Co(x)/γ -Al₂O₃非均相催化剂活化过氧乙酸处理亚甲基蓝废水的研究

Study on Co(x)/γ-Al₂O₃ Heterogeneous Catalyst Activation of Peracetic Acid for Treating Methylene Blue Wastewater

摘要

活化过氧乙酸(PAA)高级氧化技术是一种高效、清洁的水污染处理方法, 有望成为解决水体中亚甲基蓝污染的合理方案. 然而, 现有研究主要围绕活化PAA机理开展, 对如何提高催化材料的实际应用性缺乏深入讨论, 制约了活化PAA技术的工程化应用. 本文报道了一类新型钴基非均相催化剂Co(x)/γ-Al₂O₃, 在最佳浸渍时间(12 h)可实现PAA的高效活化, 对10 mg/L亚甲基蓝废水的去除率可达99.6%. 与均相的钴离子(Co²⁺)活化体系相比, Co(x)/γ-Al₂O₃活化体系可节省约25%的PAA投加量. 同时, 该催化剂还具有较宽的pH适应范围、较强的HCO₃⁻耐受能力以及低于10 μg/L的超低金属溶出浓度, 其性能、稳定性以及使用寿命均优于传统的PAA活化材料. 表面化学表征与理论计算结合表明, Co(x)/γ-Al₂O₃的催化活性源于催化剂表面Co²⁺/Co³⁺循环, 该过程中所产生的乙酰基(过)氧基自由基[CH₃C(O)O·和CH₃C(O)OO·]是攻击亚甲基蓝的主要反应物种. PAA活化主要发生在Co位点上, 其在Co₃O₄(311)平面具有较高的吸附能(1.00 eV)和d-带中心(1.55 eV), 可以增加PAA在反应平面上的吸附, 促进电荷转移, 从而增强Co(x)/γ-Al₂O₃对PAA的活化能力. 综上所述, Co(x)/γ-Al₂O₃催化剂为活化PAA工艺在亚甲基蓝废水处理领域的实际应用提供了一种可持续且高效的解决方案.

Abstract

The activated peracetic acid (PAA) advanced oxidation technology is a highly efficient and eco-friendly water pollution treatment strategy, which is expected to serve as a viable solution for addressing methylene blue contamination in water bodies. However, existing studies have primarily focused on the mechanism of PAA activation, while lacking in-depth discussions on how to improve the practical applicability of catalytic materials. This research gap has restricted the engineering application of activated PAA technology. A new type of cobalt based heterogeneous catalyst Co(x)/γ-Al₂O₃ was developed in this study. With an optimal impregnation time of 12 h, this catalyst enables efficient activation of PAA, achieving a removal rate of 99.6% for 10 mg/L methylene blue wastewater. Compared with the homogeneous cobalt ion (Co²⁺) activation system, the Co(x)/γ-Al₂O₃ activation system can reduce the dosage of PAA by approximately 25%. Meanwhile, this catalyst exhibits a wide pH adaptation range, strong tolerance to HCO₃ ⁻, and an ultra-low metal leaching concentration of less than 10 μg/L. Its overall performance, stability, and service life are all superior to those of conventional PAA activated materials. Combined analyses of surface chemical characterization and theoretical calculations demonstrate that the catalytic activity of Co(x)/γ-Al₂O₃ originates from the Co²⁺/Co³⁺ cycle on the catalyst surface. The acetyl(per)oxy radicals [CH₃C(O)O· and CH₃C(O)OO·] generated during this process are identified as the primary reactive species responsible for degrading methylene blue. The activation of PAA mainly occurs at the Co active sites, which exhibit a high adsorption energy of 1.00 eV and ad-band center of 1.55 eV on the Co₃O₄(311) plane. This characteristic enhances the adsorption of PAA on the reaction interface, facilitates charge transfer, and thereby strengthens the PAA activation capability of Co(x)/γ-Al₂O₃. In conclusion, the Co(x)/γ-Al₂O₃ catalyst provides a sustainable and highly efficient solution for the practical application of the activated PAA process in the treatment of methylene blue wastewater.

关键词

活化过氧乙酸 / 钴基催化剂 / 亚甲基蓝废水 / 有机自由基 / 密度泛函理论

Key words

Peracetic acid activation (PAA) / Cobalt based catalyst / Methylene blue (MB) wastewater / Organic radical / Density functional theory

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基金资助

辽宁省教育厅高校基本科研项目(青年项目)(LJKQZ20222300)

辽宁省自然科学基金博士启动基金项目(2024-BS-112)