氢氧化钴/生物炭活化过氧乙酸降解水中抗生素

doi:10.19965/j.cnki.iwt.2023-0449

摘要/Abstract

摘要：

通过对非均相复合催化剂进行合理的电子结构调控，可有效促进界面电荷分离和转移，进而提升催化剂的性能。近年来，以生物炭（BC）基材料活化过氧乙酸〔CH₃C（O）OOH，PAA〕的非均相高级氧化工艺因能产生多种活性氧物种（ROS）而备受关注。采用一种简易的共沉淀法合成了Co（OH）₂纳米颗粒修饰的生物炭材料（h-Co/BC），并将其应用于活化PAA降解水中的典型抗生素四环素（TC）。实验结果表明h-Co/BC在pH=7条件下，7 min内可实现对初始浓度为10 µmol/L的TC的完全降解去除。自由基猝灭实验和电子顺磁共振（EPR）分析表明，该非均相体系中主要的ROS为烷氧基自由基，包括CH₃COO·、CH₃COOO·、·OH和¹O₂。材料表征结合密度泛函理论计算表明，Co（OH）₂纳米颗粒成功地负载于生物炭上，Co 3d带中心更靠近费米能级，利于电子的定向迁移，进而被PAA捕获，随后PAA裂解生成ROS。该研究可为非均相PAA高级氧化技术中功能材料的研发提供新的理念。

关键词: 生物炭, 氢氧化钴, 过氧乙酸, 抗生素, 密度泛函理论计算

Abstract:

Reasonable regulation of electronic structures of heterogeneous composite catalysts can enhance the charge separation and transfer at the interface of materials, thus further promoting the catalytic performance of catalysts. Recently, peracetic acid〔CH₃C(O)OOH, PAA〕 based on heterogeneous advanced oxidation process with biochar(BC) materials has attacked much interests due to various reactive oxygen species(ROS) generated in the process. In this study, biochar modified with Co(OH)₂ nanoparticles(h-Co/BC) was successfully synthesized by a simple co-precipitation method, which was applied to activate PAA for tetracycline(TC) degradation. The results showed that h-Co/BC could completely degrade TC with an initial concentration of 10 µmol/L within 7 min at pH 7. The scavenger quenching tests and electron paramagnetic resonance(EPR) analysis further indicated that the produced primary ROS were alkoxy radical, which mainly including CH₃COO·, CH₃COOO·, ·OH and ¹O₂. In addition, materials characterizations combined with density functional theory calculation showed that biochar was successfully modified with Co(OH)₂ nanoparticles. Thus, the Co 3d-band in h-Co/BC was closer to Fermi level compared with that in pure Co(OH)₂, benefiting to directional electron transfer, which could then be easily captured by PAA for cleavage to ROS. This study provided a new method for synthesis of functional materials applied in PAA-based AOPs.

Key words: biochar, cobalt hydroxide, peracetic acid, antibiotics, density functional theory calculation

中图分类号:

孙丰宾, 杨旭东, 李璠, 乔林, 刘文. 氢氧化钴/生物炭活化过氧乙酸降解水中抗生素[J]. 工业水处理, 2024, 44(6): 78-87.

Fengbin SUN, Xudong YANG, Fan LI, Lin QIAO, Wen LIU. Activation of peracetic acid by cobalt hydroxide/biochar for antibiotics degradation in water[J]. Industrial Water Treatment, 2024, 44(6): 78-87.

https://www.iwt.cn/CN/Y2024/V44/I6/78

图/表 9

图1 h-Co/BC的TEM（a~b）、HRTEM（c）、SEM（d）和XRD（e）

Fig.1 TEM images（a~b）， HRTEM image（c），SEM image（d） and XRD pattern（e） of h-Co/BC

图2 不同体系下TC的去除情况

Fig.2 Removal of TC in various systems

图3 Co的溶出情况

Fig.3 Dissolution of Co

图4 h-Co/BC投加量（a）、TC初始浓度（b）以及PAA投加量（c）对TC去除的影响

Fig.4 Effects of h-Co/BC dosage（a），TC initial concentration（b） and PAA dosages （c）on TC removal

图5 猝灭剂对TC降解的影响（a）和不同ROS对TC降解的贡献率（b）

Fig.5 Effects of quenching agent on degradation of TC（a） and ROS contributions to TC degradation（b）

图6 EPR检测的·OH、CH₃COOO·和¹O₂谱图

Fig.6 The EPR spectrum of ·OH，CH₃COOO· and ¹O₂

图7 理论模型及相关计算（a）h-Co/BC的结构模型；（b）h-Co/BC的DOS谱图；（c）BC的DOS谱图；（d）Co（OH）₂的DOS谱图；（e）h-Co/BC的功函数；（f）Co（OH）₂的功函数；（g）纯BC的功函数；（h）EDD图（蓝色表示电子消耗，黄色表示电子积累）。

Fig.7 Theoretical model and the relevant calculations

图8 h-Co/BC的循环使用测试（a），不同水体中TC的降解（b）及反应后h-Co/BC的TEM谱图（c）

Fig.8 Catalysts reuse test（a），TC degradation efficiency in different waters（b） and TEM image of h-Co/BC after reaction（c）

图9 h-Co/BC活化PAA降解TC的机理示意

Fig.9 Schematic diagram of PAA degradation by h-Co/BC after PAA activation

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