纤维电池进行处理。观察到高矿化率,直至总有机碳(TOC)去除,这允许减少能量消耗。确定了每个β受体阻滞剂与 OH 的反应的绝对速率常数,并发现反应性按以下顺序增加:阿替洛尔(1.42 x 10(9) l mol(-1) s(-1)) < 美托洛尔(2.07 x 10(9) l mol(-1) s(-1)) < 普萘洛尔(3.36 x 10(9) l mol(-1) s(-1))。

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