ZIF-62(Co)玻璃催化活化过一硫酸盐降解水中微污染物

doi:10.1016/S1872-2067(23)64608-X

催化学报 ›› 2024, Vol. 59: 118-125.DOI: 10.1016/S1872-2067(23)64608-X

ZIF-62(Co)玻璃催化活化过一硫酸盐降解水中微污染物

李可欣^a, 王茀学^a, 张紫晨^a, 刘正星^a, 马宇辉^b, 王崇臣^a^,^*(), 王鹏^a

^a北京建筑大学环境与能源工程学院, 建筑结构与环境修复功能材料北京重点实验室, 北京 100044
^b中国科学院高能物理研究所, 纳米生物效应与安全性重点实验室, 北京 100049

收稿日期:2024-01-02 接受日期:2024-01-19 出版日期:2024-04-18 发布日期:2024-04-15
通讯作者: *电子信箱: wangchongchen@bucea.edu.cn, chongchenwang@126.com (王崇臣).
基金资助:
国家自然科学基金(22176012);国家自然科学基金(51878023);北京市自然科学基金(8202016);北京市教委研发计划(KM202310016007);北京市教委研发计划(KM202110016010);北京建筑大学培育项目基金(X23034)

Peroxymonosulfate activation over amorphous ZIF-62(Co) glass for micropollutant degradation

Ke-Xin Li^a, Fu-Xue Wang^a, Zi-Chen Zhang^a, Zheng-Xing Liu^a, Yu-Hui Ma^b, Chong-Chen Wang^a^,^*(), Peng Wang^a

^aBeijing Key Laboratory of Functional Materials for Building Structure and Environment Remediation, Beijing University of Civil Engineering and Architecture, Beijing 100044, China
^bKey Laboratory for Biomedical Effects of Nanomaterials and Nanosafety, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China

Received:2024-01-02 Accepted:2024-01-19 Online:2024-04-18 Published:2024-04-15
Contact: *E-mail: wangchongchen@bucea.edu.cn, chongchenwang@126.com (C.-C. Wang).
Supported by:
The National Natural Science Foundation of China(22176012);The National Natural Science Foundation of China(51878023);The Beijing Natural Science Foundation(8202016);The R&D Program of Beijing Municipal Education Commission(KM202310016007);The R&D Program of Beijing Municipal Education Commission(KM202110016010);The Cultivation project Funds for Beijing University of Civil Engineering and Architecture(X23034)

摘要/Abstract

摘要：

近年来, 在水处理领域中, 利用高级氧化技术去除水中有机污染物引起了研究者的广泛关注. 双氧水、过一硫酸盐(PMS)和过二硫酸盐(PDS)等氧化剂可以被含Fe, Mn, Cu和Co等过渡金属的催化剂活化, 并通过产生的活性氧物质、高价金属或直接电子转移等途径实现污染物高效降解. 其中, Co被认为是活化过硫酸盐最有效的物种之一. 粉体ZIF-67和ZIF-9等Co基金属有机框架(Co-MOFs)在水体污染物去除方面得到了广泛关注, 但面临稳定性差及回收困难等问题. 经熔融-淬火工艺所制备的无定形MOF玻璃颗粒克服了粉体材料难以回收再利用的缺点, 同时保持了其中催化位点的高活性. 本文利用MOF玻璃作为非均相催化剂实现高级氧化降解水体微污染物, 研究了其催化活化性能及反应机理.

本文采用熔融-淬火方式将ZIF-62(Co)晶体转化成ZIF-62(Co)玻璃(a_g-ZIF-62(Co)), 并研究了a_g-ZIF-62(Co)活化PMS降解磺胺甲恶唑(SMX)等微污染物的性能. 粉末X射线衍射、傅里叶变换红外光谱、X射线光电子能谱(XPS)等表征结果表明, 熔融-淬火过程使结构有序的ZIF-62(Co)晶体变成无定形的玻璃态a_g-ZIF-62(Co), 但并未破坏其中的有机配体和Co-N键. a_g-ZIF-62(Co)可以在较宽的溶液pH范围(3.0-9.0)内高效催化活化PMS降解SMX等污染物. 由于a_g-ZIF-62(Co)玻璃活化PMS产生的SO₄^•-自由基有可能被溶液中碳酸氢根消耗, 所以溶液中的碳酸氢根浓度越高, SMX的降解效率越差. 水中的氯离子会诱导产生HClO, 从而提高a_g-ZIF-62(Co)活化PMS降解SMX的效率. 其他阴离子(如硝酸根、硫酸根与磷酸二氢根等)对a_g-ZIF-62(Co)活化PMS降解SMX的效率无明显抑制或促进作用. 利用自来水配制模拟含SMX废水, 研究其中存在的多重阴离子和阳离子对a_g-ZIF-62(Co)活化PMS降解SMX性能的影响. 结果表明, a_g-ZIF-62(Co)在30 min内对低浓度(1.0 mg/L)和高浓度(5.0 mg/L)SMX的降解效率均保持较高的水平. 捕捉实验、电子自旋共振和自由基定量等实验证明了硫酸根自由基与单线态氧是降解SMX的主要活性物种. 结合电喷雾质谱结果提出了SMX的降解路径, 并评估了中间产物的毒性. 利用XPS分析了a_g-ZIF-62(Co)反应前后Co的价态变化, 并结合其他实验结果阐明了硫酸根自由基与单线态氧的产生路径. 为探究a_g-ZIF-62(Co)在实际应用中的潜在价值, 搭建了固定床反应器并填充a_g-ZIF-62(Co). 结果表明, a_g-ZIF-62(Co)在反应器中能连续120 h活化PMS并高效降解SMX. 此外, a_g-ZIF-62(Co)还可以高效降解多种微污染物(如阿特拉津、双酚A、磷酸氯喹、氧氟沙星和罗丹明B等). a_g-ZIF-62(Co)玻璃在水体系中活化PMS时, Co离子溶出低于GB 25467-20标准要求, 有效地避免了Co离子带来的环境压力.

综上所述, 本文报道了a_g-ZIF-62(Co)活化PMS降解水中SMX的性能, 分析了不同因素对SMX降解效率的影响, 并探究了活化PMS降解SMX的机理. 通过搭建了固定床反应器, 实现了对SMX的长时间高效降解, 显示了a_g-ZIF-62(Co)在AOPs中的应用潜力. 本研究不仅为MOF玻璃在环境污染控制中的应用提供了新思路, 也为后续MOF玻璃作为催化剂在环境催化领域的发展提供参考.

关键词: MOF玻璃, 磺胺甲恶唑降解, 高级氧化过程, 降解机理, 固定床反应器

Abstract:

Amorphous ZIF-62(Co) glass (a_g-ZIF-62(Co)) was prepared and used as peroxymonosulfate (PMS) activator for the degradation of sulfamethoxazole (SMX). In the presence of 0.1 g/L a_g-ZIF-62(Co) and 0.2 mmol/L PMS, approximately 98.6% of SMX with an initial concentration of 5.0 mg/L was degraded within 30 min. The main reactive oxygen species (ROS) involved were sulfate radical (SO₄^•-) and singlet oxygen (¹O₂), with concentrations of 41.1 and 171.9 μmol/L, respectively. A fixed-bed reactor packed with a_g-ZIF-62(Co) was constructed for continuous SMX degradation, achieving nearly complete decontamination and 50% reduction in chemical oxygen demand over a period of 120 h. This study has paved a new avenue for exploring the potential application of metal-organic framework glasses in water purification through advanced oxidation processes.

Key words: Metal-organic framework glasses, Sulfamethoxazole degradation, Advanced oxidation processes, Degradation mechanism, Fixed-bed reactor

李可欣, 王茀学, 张紫晨, 刘正星, 马宇辉, 王崇臣, 王鹏. ZIF-62(Co)玻璃催化活化过一硫酸盐降解水中微污染物[J]. 催化学报, 2024, 59: 118-125.

Ke-Xin Li, Fu-Xue Wang, Zi-Chen Zhang, Zheng-Xing Liu, Yu-Hui Ma, Chong-Chen Wang, Peng Wang. Peroxymonosulfate activation over amorphous ZIF-62(Co) glass for micropollutant degradation[J]. Chinese Journal of Catalysis, 2024, 59: 118-125.

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图/表 5

Fig. 1. (a,b) The photos of ag-ZIF-62(Co). (c) The PXRD patterns of pure ZIF-62(Co) crystals and ag-ZIF-62(Co). The XPS high resolution spectra of C 1s (d) and N 1s (e). (f) FTIR spectra of ZIF-62(Co) crystal and ag-ZIF-62(Co). (g) High-resolution FTIR spectra from 500 to 400 cm-1 of ZIF-62(Co) crystal and ag-ZIF-62(Co).

Fig. 2. (a) SMX degradation efficiencies over different conditions. The k values over different concentrations of PMS (b) and different catalyst dosages (c). (d) The SMX degradation efficiencies influenced by initial pH. Reaction conditions: PMS (0.2 mmol/L), H2O2 (3.0 mmol/L), PDS (1.0 mmol/L), SMX (5.0 mg/L), catalyst (0.1 g/L).

Fig. 3. The SMX degradation efficiencies influenced by different concentrations of SO42-; NO3-; H2PO4-; HCO3- (a) and Cl- (b). (c) HClO quench experiment in ag-ZIF-62(Co)/PMS/Cl- system. (d) The SMX degradation efficiencies in different water solutions. Reaction condition: PMS (0.2 mmol/L), SMX (5.0 mg/L), catalyst (0.1 g/L).

Fig. 4. (a) LSV curves obtained under different conditions. (b) Effects of different scavengers on SMX k values over ag-ZIF-62(Co). (c) ESR spectra of DMPO-SO4?-, DMPO-·OH and TEMP-1O2 over ag-ZIF-62(Co) with/without PMS. (d) PMS residual within 30 min during SMX degradation and (inside) standard curve of PMS. (e) SO4?- quantification in mole ratio of PMS and HBA 1:9 and 1O2 quantification. (f) XPS survey spectra of high-resolution spectra of Co 2p.

Fig. 5. The reusability of ag-ZIF-62(Co) (a) and relevant Co ion leaching (b). (c) Photo image of the fixed-bed reactor for SMX degradation over ag-ZIF-62 via. PMS activation. (d) Schematic illustration of the fixed-bed reactor. (e) The degradation of SMX in fixed-bed reactor. (f) COD residual of SMX (5 mg/L, purified water) in fixed-bed reactor.

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ZIF-62(Co)玻璃催化活化过一硫酸盐降解水中微污染物

Peroxymonosulfate activation over amorphous ZIF-62(Co) glass for micropollutant degradation

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