College of Environmental Science and Engineering, Hunan University, Changsha, Hunan 410082, China; Key Laboratory of Environmental Biology and Pollution Control (Hunan University), Ministry of Education, Changsha, Hunan 410082, China.
College of Environmental Engineering, Henan University of Technology, Zhengzhou 450001, China.
J Hazard Mater. 2023 Jun 5;451:131103. doi: 10.1016/j.jhazmat.2023.131103. Epub 2023 Feb 28.
The conventional Fenton-like system (Fe(III)/HO) is severely limited by the inferior activity of Fe(III) on HO activation to produce highly active species and the sluggish regeneration rate of Fe(II). This work significantly enhanced the oxidative breakdown of the target organic contaminant bisphenol A (BPA) by Fe(III)/HO by introducing cheap CuS at a low dose of 50 mg/L. The BPA removal (20 mg/L) in CuS/Fe(III)/HO system reached 89.5 % within 30 min under the optimal conditions: CuS dosage 50 mg/L, Fe(III) concentration 0.05 mM, HO concentration 0.5 mM and pH 5.6. Compared to CuS/HO and Fe(III)/HO systems, the reaction constants had a 47- and 12.3-fold enhancement, respectively. Even compared with the conventional Fe(II)/HO system, the kinetic constant also increased more than twice, further confirming the distinctive superiority of constructed system. Element species change analyses showed that Fe(III) in solution was adsorbed onto the CuS surface, and then Fe(III) was rapidly reduced by Cu(I) in the CuS lattice. Combining CuS and Fe(III) (in-situ formed CuS-Fe(III) composite) created a robust co-effect on the activation of HO. Also, S(-II) and its derivatives, e.g., S and S (as an electron donor), could quickly reduce Cu(II) to Cu(I) and ultimately oxidize to the harmless product SO. Notably, a mere 50 μM of Fe(III) was sufficient to maintain enough regenerated Fe(II) to effectively activate HO in CuS/Fe(III)/HO system. In addition, such a system achieved a broad range of pH applications and was more suitable for real wastewater containing anions and natural organic matter. Scavenging tests, electron paramagnetic resonance (EPR), and probes further verified the critical role of •OH. This work provides a new approach to solving the problems of Fenton systems through a solid-liquid-interfacial system design and exhibits considerable application potential in wastewater decontamination.
传统的芬顿样系统（Fe(III)/HO）在 HO 激活产生高活性物质方面，Fe(III) 的活性较差，Fe(II) 的再生速率缓慢，因此受到严重限制。本工作通过在低剂量 50mg/L 下引入廉价的 CuS，显著提高了 Fe(III)/HO 对目标有机污染物双酚 A（BPA）的氧化分解。在最佳条件下：CuS 用量 50mg/L、Fe(III)浓度 0.05mM、HO 浓度 0.5mM 和 pH 5.6，CuS/Fe(III)/HO 体系中 20mg/L 的 BPA 去除率在 30min 内达到 89.5%。与 CuS/HO 和 Fe(III)/HO 体系相比，反应常数分别提高了 47 倍和 12.3 倍。即使与传统的 Fe(II)/HO 体系相比，动力学常数也提高了两倍以上，进一步证实了所构建体系的独特优势。元素物种变化分析表明，溶液中的 Fe(III)被吸附到 CuS 表面，然后 Fe(III)被 CuS 晶格中的 Cu(I)迅速还原。CuS 和 Fe(III)（原位形成的 CuS-Fe(III)复合物）的结合对 HO 的激活产生了强大的协同作用。此外，S(-II)及其衍生物，例如 S 和 S（作为电子供体），可以迅速将 Cu(II)还原为 Cu(I)，最终氧化为无害产物 SO。值得注意的是，仅需 50μM 的 Fe(III)就足以维持足够的再生 Fe(II)，以有效激活 CuS/Fe(III)/HO 体系中的 HO。此外，该体系在广泛的 pH 范围内都能应用，并且更适合含有阴离子和天然有机物的实际废水。清除试验、电子顺磁共振（EPR）和探针进一步验证了 •OH 的关键作用。本工作通过固-液界面体系设计为解决芬顿体系的问题提供了一种新方法，在废水处理方面具有很大的应用潜力。
