Research Advances in the Preparation of Cyclodextrin-based Composite Adsorbents and the Removal of Organic Pollutants in Water
YU Fei1,2, CUI Tianran1, CHEN Dexian2, YAO Wenhao2,SUN Yiran3,MA Jie3, HE Yiwen4
1 College of Marine Ecology and Environment, Shanghai Ocean University, Shanghai 201306; 2 School of Chemical and Environmental Engineering, Shanghai Institute of Technology, Shanghai 201418; 3 State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, Shanghai 200092; 4 College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072;
Abstract: At present, the problem of aquatic organic pollution is becoming more and more serious. Among many technologies for water treatment, adsorption technology has broad application prospect in water treatment thanks to its merits, including low-cost, non-toxic, and environment-friendly etc. The research and development of high efficiency adsorbent is the key factor to determine the process of high efficiency adsorption treatment. At the same time, the cyclodextrin has an externally hydrophilic, internally hydrophobic, frustum-like unique structure that utilizes the inner cavity to form a host-guest inclusion with polar molecules, so they are used as adsorbents for the efficient removal of the organic pollutants from aqueous solutions. Cyclodextrins show a great hydrophilicity and excellent characteristics of the chemical reaction, and can be used for the efficient removal of ions in the solution due to their external structures with many hydroxyl groups. Meanwhile, cyclodextrins implement a variety of chemical modification and complete the functional expansion of cyclodextrin adsorbent. Now, the modification of cyclodextrins become a hot issue. This paper reviewes the preparation of cyclodextrin-based composite adsorbents, and mainly summarizes the applied research of the effective removal of organic pollutants in water. The research trend and research hot spot of cyclodextrin-based materials are discussed in this review. Finally, the future research direction are expected.
于飞, 崔天然, 陈德贤, 姚温浩, 孙怡然, 马杰, 和怡雯. 环糊精基复合吸附剂的制备及对水中有机污染物去除的研究进展[J]. 材料导报, 2018, 32(20): 3645-3653.
YU Fei, CUI Tianran, CHEN Dexian, YAO Wenhao, SUN Yiran, MA Jie, HE Yiwen. Research Advances in the Preparation of Cyclodextrin-based Composite Adsorbents and the Removal of Organic Pollutants in Water. Materials Reports, 2018, 32(20): 3645-3653.
1 Ali I. New generation adsorbents for water treatment[J]. Chemical Reviews,2012,112(10):5073. 2 Lumholdt L, Fourmentin S, Nielsen T T, et al. Removal of volatile organic compounds using amphiphilic cyclodextrin-coated polypropy-lene[J].Beilstein Journal of Organic Chemistry,2014,1(10):2743. 3 Abdolmaleki A, Mallakpour S, Borandeh S. Efficient heavy metal ion removal by triazinyl-beta-cyclodextrin functionalized iron nano-particles[J]. RSC Advances,2015,5(110):90602. 4 Hu X J, Liu Y G, Wang H, et al. Adsorption of copper by magnetic graphene oxide-supported β-cyclodextrin: Effects of pH, ionic strength, background electrolytes, and citric acid[J].Chemical Engineering Research & Design,2015,93:675. 5 Huang Z H, Wu Q L, Liu S X, et al. A novel biodegradable beta-cyclodextrin-based hydrogel for the removal of heavy metal ions[J].Carbohydrate Polymers,2013,97(2):496. 6 Kang H Y,Yang Z G,Huang X N.Removal of heavy metals using nanoscale zero-velent iron immobilized by sodium alginate/β-cyclodextrin[J]. Environmental Engineering,2015(6):144(in Chinese). 康海彦,杨治广,黄晓楠.海藻酸钠/β-环糊精固定化纳米FeO去除重金属的性能研究[J].环境工程,2015(6):144. 7 Ghemati D, Aliouche D. Dye adsorption behavior of polyvinyl alcohol/glutaraldehyde/beta-cyclodextrin polymer membranes[J]. Journal of Applied Spectroscopy,2014,81(2):257. 8 Yu L, Xue W, Cui L, et al. Use of hydroxypropyl-β-cyclodextrin/polyethylene glycol 400, modified Fe3O4 nanoparticles for congo red removal[J]. International Journal of Biological Macromolecules,2014,64:233. 9 Chen D L,Cao M L,Zhang X M,et al.Syntheis and dye adsorptivity of β-cyclodextrin polymer with a novel tricarboxylic acid as crosslin-king agent[J]. Petrochemical Technology,2014(2):210(in Chinese). 陈冬玲,曹曼丽,张晓梅,等.新型三元酸与β-环糊精交联聚合物的制备及其对染料吸附性能的研究[J].石油化工,2014(2):210. 10 刘志彬.磺化β-环糊精光催化降解有机磷农药久效磷的应用研究[J].广东化工,2015(18):18. 11 Kawano S, Kida T, Miyawaki K, et al. Cyclodextrin polymers as highly effective adsorbents for removal and recovery of polychlorobiphenyl (PCB) contaminants in insulating oil[J]. Environmental Science & Technology,2014,48(14):8094. 12 Yang Z, Liu J, Yao X, et al. Efficient removal of BTEX from aqueous solution by β-cyclodextrin modified poly(butyl methacrylate) resin[J].Separation and Purification Technology,2016,158:417. 13 Han Y Q,Zhou W J,Shen H M,et al. Progress in the immobilization of β-cyclodextrin and their application in adsorption of environmental pollutants[J]. Chinese Journal of Organic Chemistry,2016(2):248(in Chinese). 韩叶强,周文杰,沈海民,等.固载化β-环糊精吸附环境污染物的研究进展[J].有机化学,2016(2):248. 14 Shen H M,Fang H G,Wu H K,et al. Progress in the molecular morphology of cyclodextrin derivatives and their construction strategy[J]. Chemical Industry and Engineering Progress,2015(2):430(in Chinese). 沈海民,方红果,武宏科,等.环糊精衍生物的分子形态及其构筑策略研究进展[J].化工进展,2015(2):430. 15 Chen Q, Wen Y, Cang Y, et al. Selective removal of phenol by spherical particles of alpha-, beta-and gamma-cyclodextrin polymers: Kinetics and isothermal equilibrium[J].Frontiers of Chemical Science and Engineering,2013,7(2):162. 16 Alsbaiee A, Smith B J, Xiao L, et al. Rapid removal of organic micropollutants from water by a porous β-cyclodextrin polymer[J]. Nature,2016,529(7585):190. 17 Moulahcene L, Skiba M, Senhadji O, et al. Inclusion and removal of pharmaceutical residues from aqueous solution using water-insoluble cyclodextrin polymers[J].Chemical Engineering Research & Design,2015,97:145. 18 Zhao F, Repo E, Yin D, et al. EDTA-cross-linked β-cyclodextrin: An environmentally friendly bifunctional adsorbent for simultaneous adsorption of metals and cationic dyes[J].Environmental Science & Technology,2015,49(17):10570. 19 Raoov M, Mohamad S, Abas M R. Removal of 2,4-dichlorophenol using cyclodextrin-ionic liquid polymer as a macroporous material: Characterization, adsorption isotherm, kinetic study, thermodyna-mics[J]. Journal of Hazardous Materials,2013,263:501. 20 Kawano S, Kida T, Miyawaki K, et al. Adsorption capability of urethane-crosslinked heptakis (2,6-di-O-methyl)-beta-cyclodextrin polymers toward polychlorobiphenyls in nonpolar organic media[J]. Polymer Journal,2015,47(6):443. 21 Zhang X, Shi L, Xu G, et al. Synthesis of beta-cyclodextrin-calix 4 arene coupling product and its adsorption of basic fuchsin and methylene blue from water[J].Journal of Inclusion Phenomena and Macrocyclic Chemistry,2013,75(1-2):147. 22 Surikumaran H, Mohamad S,Sarih N M. Molecular imprinted polymer of methacrylic acid functionalised beta-cyclodextrin for selective removal of 2,4-dichlorophenol[J]. International Journal of Molecular Sciences,2014,15(4):6111. 23 Cheng J, Chang P R, Zheng P, et al. Characterization of magnetic carbon nanotube-cyclodextrin composite and its adsorption of dye[J]. Industrial & Engineering Chemistry Research,2014,53(4):1415. 24 Liu W, Jiang X Y, Chen X Q. A novel method of synthesizing cyclodextrin grafted multiwall carbon nanotubes/iron oxides and its adsorption of organic pollutant[J].Applied Surface Science,2014,320:764. 25 Wang D X, Liu L L, Jiang X Y, et al. Adsorbent for p-phenylene-diamine adsorption and removal based on graphene oxide functiona-lized with magnetic cyclodextrin[J].Applied Surface Science,2015,329:197. 26 Fan L, Luo C, Sun M, et al. Synthesis of magnetic β-cyclodextrin-chitosan/graphene oxide as nanoadsorbent and its application in dye adsorption and removal[J].Colloids and Surfaces B: Biointerfaces,2013,103:601. 27 Shen H M, Zhu G Y, Yu W B, et al. Surface immobilization of beta-cyclodextrin on hybrid silica and its fast adsorption performance of p-nitrophenol from the aqueous phase[J]. RSC Advances,2015,5(103):84410. 28 Carvalho L B D, Carvalho T G, Magriotis Z M, et al. Cyclodextrin/silica hybrid adsorbent for removal of methylene blue in aqueous media[J].Journal of Inclusion Phenomena and Macrocyclic Chemistry,2014,78(1-4):77. 29 Xue X, Gu Q, Pan G, et al. Nanocage structure derived from sulfonated β-cyclodextrin intercalated layered double hydroxides and selective adsorption for phenol compounds[J].Inorganic Chemistry,2014,53(3):1521. 30 Zhang X B, Wang Y, Yan S T. Simultaneous removal of Co(Ⅱ) and 1-naphthol by core-shell structured Fe3O4@cyclodextrin magnetic nanoparticles[J].Carbohydrate Polymers,2014,114:521. 31 Ebadi A, Rafati A A. Preparation of silica mesoporous nanoparticles functionalized with β-cyclodextrin and its application for methylene blue removal[J].Journal of Molecular Liquids,2015,209(1):239. 32 Ennist J H, Gobrogge E A, Schlick K H, et al. Cyclodextrin-functionalized chromatographic materials tailored for reversible adsorption[J]. ACS Applied Materials & Interfaces,2014,6(20):18087. 33 Wang D, Liu L, Jiang X, et al. Adsorption and removal of malachite green from aqueous solution using magnetic β-cyclodextrin-graphene oxide nanocomposites as adsorbents[J].Colloids and Surfaces A,2015,466:166. 34 Li L, Fan L, Sun M, et al. Adsorbent for hydroquinone removal based on graphene oxide functionalized with magnetic cyclodextrin-chitosan[J]. International journal of biological macromolecules,2013,58(7):169. 35 Hu J, Shao D, Chen C, et al. Removal of 1-naphthylamine from aqueous solution by multiwall carbon nanotubes/iron oxides/cyclodextrin composite[J]. Journal of Hazardous Materials,2011,185(1):463. 36 Zhou Y, Gu X, Zhang R, et al. Removal of aniline from aqueous solution using pine sawdust modified with citric acid and β-cyclodextrin[J].Industrial & Engineering Chemistry Research,2014,53(2):887. 37 Hu Q, Gao D W, Pan H, et al. Equilibrium and kinetics of aniline adsorption onto crosslinked sawdust-cyclodextrin polymers[J]. RSC Advances,2014,4(75):40071. 38 Zha F,Li S G,Chang Y. Preparation and adsorption property of chitosan beads bearing β-cyclodextrin cross-linked by 1,6-hexameth-ylene diisocyanate[J]. Carbohydrate Polymers,2008,72(3):456. 39 Sawicki R, Mercier L.Evaluation of mesoporous cyclodextrin-silica nanocomposites for the removal of pesticides from aqueous media[J].Environmental Science & Technology,2006,40(6):1978. 40 Chai K G,Ji H B. Dual functional adsorption of benzoic acid from wastewater by biological-based chitosan grafted β-cyclodextrin[J].Chemical Engineering Journal,2012,203:309. 41 Wang D,Liu L,Jiang X,et al.Adsorbent for P-phenylendediamine adsorption and removal based on graphene oxide functionalized with magnetic cyclodextrin[J]. Applied Surface Science,2015,329:197. 42 Chalasani R,Vasudevan S. Cyclodextrin functionalized magnetic iron oxide nanocrystals: A host-carrier for magnetic separation of non-polar molecules and arsenic from aqueous media[J]. Journal of Mate-rials Chemistry,2012,22(30):14925. 43 Qin B,Yang K. Preparation of acetylated β-cyclodextrin polymer microspheres and it’s adsorption study[J]. Applied Chemical Industry,2016(4):645(in Chinese). 秦蓓,杨宽.乙酰化β-环糊精聚合物微球对α-萘酚的吸附性能研究[J].应用化工,2016(4):645. 44 Kono H, Onishi K, Nakamura T. Characterization and bisphenol A adsorption capacity of β-cyclodextrin-carboxymethylcellulose-based hydrogels[J].Carbohydrate Polymers,2013,98(1):784. 45 Yuan W Z, Shen J, Li L L, et al. Preparation of POSS-poly(ε-caprolactone)-β-cyclodextrin/Fe3O4 hybrid magnetic micelles for remo-val of bisphenol A from water[J]. Carbohydrate Polymers,2014,113:353. 46 Wang N J,Zhou L L,Guo J,et al.Adsorption of environmental pollutants using magnetic hybridnanoparticles modified with β-cyclodextrin[J]. Applied Surface Science,2014,305:267. 47 Kono H, Nakamura T. Polymerization of β-cyclodextrin with 1,2,3,4-butanetetracarboxylic dianhydride: Synthesis, structural characterization, and bisphenol A adsorption capacity[J].Reactive & Functional Polymers,2013,73(8):1096. 48 王章慧,张培斌,胡帆等.用于去除水中有机微污染物的交联β-环糊精聚合物的制备及性能[C]//中国化学会2017全国高分子学术论文报告会.成都,2017. 49 Wang H J, Wang Y T, Zhou Y Q, et al. A facile removal of phenol in coking wastewater using beta-cyclodextrin modified with hexa-methylene diisocyanate[J]. Chinese Journal of Biochemistry and Molecular Biol,2013,11(6):82. 50 Hu S Y. Synthesis of M-xylylenediamine bridged bis (6-Amino-6-Deoxy-β-CD) and its sdsorption capacity for phenol[D]. Hengyang: University of South China,2015(in Chinese). 胡胜勇.1,3-二甲基氨基苯桥联β-环糊精的制备及其对苯酚的吸附性能研究[D].衡阳:南华大学,2015. 51 Shen H M, Zhu G Y, Yu W B, et al. Fast adsorption of p-nitrophenol from aqueous solution using beta-cyclodextrin grafted silica gel[J].Applied Surface Science,2015,356:1155. 52 Han J X,Xie K J,Du Z J,et al.β-Cyclodextrin functionalized polystyrene porous monoliths for separating phenol from wastewater[J].Carbohydrate Polymers,2015,120:85. 53 Badruddoza A,Hazel G S S, Hidajat K,et al. Synthesis of carboxymethyl-β-cyclodextrin conjugated magnetic nano-adsorbent for removal of methylene blue[J].Colloids and Surfaces A,2010,367:85. 54 Fan L, Zhang Y, Luo C, et al. Synthesis and characterization of magnetic beta-cyclodextrin-chitosan nanoparticles as nano-adsorbents for removal of methyl blue[J]. International Journal of Biological Macromolecules,2012,50(2):444. 55 Liu Y. Study on adsorption performance of β-cyclodextrin/poiyethy-leneimine bifunctional magnetic nanoparticles for removal of anionic dyes from aqueous solution[D].Kunming: Kunming University of Science and Technology,2013(in Chinese). 刘旸.β-环糊精/聚乙烯亚胺双功能化磁性纳米颗粒吸附水中阴离子染料的性能研究[D].昆明:昆明理工大学,2013. 56 Massaro M, Colletti C G, Lazzara G, et al. Synthesis and characte-rization of HNT-cyclodextrin nanosponges for enhanced dyes adsorption[J].ACS Sustainable Chemistry & Engineering,2017,5(4):3346. 57 Li X M, Zhou M J, Jia X,et al. Water-insoluble viologen-based β-cyclodextrin polymer for selective adsorption toward anionic dyes[J]. Reactive and Functional Polymers,2018,126:20. 58 Crini G. Kinetic and equilibrium studies on the removal of cationic dyes from aqueous solution by adsorption onto a cyclodextrin polymer[J]. Dyes and Pigments,2008,77(2):415. 59 Hai W. Preparation of novel β-cyclodextrin polymer and its adsorption properties to organic dyes [D].Nanchang: Nanchang Hangkong University, 2017(in Chinese). 海伟.基于β-环糊精新型聚合物的制备及对有机染料吸附性研究[D].南昌:南昌航空大学,2017. 60 Huang Z. Preparation of magnetic nanomaterial based on β-cyclodextrin modification and its adsorption property[D]. Lanzhou: Lanzhou University,2018(in Chinese). 黄峥.基于β-环糊精改性的磁性纳米材料的制备及其吸附性能的研究[D].兰州:兰州大学,2018. 61 Xie Y P,Yang G,Xing W H.Study on adsorption property of methy-lene blue by the magnetic chitosan microspheres modified with β-Cyclodextrin[J]. New Chemical Materials,2017(6):191(in Chinese). 谢亚平,杨刚,邢卫红.β-环糊精改性磁性壳聚糖微球对亚甲基蓝吸附性能研究[J].化工新型材料,2017(6):191. 62 Huang Y L,Wang Q Y. Preparation of β-cyclodextrin /cellulose acetate nanofibers and its application for dye wastewater taeatment[J]. Environmental Engineering, 2017(6):29(in Chinese). 黄永兰,王沁宇.β-环糊精/醋酸纤维素纳米纤维的制备及对染料废水的处理[J].环境工程,2017(6):29.
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2018, Vol. 32 
