针对常规碳纳米纤维力学柔韧性能和亲水性不足的问题,为了提高其对水中有机物污染物的吸附去除应用性能,以聚丙烯腈和苯并𫫇嗪为纺丝聚合物,以氧化铜纳米颗粒作为掺杂物质,通过静电纺丝制备了复合前驱体纳米纤维膜;随后经过热处理、高温碳化工艺制备出了Cu/CuO杂化碳纳米纤维膜。结果表明:所制备的杂化碳纳米纤维膜具有良好的力学柔韧性和超亲水性,其在室温条件下可实现对水中有机染料和乳化油滴的有效吸附分离,去除有机染料效率可达97.1%,去除乳化油滴效率在90%以上,在水体有机污染物治理领域表现出良好的应用前景。
Aiming at the problems of insufficient mechanical flexibility and hydrophilicity of conventional carbon nanofibers,in order to improve their adsorption and removal application performance for organic pollutants in water,polyacrylonitrile and benzoxazine were used as spinning polymers,and copper oxide nanoparticles were used as dopants to prepare composite precursor nanofiber membranes by electrospinning.Subsequently,Cu/CuO hybrid carbon nanofiber membranes were obtained by heat treatment and high-temperature carbonization.The results showed that the prepared hybrid carbon nanofiber membranes exhibited excellent mechanical flexibility and super-hydrophilicity.They could effectively adsorb and separate organic dyes and emulsified oil droplets in water at room temperature.The removal efficiency for organic dyes reached 97.1%,and the removal efficiency for emulsified oil droplets was more than 90%,demonstrating promising application prospect in the field of organic pollutant treatment in water.
[1] Wang Z,Wang H,Wang P,et al.Application of MOFs driven by various energy sources for degradation the organic pollutants in water:a review[J].Coordination Chemistry Reviews,2024,499:215506.
[2] 刘媛,吴志跃,姚军强,等.厌氧膜生物反应器处理有机垃圾渗滤液的COD去除率与膜过滤性能研究[J].新能源进展,2022,10(4):291-297.
[3] 张鸥,赵娜,刘璐,等.基于膜分离技术的化工废水净化研究[J].中国轮胎资源综合利用,2024,12(10):74-76.
[4] 郭榕.复合金属硅酸盐的制备及其臭氧催化氧化含环丙沙星废水的研究[D].郑州:中原工学院,2024.
[5] Rajan Y,Ngaini Z,Wahi R.Novel adsorbent from sago-grafted silica for removal of methylene blue[J].International Journal of Environmental Science and Technology,2018,16(8):4531-4542.
[6] Ha Y,Park Y,Hyun K,et al.Basic zeolites as efficient adsorbents for removing trace amounts of acetylene from ethylene[J].Chemistry of Materials,2024,36(7):3259-3266.
[7] 李海霞,左钧元,李欣彤,等.生物质活性炭的制备及其吸附处理染料污染物的行为与机理研究进展[J].化工新型材料,2025,53(2):28-33.
[8] 刘博文,李文,廖悦,等.碳基纳米复合材料吸附剂的制备及应用进展[J].化工新型材料,2023,51(12):294-297.
[9] Ren X,Liu H,Wang J,et al.Electrospinning-derived functional carbon-based materials for energy conversion and storage[J].Chinese Chemical Letters,2024,35(6):109282.
[10] Bai Y,Huang Z H,Kang F.Surface oxidation of activated electrospun carbon nanofibers and their adsorption performance for benzene,butanone and ethanol[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2014,443:66-71.
[11] Betar B O,Alsaadi M A,Chowdhury Z Z,et al.High yield super-hydrophobic carbon nanomaterials using cobalt/iron Co-catalyst impregnated on powder activated carbon[J].Processes,2021,9(1):134.
[12] Ren T,Si Y,Yang J,et al.Polyacrylonitrile/polybenzoxazine-based Fe3O4@carbon nanofibers:hierarchical porous structure and magnetic adsorption property[J].Journal of Materials Chemistry,2012,22(31):15919-15927.
[13] Bai Y,Huang Z H,Kang F.Electrospun preparation of microporous carbon ultrafine fibers with tuned diameter,pore structure and hydrophobicity from phenolic resin[J].Carbon,2014,66:705-712.
[14] Zhou A,Du J,Shi Y,et al.Hierarchical porous carbon nanofibrous membranes with elaborated chemical surfaces for efficient adsorptive removal of volatile organic compounds from air[J].Journal of Colloid and Interface Science,2024,673:860-873.
[15] Cheng F,Zhang X,Wen R,et al.Thermal conductivity enhancement of form-stable tetradecanol/expanded perlite composite phase change materials by adding Cu powder and carbon fiber for thermal energy storage[J].Applied Thermal Engineering,2019,156:653-659.
[16] Jung H S,Park Y,Nah C W,et al.Evaluation of the mechanical properties of polyether sulfone-toughened epoxy resin for carbon fiber composites[J].Fibers and Polymers,2021,22(1):184-195.
[17] 戎旭东.基于铝-氧化铜原位反应的铝基复合材料制备及性能研究[D].天津:天津大学,2021.
[18] Kong F,Xin B.Three-dimensional and flexible carbon nanofiber mat by one-step electrospinning for efficient oil/water separation[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2022,652:129824.
[19] Weidenthaler C,Lu A H,Schmidt W,et al.X-ray photoelectron spectroscopic studies of PAN-based ordered mesoporous carbons (OMC)[J].Microporous and Mesoporous Materials,2006,88(1-3):238-243.
[20] Starowicz Z,Neęcek K G,Socha R P,et al.Materials studies of copper oxides obtained by low temperature oxidation of copper sheets[J].Materials Science in Semiconductor Processing,2021,121:105368.
[21] Gherasim C,Pascariu P,Asandulesa M,et al.Copper oxide nanostructures:preparation,structural,dielectric and catalytic properties[J].Ceramics International,2022,48(17):25556-25568.
[22] 陈妍明,景连霞,高云玲.CuSO4@GA@PEI@CA复合膜的制备及其分离性能研究[J].化工新型材料,2025,53(6):99-104.
[23] Jafari A,Tahani K,Dastan D,et al.Ion implantation of copper oxide thin films;statistical and experimental results[J].Surfaces and Interfaces,2020,18:100463.
[24] Kaewyai K,Choopun S,Gardchareon A,et al.Mechanism and experimental evidence of rapid morphological variant of copper oxide nanostructures by microwave heating[J].Applied Surface Science,2019,474:9-16.
[25] Moseenkov S I,Kuznetsov V L,Zolotarev N A,et al.Investigation of amorphous carbon in nanostructured carbon materials (a comparative study by TEM,XPS,Raman Spectroscopy and XRD)[J].Materials,2023,16(3):1112.
[26] Sharma C,Kaur M,Choudhary A,et al.Nitrogen doped carbon-silica based Cu(0) nanometal catalyst enriched with well-defined N-moieties:synthesis and application in one-pot synthesis of 1,4-disubstituted-1,2,3-triazoles[J].Catalysis Letters,2020,150(1):82-94.
[27] Jellicoe M,Yang Y,Stokes W,et al.Continuous flow synthesis of copper oxide nanoparticles enabling rapid screening of synthesis-structure-property relationships[J].Small,2025,21(6):2403529.
[28] 胡崟,莫立焕,李军,等.煤气化渣制备碳硅介孔材料及甲基橙吸附性能研究[J].应用化工,2024,53(5):1009-1014.
[29] 孟嘉民.基于ZIF-67衍生炭材料的制备及染料吸附性能研究[D].长春:长春工业大学,2025.
[30] Hua T,Li D,Li X,et al.Synthesis of mesoporous-structured MIL-68(Al)/MCM-41-NH2 for methyl orange adsorption:optimization and selectivity[J].Environmental Research,2022,215:114433.
[31] Zhang P,Xu Y,Guo K,et al.Hierarchical-pore UiO-66 modified with Ag for π-complexation adsorption desulfurization[J].Journal of Hazardous Materials,2021,418:126247.
[32] Duan Z,Song M,Li T,et al.Characterization and adsorption properties of cross-linked yeast/β-cyclodextrin polymers for Pb(Ⅱ) and Cd(Ⅱ) adsorption[J].RSC Advances,2018,8(55):31542-31554.
[33] Seon J,Hwang Y.Cu/Cu2O-immobilized cellulosic filter for enhanced iodide removal from water[J].Journal of Hazardous Materials,2021,409:124415.
[34] Özcan A,Özcan A S.Adsorption of Acid Red 57 from aqueous solutions onto surfactant-modified sepiolite[J].Journal of Hazardous Materials,2005,125(1):252-259.
[35] Yao Y,Xu F,Chen M,et al.Adsorption behavior of methylene blue on carbon nanotubes[J].Bioresource Technology,2010,101(9):3040-3046.
[36] Yang X,Wang C,Zhou B,et al.Characterization of an iron-copper bimetallic metal-organic framework for adsorption of methyl orange in aqueous solution[J].Journal of Analytical Methods in Chemistry,2023,2023(1):9985984.
[37] Teng D,Jin P,Guo W,et al.Recyclable magnetic iron immobilized onto chitosan with bridging Cu ion for the enhanced adsorption of methyl orange[J].Molecules,2023,28(5):2307.
[38] Prajapati A K,Mondal M K.Comprehensive kinetic and mass transfer modeling for methylene blue dye adsorption onto CuO nanoparticles loaded on nanoporous activated carbon prepared from waste coconut shell[J].Journal of Molecular Liquids,2020,307:112949.
[39] Srivastava V,Choubey A K.Investigation of adsorption of organic dyes present in wastewater using chitosan beads immobilized with biofabricated CuO nanoparticles[J].Journal of Molecular Structure,2021,1242:130749.
[40] Sankaranarayanan S,Lakshmi D S,Vivekanandhan S,et al.Biocarbons as emerging and sustainable hydrophobic/oleophilic sorbent materials for oil/water separation[J].Sustainable Materials and Technologies,2021,28:e00268.
[41] Liu W,Huang X,Peng K,et al.PDA-PEI copolymerized highly hydrophobic sponge for oil-in-water emulsion separation via oil adsorption and water filtration[J].Surface and Coatings Technology,2021,406:126743.
[42] Chen W,Huang X,Zhou M,et al.Rose-petal-inspired fabrication of conductive superhydrophobic/superoleophilic carbon with high adhesion to water from orange peels for efficient oil adsorption from oil-water emulsion[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2023,661:130920.
基金资助
南通市自然科学基金面上项目(JC2024092);国家自然科学基金青年项目(52003125和22408181);江苏省科技厅基础研究计划(自然科学基金)青年基金项目(BK20200968和BK20240953)
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