CoMoO<sub>4</sub>@rGO复合膜的制备及其对染料废水的处理性能

doi:10.19965/j.cnki.iwt.2024-0412

摘要/Abstract

摘要：

将高级氧化技术与膜分离技术相耦合，制备具有催化降解污染物功能的复合分离膜，能有效提高对污染物的处理性能。通过水热法合成了CoMoO₄@rGO复合催化剂，并采用抽滤和高压固定方式制备了CoMoO₄@rGO复合膜。通过SEM可以观察到CoMoO₄纳米棒分散在薄片状rGO中，XRD和FTIR等表征手段均证实了复合膜的成功制备。进一步研究了复合膜在过一硫酸盐（PMS）辅助下对亚甲基蓝（MB）的处理性能。结果表明，在rGO掺杂量为1%（质量分数），PMS浓度为0.3 mmol/L，催化功能层负载量为79.37 g/m²，操作压力为5.00×10^-3 MPa以及pH为3~7条件下，复合膜在2 min内对MB的去除率达到100%。同时，催化功能层通过活化PMS对污染物的分解可有效缓解膜污染。10次连续循环使用后，该复合膜仍展现出优异的稳定性。自由基猝灭实验证明了非自由基（¹O₂与表面介导氧化）和自由基（O₂ ^·-）协同机制均对CoMoO₄@（1%）rGO复合膜去除MB起到重要作用。

关键词: CoMoO₄, rGO, 高级氧化, 复合膜, 染料废水

Abstract:

Coupling advanced oxidation technology with membrane separation technology to form composite membrane can efficiently improve the treatment performance of pollutants. The CoMoO₄@rGO composite were synthesized by hydrothermal method, and CoMoO₄@rGO composite membrane were prepared by pumping filtration and high pressure immobilization. It could be observed that CoMoO₄ nanorods were dispersed in thin rGO sheets through SEM. The characterization methods such as XRD and FTIR confirmed the successful preparation of the composite membrane. The treatment performance of the composite membrane towards methylene blue(MB) with the assistance of persulfate(PMS) was further investigated. The results showed that the composite membrane could remove 100% of MB within 2 min, under the conditions of rGO doping of 1%(mass fraction), PMS concentration of 0.3 mmol/L, catalytic functional layer loading of 79.37 g/m², operating pressure of 5.00×10^-3 MPa, and pH of 3-7. Meanwhile, the catalytic functional layer could effectively alleviate membrane fouling by activating PMS to decompose pollutants. After 10 consecutive cycles of use, the composite membrane still exhibited excellent stability. The free radical quenching experiments demonstrated that both non free radical (¹O₂ and surface-mediated oxidation) and free radical (O₂ ^·-) synergistic mechanisms played an important role in the removal of MB by CoMoO₄@(1%) rGO composite membrane.

Key words: CoMoO₄, rGO, advanced oxidation technology, composite membrane, dye wastewater

中图分类号:

X703

韦浩桐, 陈文凯, 吴丹, 刘宇琪, 赵焕新. CoMoO₄@rGO复合膜的制备及其对染料废水的处理性能[J]. 工业水处理, 2025, 45(5): 102-110.

Haotong WEI, Wenkai CHEN, Dan WU, Yuqi LIU, Huanxin ZHAO. The synthesis of CoMoO₄@rGO composite membrane and its performance on dye wastewater treatment[J]. Industrial Water Treatment, 2025, 45(5): 102-110.

https://www.iwt.cn/CN/Y2025/V45/I5/102

图/表 9

图1 CoMoO₄膜及CoMoO₄@rGO复合膜的照片及SEM （a）CoMoO₄膜照片；（b）CoMoO₄@（1%）rGO复合膜照片；（c）CoMoO₄@（10%）rGO复合膜照片；（d）CoMoO₄@（20%）rGO复合膜照片；（e）CoMoO₄膜SEM；（f）CoMoO₄@（1%）rGO复合膜SEM；（g）CoMoO₄@（10%）rGO复合膜SEM；（h）CoMoO₄@（20%）rGO复合膜SEM。

Fig.1 Photographs and SEM of CoMoO₄ and CoMoO₄@rGO composite membranes

图2 CoMoO₄及CoMoO₄@rGO的XRD、FTIR、交流阻抗及XPS表征（a）CoMoO₄及CoMoO₄@rGO的XRD；（b）CoMoO₄及CoMoO₄@rGO的FTIR；（c）CoMoO₄及CoMoO₄@rGO的电化学交流阻抗；（d）CoMoO₄@（1%）rGO的XPS全谱图；（e）~（g）CoMoO₄@（1%）rGO中Co、Mo和C元素的XPS。

Fig.2 XRD，FTIR，AC impedance and XPS characterization of CoMoO₄ and CoMoO₄@rGO

图3 CoMoO₄@rGO复合膜处理MB的性能（c） CoMoO₄@rGO复合膜处理MB的稳定性

Fig.3 Performance of CoMoO₄@rGO composite membrane for MB treatment

图4 各要素对复合膜去除MB效果的影响

Fig.4 Effect of each factor on MB removal by composite membrane

图5 自由基捕获实验结果

Fig.5 Results of free radical trapping experiments

图6 使用前后CoMoO₄@（1%）rGO复合膜的XPS表征

Fig.6 XPS characterization of CoMoO₄@（1%）rGO composite membrane before and after use

图7 CoMoO₄@（1%）rGO复合膜使用前后的SEM（a~b）及XRD（c）

Fig.7 SEM （a-b） and XRD （c） of CoMoO₄@（1%）rGO composite membrane before and after use

图8 CoMoO₄@（1%）rGO复合膜对TC的去除性能

Fig.8 The removal performance of TC by CoMoO₄@（1%）rGO composite membrane

图9 CoMoO₄@（1%）rGO复合膜处理不同水样的渗透通量变化情况

Fig.9 Variation of permeate flux of different water samples treated by CoMoO₄@（1%）rGO composite membrane

参考文献 18

1	ZHANG Yuting， AN Yechen， LIU Chao，et al. Catalytic ozonation of emerging pollutant and reduction of toxic by-products in secondary effluent matrix and effluent organic matter reaction activity［J］. Water Research，2019，166：115026. doi:10.1016/j.watres.2019.115026
2	薛罡. 印染废水治理技术进展［J］. 工业水处理，2021，41（9）：10-17. doi:10.19965/j.cnki.iwt.2021-0433
	XUE Gang. Technical progress of dyeing wastewater treatment［J］. Industrial Water Treatment，2021，41（9）：10-17. doi:10.19965/j.cnki.iwt.2021-0433
3	YE Wenyuan， LIU Hongwei， LIN Fang，et al. High-flux nanofiltration membranes tailored by bio-inspired co-deposition of hydrophilic g-C₃N₄ nanosheets for enhanced selectivity towards organics and salts［J］. Environmental Science：Nano，2019，6（10）：2958-2967. doi:10.1039/c9en00692c
4	HU Peidong， LONG Mingce. Cobalt-catalyzed sulfate radical-based advanced oxidation：A review on heterogeneous catalysts and applications［J］. Applied Catalysis B：Environmental，2016，181：103-117. doi:10.1016/j.apcatb.2015.07.024
5	DAS S， MAHALINGAM H. Novel immobilized ternary photocatalytic polymer film based airlift reactor for efficient degradation of complex phthalocyanine dye wastewater［J］. Journal of Hazardous Materials，2020，383：121219. doi:10.1016/j.jhazmat.2019.121219
6	OH W D， DONG Zhili， LIM T T. Generation of sulfate radical through heterogeneous catalysis for organic contaminants removal：Current development，challenges and prospects［J］. Applied Catalysis B：Environmental，2016，194：169-201. doi:10.1016/j.apcatb.2016.04.003
7	NIE Minghua， YANG Yi， ZHANG Zhijian，et al. Degradation of chloramphenicol by thermally activated persulfate in aqueous solution［J］. Chemical Engineering Journal，2014，246：373-382. doi:10.1016/j.cej.2014.02.047
8	FAN Yiang， ZHOU Ying， FENG Yong，et al. Fabrication of reactive flat-sheet ceramic membranes for oxidative degradation of ofloxacin by peroxymonosulfate［J］. Journal of Membrane Science，2020，611：118302. doi:10.1016/j.memsci.2020.118302
9	WANG Songxue， TIAN Jiayu， WANG Zhihui，et al. Integrated process for membrane fouling mitigation and organic pollutants removal using copper oxide modified ceramic hollow fiber membrane with in situ peroxymonosulfate activation［J］. Chemical Engineering Journal，2020，396：125289. doi:10.1016/j.cej.2020.125289
10	CHEN Peng， GOU Yejing， NI Jiaming，et al. Efficient ofloxacin degradation with Co（Ⅱ）-doped MoS₂ nano-flowers as PMS activator under visible-light irradiation［J］. Chemical Engineering Journal，2020，401：125978. doi:10.1016/j.cej.2020.125978
11	GUO Xiaojun， WANG Kebai， LI Dai，et al. Heterogeneous photo-Fenton processes using graphite carbon coating hollow CuFe₂O₄ spheres for the degradation of methylene blue［J］. Applied Surface Science，2017，420：792-801. doi:10.1016/j.apsusc.2017.05.178
12	LIU Dongdong， CHEN Dengqian， HAO Zhengkai，et al. Efficient degradation of rhodamine B in water by CoFe₂O₄/H₂O₂ and CoFe₂O₄/PMS systems：A comparative study［J］. Chemosphere，2022，307：135935. doi:10.1016/j.chemosphere.2022.135935
13	ZHOU Hongyu， LAI Leiduo， WAN Yanjian，et al. Molybdenum disulfide（MoS₂）：A versatile activator of both peroxymonosulfate and persulfate for the degradation of carbamazepine［J］. Chemical Engineering Journal，2020，384：123264. doi:10.1016/j.cej.2019.123264
14	LIU Jia， WANG Jinsong， ZHANG Bao，et al. Mutually beneficial Co₃O₄@MoS₂ heterostructures as a highly efficient bifunctional catalyst for electrochemical overall water splitting［J］. Journal of Materials Chemistry A，2018，6（5）：2067-2072. doi:10.1039/c7ta10048e
15	TANG Zhiling， HE Wenjie， WANG Yingli，et al. Ternary heterojunction in rGO-coated Ag/Cu₂O catalysts for boosting selective photocatalytic CO₂ reduction into CH₄ ［J］. Applied Catalysis B：Environmental，2022，311：121371. doi:10.1016/j.apcatb.2022.121371
16	MA Huanran， WANG Guanlong， XU Zhouhang，et al. Confining peroxymonosulfate activation in carbon nanotube intercalated nitrogen doped reduced graphene oxide membrane for enhanced water treatment：The role of nanoconfinement effect［J］. Journal of Colloid and Interface Science，2022，608：2740-2751. doi:10.1016/j.jcis.2021.11.007
17	MARCANO D C， KOSYNKIN D V， BERLIN J M，et al. Improved synthesis of graphene oxide［J］. ACS Nano，2010，4（8）：4806-4814. doi:10.1021/nn1006368
18	LIU Zhechen， ZHONG Yuan， CHEN Long，et al. Co₃O₄/CuO@C catalyst based on cobalt-doped HKUST-1 as an efficient peroxymonosulfate activator for pendimethalin degradation：Catalysis and mechanism［J］. Journal of Hazardous Materials，2024，478：135437. doi:10.1016/j.jhazmat.2024.135437

[1]	钟全发, 钟琳, 徐国徽, 金青海, 余瑾, 徐飞, 何頔. 垃圾渗滤液膜浓缩液全量化处理中溶解性有机物分子水平转化特征[J]. 工业水处理, 2025, 45(2): 109-117.
[2]	郑国庆, 黄煜坤, 韩要丛, 薛兴勇, 卢彦越, 蓝丽红, 陈贞南. 锰渣活化过一硫酸盐降解罗丹明B[J]. 工业水处理, 2025, 45(1): 79-86.
[3]	周朝云, 令玉林, 蒋文雪, 周建红. WO₃/rGO/BiOBr的制备及其光催化降解环丙沙星废水的性能研究[J]. 工业水处理, 2025, 45(1): 73-78.
[4]	贾仲琪, 卫金秋, 宿辉, 刘宪斌. 纳米零价铁耦合高级氧化技术处理废水的研究进展[J]. 工业水处理, 2024, 44(7): 9-18.
[5]	傅翔宇, 李亚峰. 三维电极电Fenton处理阿奇霉素制药废水研究[J]. 工业水处理, 2024, 44(6): 158-164.
[6]	张玉红, 张盾超, 宋秀兰, 何娜. 碱激活PMS氧化法协同SBBR深度处理焦化废水研究[J]. 工业水处理, 2024, 44(6): 94-100.
[7]	商伟伟, 杨焱, 沈芸, 赵世荣, 薛罡, 钱雅洁. 高铁酸盐耦合过氧乙酸深度处理水中甲硝唑的特性研究[J]. 工业水处理, 2024, 44(5): 111-119.
[8]	刘臻, 刘浪, 郑鹏, 刘荣, 袁绍春, 李聪, 陈垚. 电化学高级氧化技术再生活性炭研究进展[J]. 工业水处理, 2024, 44(5): 42-51.
[9]	王俩, 吴霜, 程小双, 梁澜, 李宁, 陈冠益, 侯立安. 含碳铁泥基催化剂活化H₂O₂处理亚甲基蓝废水[J]. 工业水处理, 2024, 44(2): 125-132.
[10]	李天羽, 张峰, 杨艳青, 窦哲华, 崔建国. 基于亚硫酸盐活化体系的Cr（Ⅵ）和罗丹明B同步去除[J]. 工业水处理, 2024, 44(2): 157-165.
[11]	李倩, 龚豪, 薛罡, 钱雅洁. 铁刨花活化过一硫酸盐氧化破络Cu-EDTA的特性研究[J]. 工业水处理, 2024, 44(1): 73-79.
[12]	徐莹莹, 赵秋雨, 常志淼, 于翔霏. 有机磷阻燃剂水体污染处理技术的研究进展[J]. 工业水处理, 2023, 43(5): 25-33.
[13]	刘佳露, 朱彧, 刘兆煐, 胡苧尹, 肖调兵. PDS/CoFe₂O₄活化体系在四环素废水处理中的应用[J]. 工业水处理, 2023, 43(4): 139-143.
[14]	李明安, 王榕, 罗从伟, 宋阳, 武道吉, 谭凤训, 成小翔. LED-UV₃₆₅/PDS体系降解碘帕醇的效能及机制研究[J]. 工业水处理, 2023, 43(4): 63-70.
[15]	徐啸, 刘杰, YUN Jiayin, 彭伟, 左梅梅, 丁昭霞, 胡家兴. Mn₃O₄-MnOOH复合材料催化过硫酸氢钾降解罗丹明B[J]. 工业水处理, 2023, 43(3): 124-131.

选择文件类型/文献管理软件名称

选择包含的内容

CoMoO₄@rGO复合膜的制备及其对染料废水的处理性能

The synthesis of CoMoO₄@rGO composite membrane and its performance on dye wastewater treatment

RichHTML

PDF

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 18

相关文章 15

编辑推荐

Metrics

本文评价

模态框（Modal）标题

选择文件类型/文献管理软件名称

选择包含的内容

CoMoO4@rGO复合膜的制备及其对染料废水的处理性能

The synthesis of CoMoO4@rGO composite membrane and its performance on dye wastewater treatment

RichHTML

PDF

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 9

参考文献 18

相关文章 15

编辑推荐

Metrics

本文评价

CoMoO₄@rGO复合膜的制备及其对染料废水的处理性能

The synthesis of CoMoO₄@rGO composite membrane and its performance on dye wastewater treatment