膜科学与技术

位置：首页 >> 期刊内容阅读

双金属负载PTFE中空纤维催化膜的制备与性能研究

作者：郑礼芃，林海波，王晓，刘富

单位： 1. 宁波大学材料科学与化学工程学院，浙江省宁波市 315211；2. 中国科学院宁波材料技术与工程研究所，浙江省宁波市 315201；3. 中国科学院大学，北京 100049

关键词：催化；PTFE中空纤维膜；钴铁双金属；单线态氧；

DOI号：

分类号： O63

出版年,卷(期):页码： 2023,43(2):24-34

摘要：

以聚四氟乙烯(PTFE)中空纤维膜为载体，通过亲水和胺化修饰，原位生长钴铁普鲁士蓝类似物，经低温煅烧（300℃）得到钴铁双金属负载的PTFE中空纤维催化膜。利用扫描电镜(SEM)、显微红外光谱仪(FTIR)和接触角测量仪(CA)等手段对膜的物化特性进行表征，还研究了其催化降解性能和长效稳定性。在连续24 h错流过滤下，催化活化过硫酸盐(PMS)产生以单线态氧(1O2)为主的多种活性氧(ROS)，实现了对罗丹明B(RhB)的瞬时去除，去除率达99%以上，分别研究了pH值、PMS用量以及阴离子种类和浓度对催化性能的影响。结果表明，钴铁双金属负载的PTFE中空纤维催化膜可有效实现高含盐废水中有机污染物的降解，并具有较好的运行稳定性，有望用于实际的工业废水的深度处理。

In this study, polytetrafluoroethylene (PTFE) hollow fiber membranes were used as carriers to grow cobalt-iron Prussian blue analogs in situ by hydrophilic and amination modifications, following with calcination at low temperature (300 °C) to obtain cobalt-iron bimetallic loaded PTFE hollow fiber catalytic membranes. The physical and chemical properties of the membranes were characterized by scanning electron microscopy (SEM),Micro-Fourier transform infrared (Micro-FTIR) spectrometer and contact angle (CA) measurement, and the membranes catalytic degradation performance and long-term stability were also investigated. Under cross-flow filtration for 24 h, the catalytic activation of peroxymonosulfate (PMS) produced 1O2 dominated reactive oxygen species (ROSs), achieving instantaneous removal of Rhodamine B(RhB) (> 99%). The effects of pH value, PMS dosage, type and concentration of anions on the catalytic performance were studied. The effects of pH value, the amount of PMS, the type and concentration of anions on the catalytic performance were investigated. The effects of pH, PMS dosage, and anion species and concentration on the catalytic performance were investigated separately. The results showed that the cobalt-iron bimetallic loaded PTFE hollow fiber catalytic membrane could effectively achieve the degradation of organic pollutants in the high-salinity wastewater with good operational stability. It is expected to be used in the actual advanced treatment of industrial wastewater.

基金项目：

中科院国际伙伴计划—全球共性挑战专项（181GJHZ2022038GC）；浙江省重点研发计划(2021C03170)

作者简介：

郑礼芃（1997-），男，江西赣州人，硕士，从事膜催化耦合及应用研究，E-mail：zhenglipeng@nimte.ac.cn.

参考文献：

[1] Shannon M A, Bohn P W, Elimelech M, et al. Science and technology for water purification in the coming decades [J]. Nature, 2008, 452(7185): 301-310.
[2] Alvarez P J J, Chan C K, Elimelech M, et al. Emerging opportunities for nanotechnology to enhance water security [J]. Nature Nanotechnology, 2018, 13(8): 634-641.
[3] Gao Y, Wu T W, Yang C D, et al. Activity Trends and Mechanisms in Peroxymonosulfate-Assisted Catalytic Production of Singlet Oxygen over Atomic Metal-N-C Catalysts [J]. Angewandte Chemie-International Edition, 2021, 60(41): 22513-22521.
[4] Dai Y, Zhang N, Xing C, et al. The adsorption, regeneration and engineering applications of biochar for removal organic pollutants: A review [J]. Chemosphere, 2019, 223: 12-27.
[5] Tiwari B, Sellamuthu B, Ouarda Y, et al. Review on fate and mechanism of removal of pharmaceutical pollutants from wastewater using biological approach [J]. Bioresource Technology, 2017, 224: 1-12.
[6] 杨静, 徐志康. 聚合物分离膜的表界面工程 [J]. 膜科学与技术, 2018, 38(01): 1-8.
[7] Cao J, Nie W, Huang L, et al. Photocatalytic activation of sulfite by nitrogen vacancy modified graphitic carbon nitride for efficient degradation of carbamazepine [J]. Applied Catalysis B: Environmental, 2019, 241: 18-27.
[8] Hodges B C, Cates E L, Kim J-H. Challenges and prospects of advanced oxidation water treatment processes using catalytic nanomaterials [J]. Nature Nanotechnology, 2018, 13(8): 642-650.
[9] Dong X, Chen Z, Tang A, et al. Mineral Modulated Single Atom Catalyst for Effective Water Treatment [J]. Advanced Functional Materials, 2022, 32(16): 2111565.
[10] Shih Y-J, Putra W N, Huang Y-H, et al. Mineralization and deflourization of 2,2,3,3-tetrafluoro-1-propanol (TFP) by UV/persulfate oxidation and sequential adsorption [J]. Chemosphere, 2012, 89(10): 1262-1266.
[11] Hori H, Nagano Y, Murayama M, et al. Efficient decomposition of perfluoroether carboxylic acids in water with a combination of persulfate oxidant and ultrasonic irradiation [J]. Journal of Fluorine Chemistry, 2012, 141: 5-10.
[12] Ji Y, Shi Y, Dong W, et al. Thermo-activated persulfate oxidation system for tetracycline antibiotics degradation in aqueous solution [J]. Chemical Engineering Journal, 2016, 298: 225-233.
[13] Song C, Zhan Q, Liu F, et al. Overturned Loading of Inert CeO2 to Active Co3O4 for Unusually Improved Catalytic Activity in Fenton-Like Reactions [J]. Angewandte Chemie International Edition, 2022, 61(16): e202200406.
[14] Zhou X, Luo M, Xie C, et al. Tunable S doping from Co3O4 to Co9S8 for peroxymonosulfate activation: Distinguished Radical/Nonradical species and generation pathways [J]. Applied Catalysis B: Environmental, 2021, 282: 119605.
[15] Su S, Guo W, Leng Y, et al. Heterogeneous activation of Oxone by CoxFe3−xO4 nanocatalysts for degradation of rhodamine B [J]. Journal of Hazardous Materials, 2013, 244-245: 736-742.
[16] Fu H, Zhao P, Xu S, et al. Fabrication of Fe3O4 and graphitized porous biochar composites for activating peroxymonosulfate to degrade p-hydroxybenzoic acid: Insights on the mechanism [J]. Chemical Engineering Journal, 2019, 375: 121980.
[17] Guo R, Li Y, Chen Y, et al. Efficient degradation of sulfamethoxazole by CoCu LDH composite membrane activating peroxymonosulfate with decreased metal ion leaching [J]. Chemical Engineering Journal, 2021, 417: 127887.
[18] 张昊, 马晓华, 许振良. 催化与分离双功能膜及膜反应器 [J]. 膜科学与技术, 2019, 39(01): 116-124.
[19] Dotzauer D M, Dai J, Sun L, et al. Catalytic Membranes Prepared Using Layer-by-Layer Adsorption of Polyelectrolyte/Metal Nanoparticle Films in Porous Supports [J]. Nano Letters, 2006, 6(10): 2268-2272.
[20] Lu N, Lin H, Xu S, et al. Bone/muscle-inspired polymer porous matrix toughened carbon nanofibrous catalytic membranes for robust emerging contaminants removal [J]. Chemical Engineering Journal, 2022, 442.
[21] Wang X, Li Y, Yu H, et al. High-flux robust ceramic membranes functionally decorated with nano-catalyst for emerging micro-pollutant removal from water [J]. Journal of Membrane Science, 2020, 611.
[22] Feng S, Zhong Z, Wang Y, et al. Progress and perspectives in PTFE membrane: Preparation, modification, and applications [J]. Journal of Membrane Science, 2018, 549: 332-349.
[23] Ji J, Liu F, Hashim N A, et al. Poly(vinylidene fluoride) (PVDF) membranes for fluid separation [J]. Reactive and Functional Polymers, 2015, 86: 134-153.
[24] 王宇阳, 肖泽仪, 樊森清, et al. MnO2@ZIF-8/PES复合催化膜的制备及甲醛催化氧化研究 [J]. 膜科学与技术, 2020, 40(03): 65-71+80.
[25] Lin H, Fang Q, Wang W, et al. Prussian blue/PVDF catalytic membrane with exceptional and stable Fenton oxidation performance for organic pollutants removal [J]. Applied Catalysis B: Environmental, 2020, 273: 119047.
[26] Lu N, Lin H, Li G, et al. ZIF-67 derived nanofibrous catalytic membranes for ultrafast removal of antibiotics under flow-through filtration via non-radical dominated pathway [J]. Journal of Membrane Science, 2021, 639.
[27] Deng J, Shao Y, Gao N, et al. CoFe2O4 magnetic nanoparticles as a highly active heterogeneous catalyst of oxone for the degradation of diclofenac in water [J]. Journal of Hazardous Materials, 2013, 262: 836-844.
[28] Wang F, Li J, Zhu H, et al. Physical modification of polytetrafluoroethylene flat membrane by a simple heat setting process and membrane wetting remission in SGMD for desalination [J]. Desalination, 2014, 354: 143-152.
[29] Wang Y, Lin H, Xiong Z, et al. A silane-based interfacial crosslinking strategy to design PVDF membranes with versatile surface functions [J]. Journal of Membrane Science, 2016, 520: 769-778.
[30] Fang Q, Li G, Lin H, et al. Solar-driven organic solvent purification enabled by the robust cubic Prussian blue [J]. Journal of Materials Chemistry A, 2019, 7(15): 8960-8966.
[31] Tian W, Hu H, Wang Y, et al. Metal–Organic Frameworks Mediated Synthesis of One-Dimensional Molybdenum-Based/Carbon Composites for Enhanced Lithium Storage [J]. ACS Nano, 2018, 12(2): 1990-2000.
[32] Li T, Liu F, Lin H, et al. Fabrication of anti-fouling, anti-bacterial and non-clotting PVDF membranes through one step “outside-in” interface segregation strategy [J]. Journal of Colloid and Interface Science, 2018, 517: 93-103.
[33] Khan N A, Najam T, Shah S S A, et al. Development of Mn-PBA on GO sheets for adsorptive removal of ciprofloxacin from water: Kinetics, isothermal, thermodynamic and mechanistic studies [J]. Materials Chemistry and Physics, 2020, 245: 122737.
[34] Hao J, Zhao S, Mao R, et al. Activation of peroxymonosulfate by cobalt doped graphitic carbon nitride for ammonia removal in chloride-containing wastewater [J]. Separation and Purification Technology, 2021, 271: 118858.
[35] Song N, Ren S, Zhang Y, et al. Confinement of Prussian Blue Analogs Boxes Inside Conducting Polymer Nanotubes Enables Significantly Enhanced Catalytic Performance for Water Treatment [J]. Advanced Functional Materials, 2022, 32(34): 2204751.
[36] Lai L, Yan J, Li J, et al. Co/Al2O3-EPM as peroxymonosulfate activator for sulfamethoxazole removal: Performance, biotoxicity, degradation pathways and mechanism [J]. Chemical Engineering Journal, 2018, 343: 676-688.
[37] Chen F, Liu L-L, Chen J-J, et al. Efficient decontamination of organic pollutants under high salinity conditions by a nonradical peroxymonosulfate activation system [J]. Water Research, 2021, 191: 116799.

服务与反馈：

【文章下载】【加入收藏】

《膜科学与技术》编辑部地址：北京市朝阳区北三环东路19号蓝星大厦邮政编码：100029 电话：010-64426130/64433466 传真：010-80485372邮箱：mkxyjs@163.com