Cu~(2+)印迹交联壳聚糖微球的合成及吸附性能
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摘要
利用分子印迹技术,以壳聚糖(CS)为功能单体,Cu~(2+)为印迹离子,通过稀氨水固化、环氧氯丙烷交联、盐酸洗脱Cu~(2+),制得了Cu~(2+)印迹交联壳聚糖微球(Cu~(2+)-ICM)。采用FTIR、XRD和FESEM对产品进行了表征,并测定了微球的骨架密度、含水量和交联度。结果表明:交联改性可使微球具有多孔结构和良好的结构稳定性,能够很好地降低CS的酸溶性,提高微球对Cu~(2+)的吸附性能。通过正交实验L_9(3~4)得到Cu~(2+)-ICM的最优制备条件为:CS 1.5 g,环氧氯丙烷2.5 mL,80℃下交联3.0 h,制得的微球对Cu~(2+)吸附量为67.80 mg/g。在单组分体系中考察了微球对Cu~(2+)的吸附性能。结果表明:当微球投加量为50 mg,Cu~(2+)初始质量浓度为338.7 mg/L,pH=5.0时,吸附量为72.80 mg/g。
By using the molecular imprinting technique, Cu~(2+) imprinted cross-linked chitosan microspheres(Cu~(2+)-ICM) with chitosan(CS) as functional monomer, Cu~(2+) as template ion were prepared by curing with dilute ammonia, crosslinking with epoxy chloropropane and elution with hydrochloric acid. The products were characterized by FTIR, XRD and FESEM. Their physical properties such as skeleton density, water content and crosslinking degree were measured. The results showed that the crosslinking modification made the microspheres have porous structure and good structural stability, reduced the acid solubility of CS very well, and improved the adsorption properties of microspheres on Cu~(2+). An orthogonal test L_9(3~4) was used to investigate the optimum preparation conditions of Cu~(2+)-ICM. It was found that CS 1.5 g, epoxy chloropropane 2.5 m L, crosslinking temperature 80 ℃, crosslinking time 3.0 h were optimal. Under the optimum conditions, the adsorption capacity of the prepared Cu~(2+)-ICM to Cu~(2+) was 67.80 mg/g. The adsorption properties of microspheres to Cu~(2+) were also studied in single component system. The results demonstrated that when the dosage of microspheres was 50 mg, initial concentration of Cu~(2+) was 338.7 mg/L,and pH value was 5.0, the Cu~(2+) adsorption capacity of microspheres was 72.80 mg/g.
By using the molecular imprinting technique, Cu~(2+) imprinted cross-linked chitosan microspheres(Cu~(2+)-ICM) with chitosan(CS) as functional monomer, Cu~(2+) as template ion were prepared by curing with dilute ammonia, crosslinking with epoxy chloropropane and elution with hydrochloric acid. The products were characterized by FTIR, XRD and FESEM. Their physical properties such as skeleton density, water content and crosslinking degree were measured. The results showed that the crosslinking modification made the microspheres have porous structure and good structural stability, reduced the acid solubility of CS very well, and improved the adsorption properties of microspheres on Cu~(2+). An orthogonal test L_9(3~4) was used to investigate the optimum preparation conditions of Cu~(2+)-ICM. It was found that CS 1.5 g, epoxy chloropropane 2.5 m L, crosslinking temperature 80 ℃, crosslinking time 3.0 h were optimal. Under the optimum conditions, the adsorption capacity of the prepared Cu~(2+)-ICM to Cu~(2+) was 67.80 mg/g. The adsorption properties of microspheres to Cu~(2+) were also studied in single component system. The results demonstrated that when the dosage of microspheres was 50 mg, initial concentration of Cu~(2+) was 338.7 mg/L,and pH value was 5.0, the Cu~(2+) adsorption capacity of microspheres was 72.80 mg/g.
引文
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[25]Ma Licheng(马立成).Synthesis and properties of Cu2+ion-imprinted magnetic chitosan beads for selective recognition of Cu2+ion in aqueous solution[D].Beijing:General Research Institute for Nonferrous Metals(北京有色金属研究总院),2015.
[26]Li Zhuangzhi(李壮志).Cross-linked chitosan adsorbent under microwave irradiation[D].Shenyang:Shenyang Ligong University(沈阳理工大学),2015.
[27]Ma Xiaojie(马晓杰).Preparation and application of molecularly imprinted chitosan in water treatment[D].Shenyang:Shenyang Ligong University(沈阳理工大学),2014.
[2]Dong J,Li B W,Bao Q.In situ reactive zone with modified Mg(OH)2for remediation of heavy metal polluted groundwater:Immobilization and interaction of Cr(Ⅲ),Pb(Ⅱ)and Cd(Ⅱ)[J].Journal of Contaminant Hydrology,2017,199:50-57.
[3]Cui Qing(崔青),Zhao Hong(赵红),Zhang Changqiao(张长桥),et al.Research progress in noble metal-supported chitosan functional microspheres[J].Chemical Industry and Engineering Progress(化工进展),2017,36(2):595-601.
[4]Pu Shengyan(蒲生彦),Zhou Yan(周艳),Wang Miaoting(王妙婷),et al.Review on preparation of cross-linked chitosan and adsorption of heavy metal ions[J].Technology of Water Treatment(水处理技术),2016,42(11):1-4.
[5]Sami G.Biosorption of heavy metal from aqueous solution using cellulosic waste orange peel[J].Ecological Engineering,2017,99:134-140.
[6]Chitpong N,Husson S M.High-capacity,nanofiber-based ion-exchange membranes for the selective recoveryof heavy metals from impaired waters[J].Separation and Purification Technology,2017,179:94-103.
[7]Pathania D,Sharma G,Thakur R.Pectin@zirconium(Ⅳ)silicophosphate nanocomposite ion exchanger:Photocatalysis,heavy metal separation and antibacterial activity[J].Chemical Engineering Journal,2015,267:235-244.
[8]Liu B J,Wang D F,Yu G L,et al.Adsorption of heavy metal ions,dyes and proteins by chitosan composites and derivatives-A review[J].Journal of Ocean University of China,2013,12(3):500-508.
[9]Reddy D K,Lee S M.Application of magnetic chitosan composites for the removal of toxic metal and dyes from aqueous solutions[J].Advances in Colloid and Interface Science,2013,201/202(4):68-93.
[10]Fan L,Luo C,Sun M,et al.Highly selective adsorption of lead ions by water dispersible magnetic chitosan/graphene oxide composites[J].Colloids and Surfaces B:Biointerfaces,2013,103(1):523-529.
[11]Qu J,Zhao X,Ma P X,et al.pH-responsive self-healing injectable hydrogel based on N-carboxyethyl chitosan for hepatocellular carcinoma therapy[J].Acta Biomaterialia,2017,58:168-180.
[12]Xin Lulu(辛露露),Zhang Yu(张雨),Liu Baochuan(刘宝传),et al.Preparation and release behavior of avermectin microspheres[J].Fine Chemicals(精细化工),2018,35(4):652-657.
[13]Nan Wei(南伟),Sun Ailan(孙爱兰).Application of chitosan and oligochitosan in the field of cosmetics[J].Chemical Industry and Engineering Progress(化工进展),2003,22(12):1304-1307.
[14]Guo Junyuan(郭俊元),Chen Cheng(陈诚),Zhang Ping(张萍),et al.Modification of a chitosan and its performances in dye substance removal from wastewater[J].Acta Scientiae Circumstantiae(环境科学学报),2018,38(4):1529-1536.
[15]Zhou Yaozhen(周耀珍).Preparation of crosslinked and grafted chitosan and its adsorption performance[D].Nanjing:Nanjing Forestry University(南京林业大学),2014.
[16]Peng Qingqing(彭庆庆).Study on chitosan modified materials preparation and their adsorption performance and mechanism of heavy metal ions in aqueous solution[D].Changsha:Hunan University(湖南大学),2017.
[17]Zhang Jin(张进),Tian Lang(田浪),Tang Honglin(唐红林),et al.Synthesis of dibutyl phthalate molecularly imprinted sorbent material and evaluation of its adsorption properties[J].Fine Chemicals(精细化工),2013,30(8):866-870.
[18]Cheong W J,Yang S H,Ali F.Molecular imprinted polymers for separation science:A review of reviews[J].Journal of Separation Science,2013,36(3):609-628.
[19]Viswanathan S,Rani C,RibeiorS,et al.Molecular imprinted nanoelectrodes for ultra sensitive detection of ovarian cancer marker[J].Biosensors and Bioelectronics,2012,33(1):179-183.
[20]Chen H J,Zhang Z H,Luo L J,et al.Surface-imprinted chitosan-coated magnetic nanoparticles modified multi-walled carbon nanotubes biosensor for detection of bovine serum albumin[J].Sensors and Actuators,2012,163(1):76-83.
[21]Ying X G,Yoshioka H T,Liu C J,et al.Molecular imprinting technique in putrescine visualized detection[J].Sensors and Actuators B:Chemical,2018,258:870-880.
[22]Xu Long(许龙),Huang Yun’an(黄运安),Zhu Qiujin(朱秋劲),et al.Preparation and application of molecularly imprinted polymers based on chitosan[J].Chemical Industry and Engineering Progress(化工进展),2016,35(3):847-855.
[23]Bi Shaodan(毕韶丹),Li Zhihua(李志华),Guo Jing(郭静),et al.Preparation and adsorption properties of Cu2+imprinted chitosan microspheres[J].Journal of Shenyang Ligong University(沈阳理工大学学报),2015,34(6):11-19.
[24]Shi Guang(石光),Hu Xiaoyan(胡小艳),Zheng Jianhong(郑建泓),et al.Removal of metal ions from aqueous solution using Cu(Ⅱ)imprinted chitosan cross-linked porous microspheres[J].Ion Exchange and Adsorption(离子交换与吸附),2010,26(2):103-110.
[25]Ma Licheng(马立成).Synthesis and properties of Cu2+ion-imprinted magnetic chitosan beads for selective recognition of Cu2+ion in aqueous solution[D].Beijing:General Research Institute for Nonferrous Metals(北京有色金属研究总院),2015.
[26]Li Zhuangzhi(李壮志).Cross-linked chitosan adsorbent under microwave irradiation[D].Shenyang:Shenyang Ligong University(沈阳理工大学),2015.
[27]Ma Xiaojie(马晓杰).Preparation and application of molecularly imprinted chitosan in water treatment[D].Shenyang:Shenyang Ligong University(沈阳理工大学),2014.