Comparative study of MMO and BDD anodes for electrochemical degradation of diuron in methanol medium.

Chemosphere Pub Date : 2024-10-01 Epub Date: 2024-10-10 DOI:10.1016/j.chemosphere.2024.143517
William Santacruz, Julia Faria, Rodrigo De Mello, Maria Valnice Boldrin, Artur de Jesus Motheo
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Abstract

Treating emerging pollutants at low concentrations presents significant challenges in terms of degradation efficiency. Anodic oxidation using active and non-active electrodes shows great potential for wastewater treatment. Thus, this study compared the efficiency of a commercial mixed metal oxide anode (MMO: Ti/Ti0.7Ru0.3O2) and a boron-doped diamond anode (BDD) for the electrochemical oxidation of diuron in methanol, in chloride and sulfate media. The MMO anode achieved diuron removal rates of 94.9% and 92.8% in chloride and sulfate media, respectively, with pseudo-first-order kinetic constants of 0.0177 and 0.0143 min-1. The BDD anode demonstrated slightly higher removal rates, achieving 96.2% in sulfate medium and 96.9% in chloride medium, with respective kinetic constants of 0.0193 min⁻1 and 0.0177 min⁻1. Increasing the current density enhanced diuron removal by up to 15% for both electrodes; however, excessively high current densities led to increased energy consumption due to side reactions. The present of water had antagonistic effects, resulting in removal rates of 91.1% for chloride media using the BDD anode; and 87.4% and 90.4% in sulfate media with MMO and BDD anodes, respectively. The MMO anode in chloride medium did not show significant difference in the degradation percentage, reaching 96% of diuron removals. The degradation mechanism was proposed based on the detection of various by-products. The primary reactions observed during the oxidation of diuron in methanol involved chlorine substitution in the aromatic ring and dealkylation. These processes generated several intermediates and by-products at low concentrations, ultimately leading to high diuron removal.

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MMO 和 BDD 阳极在甲醇介质中电化学降解利谷隆的比较研究。
处理低浓度的新兴污染物对降解效率提出了巨大挑战。使用活性和非活性电极的阳极氧化法在废水处理方面显示出巨大的潜力。因此,本研究比较了商用混合金属氧化物阳极(MMO:Ti/Ti0.7Ru0.3O2)和掺硼金刚石阳极(BDD)在氯化物和硫酸盐介质中电化学氧化甲醇中的双脲的效率。MMO 阳极在氯化物和硫酸盐介质中的利谷隆去除率分别达到 94.9% 和 92.8%,伪一阶动力学常数分别为 0.0177 和 0.0143 min-1。BDD 阳极的去除率略高,在硫酸盐介质中达到 96.2%,在氯化物介质中达到 96.9%,动力学常数分别为 0.0193 min-1 和 0.0177 min-1。提高电流密度可使两种电极的利谷隆去除率提高 15%;但过高的电流密度会因副反应而导致能耗增加。水的存在具有拮抗作用,使用 BDD 阳极对氯化物介质的去除率为 91.1%;使用 MMO 和 BDD 阳极对硫酸盐介质的去除率分别为 87.4% 和 90.4%。MMO 阳极在氯化物介质中的降解率没有明显差异,对利谷隆的去除率达到 96%。根据各种副产物的检测结果提出了降解机制。在甲醇中氧化利谷隆的过程中观察到的主要反应涉及芳香环中的氯取代和脱烷基化。这些过程在低浓度时会产生多种中间产物和副产品,最终导致利谷隆的高去除率。
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