新型磁性超分子基功能吸附材料的制备及性能研究
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摘要
在重金属复合污染治理中,为开发具备高性能的新型功能吸附剂,研究采用共沉淀法制备磁性载体粒子(MNP),硅烷化、Michael加成及酰胺化反应以"发散"形态于表面合成端氨基超支化分子(MD),交联活化改性壳聚糖(CMCS),制备出新型磁性功能吸附材料(CCMD)。利用傅立叶变换红外光谱(FT-IR)、比表面积分析仪、元素分析仪结构表征产物;X射线衍射仪(XRD)、扫描/透射电镜(SEM/TEM)分析产物晶型及表观形貌;热重分析仪(TG)测试产物的热敏感性能;振动样品磁强计(VSM)和Zeta电位分析仪测试样品光电磁性;并开展吸附性能研究。结果表明:成功制备出目标功能化合物(CCMD),CCMD粒径为13～19nm,呈顺磁性磁铁矿晶型,MNP、MD、CCMD磁化值分别为11.6,11.3和9.0 emu×g~(-1),Zeta电位测试显示MD和CCMD电位随pH升高而降低,且CCMD表面电位高于MD,以上测试结果同时也进一步证实产物的成功制备。吸附研究结果表明:当pH分别为11和5时,对重金属Cd(II)离子与F离子表现出高效吸附能力,具有pH智能响应特征,且最大吸附容量为79.12和65.05mg×g~(-1)。重复吸附-脱附实验表明CCMD对Cd(II)和F去除率均在75%以上,再生性能良好。
Magnetic carrier particles(MNP) were prepared by co-precipitation, which was treated by silanization, Michael addition and amidation reactions on surface to form amino hyperbranched molecule(MD). This intermediate was cross-linked with activated modified chitosan(CMCS) to prepare a new magnetic functional adsorption material(CCMD) for heavy metal adsorption. The product was characterized by Fourier transform infrared spectroscopy(FT-IR), specific surface area analyzer and elemental analysis. X-ray diffractometer(XRD) and scanning/transmission electron microscopy(SEM/TEM) were used to analyze the crystal form and morphology. Thermogravimetric analysis(TG), vibrating sample magnetometer(VSM) and Zeta potential analysis were performed for thermal and photomagnetism property measurements. The adsorption performance of the product was studied. The results show that the target functional compound(CCMD) is successfully prepared in paramagnetic magnetite crystal form with particle size of 13～19 nm. The magnetization values of MNP, MD and CCMD were 11.6, 11.3 and 9.0 emu×g~(-1), respectively. Zeta potential results show that the surface potential of MD and CCMD decrease with the increase of pH, and the CCMD surface potential is higher than that of MD. These results also confirm the successful preparation of the product. Adsorption results show that the material has high adsorption capacity for Cd(II) and F ions at pH 11 and pH 5 with pH intelligent response characteristics. The maximum adsorption capacities are 79.12 mg×g~(-1) and 65.05 mg×g~(-1), respectively. Repeated adsorption-desorption experiments show that CCMD has Cd(II) and F removal rates over 75% with good regeneration performance.
Magnetic carrier particles(MNP) were prepared by co-precipitation, which was treated by silanization, Michael addition and amidation reactions on surface to form amino hyperbranched molecule(MD). This intermediate was cross-linked with activated modified chitosan(CMCS) to prepare a new magnetic functional adsorption material(CCMD) for heavy metal adsorption. The product was characterized by Fourier transform infrared spectroscopy(FT-IR), specific surface area analyzer and elemental analysis. X-ray diffractometer(XRD) and scanning/transmission electron microscopy(SEM/TEM) were used to analyze the crystal form and morphology. Thermogravimetric analysis(TG), vibrating sample magnetometer(VSM) and Zeta potential analysis were performed for thermal and photomagnetism property measurements. The adsorption performance of the product was studied. The results show that the target functional compound(CCMD) is successfully prepared in paramagnetic magnetite crystal form with particle size of 13～19 nm. The magnetization values of MNP, MD and CCMD were 11.6, 11.3 and 9.0 emu×g~(-1), respectively. Zeta potential results show that the surface potential of MD and CCMD decrease with the increase of pH, and the CCMD surface potential is higher than that of MD. These results also confirm the successful preparation of the product. Adsorption results show that the material has high adsorption capacity for Cd(II) and F ions at pH 11 and pH 5 with pH intelligent response characteristics. The maximum adsorption capacities are 79.12 mg×g~(-1) and 65.05 mg×g~(-1), respectively. Repeated adsorption-desorption experiments show that CCMD has Cd(II) and F removal rates over 75% with good regeneration performance.
引文
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[2]朱冰韧,厉炯慧,沈海云,等.大容量阴离子交换树脂D296对水中铬(VI)的吸附[J].高校化学工程学报,2017,31(3):743-748.ZHU B R,LI J H,SHEN H Y,et al.Cr(VI)removal from aqueous solutions by a high-capacity strong acid resin D296[J].Journal of Chemical Engineering of Chinese Universities,2017,31(3):743-748.
[3]杨金燕,苟敏.中国土壤氟污染研究现状[J].生态环境学报,2017,26(3):506-513.YANG J Y,GOU M.The research status of fluorine contamination in soils of china[J].Ecology and Environmental Sciences,2017,26(3):506-513.
[4]LIU R X,TAN R J,LI B,et al.Overview of pops and heavy metals in Liao river basin[J].Environmental Earth Sciences,2015,73(9):5007-5017.
[5]SALEHINIA S,GHOREISHI S M,MAYA F,et al.Hydrophobic magnetic montmorillonite composite material for the efficient adsorption and microextraction of bisphenol A from water samples[J].Journal of Environmental Chemical Engineering,2016,4(4):4062-4071.
[6]MORAIS E C,CORREA G G,BRAMBILLA R,et al.Selective silica-based sorbent materials synthesized by molecular imprinting for adsorption of pharmaceuticals in aqueous matrices[J].Journal of Separation Science,2013,36(3):636-643.
[7]吴晨,刘涛,陈立钢,等.磁性金属有机骨架材料吸附分离靛蓝二磺酸钠[J].环境科学与技术,2017(10):43-48.WU C,LIU T,CHEN L G,et al.Adsorption and removal of indigo carmine by magnetic metal organic framework materials[J].Environmental Science&Technology,2017(10):43-48.
[8]UYGUN M,FEYZIO?LU E,?Z?ALI?KAN E,et al.New generation ion-imprinted nanocarrier for removal of Cr(VI)from wastewater[J].Journal of Nanoparticle Research,2013,15(8):1-11.
[9]朱寿进,刘法谦,王璟朝,等.新型羧甲基壳聚糖水凝胶的合成与表征[J].高等化学学报,2014,35(4):863-868.ZHU S J,LIU F Q,WANG J C,et al.Systhesis and characterization of novel carboxymethyl chitosan hydrogel[J].Chemical Journal of Chinese Universities,2014,35(4):863-868.
[10]杨美琪,孙雪菲,王曙光.羧甲基壳聚糖-葡聚糖微球对氟离子吸附性能研究[J].环境科学学报,2017,37(12):4562-4568.YANG M Q,SUN X F,WANG S G.Preparation of carboxymethyl chitosan-glucan composite microspheres and its adsorption behavior to fluorine ion[J].Acta Scientiae Circumstantiae,2017,37(12):4562-4568.
[11]HABIBA U,AFIFI A M,SALLEH A,et al.Chitosan/(polyvinyl alcohol)/zeolite electrospun composite nanofibrous membrane for adsorption of Cr6+,Fe3+and Ni2+[J].Journal of Hazardous Materials,2017,322:182-194.
[12]布林朝克,郭婷,张邦文,等.部分还原氧化石墨烯-Fe3O4对水中Mn(Ⅱ)的快速去除[J].高等学校化学学报,2017,38(2):217-224.BULIN C K,GUO T,ZHANG B W,et al.Fast removal of aqueous Mn(II)using partially reduced graphene oxide-Fe3O4[J].Chemical Journal of Chinese Universities,2017,38(2):217-224.
[13]苏立强,滕跃,王媛媛,等.磁性壳聚糖表面印迹四环素材料的制备及其吸附性能研究[J].分析试验室,2017(9):1071-1075.SU L Q,TENG Y,WANG Y Y,et al.Study on preparation and adsorption properties of magnetic-chitosan surface imprinted tetracycline[J].Chinese Journal of Analysis Laboratory,2017(9):1071-1075.
[14]刘明强.超支化结构磁性纳米复合材料对污染物吸附行为研究[D].天津:天津工业大学,2017.LIU M Q.Adsorption behavior of hyperbranched structure magnetic nanocomposites on pollutants[D].Tianjin:Tianjin Polytechnic University,2017.
[15]YAN L,LV M,SU C,et al.An efficient supramolecular adsorbent for co-adsorption of dyes and metal ions from wastewater and its application in self-healing materials[J].Soft Matter,2017,13(46):8772-8780.
[16]HAMZA M F,ALY M M,ABDEL-RAHMAN A A,et al.Functionalization of magnetic chitosan particles for the sorption of U(VI),Cu(II)and Zn(II)-hydrazide derivative of glycine-grafted chitosan[J].Materials,2017,10(5):539-560.
[17]PAN S,ZHANG Y,SHEN H,et al.An intensive study on the magnetic effect of mercapto-functionalized nano-magnetic Fe3O4,polymers and their adsorption mechanism for the removal of Hg(II)from aqueous solution[J].Chemical Engineering Journal,2012,210(6):564-574.
[18]张明磊,张朝晖,罗丽娟,等.磁性Fe3O4@SiO2@CS镉离子印迹聚合物的制备及吸附性能[J].高等学校化学学报,2011,32(12):2763-2768.ZHANG M L,ZHANG C H,LUO L J,et al.Preparation and adsorption properties of magnetic Fe3O4@SiO2@CS cadmium imprinted polymers[J].Chemical Journal of Chinese Universities,2011,32(12):2763-2768.
[19]俞洁,张海涛,陆泉芳,等.坡缕石/聚乙二醇/丙烯酸水凝胶的表征及其对阳离子染料的吸附性能[J].化工进展,2015,34(4):1115-1121.YU J,ZHANG H T,LU Q F,et al.Characterization of Palygorskite/polyethylene glycol/acrylic acid hydrogel and its adsorption properties for cationic dyes[J].Chemical Industry and Engineering Progress,2015,34(4):1115-1121.
[20]LIN H,HAN S,DONG Y,et al.The surface characteristics of hyperbranched polyamide modified corncob and its adsorption property for Cr(VI)[J].Applied Surface Science,2017,412:152-159.
[21]CHANG Y C,CHANG S W,CHEN D H.Magnetic chitosan nanoparticles:studies on chitosan binding and adsorption of Co(II)ions[J].Reactive and Functional Polymers,2005,26(3):335-341.
[22]商娟,赵军.壳聚糖改性对磁性Fe3O4吸附去除Pb(II)和Cd(II)的影响研究[J].环境污染与防治,2017,39(7):746-751.SHANG J,ZHAO J.Effect of chitosan modification on Pb(II)and Cd(II)adsorption by magnetic Fe3O4[J].Environmental Pollution and Control,2017,39(7):746-751.
[23]CHARPENTIER T V J,NEVILLE A,LANIGAN J L,et al.Preparation of magnetic carboxymethylchitosan nanoparticles for adsorption of heavy metal ions[J].ACS Omega,2016,1(1):77-83.
[24]司汇通,王兵,孙智纯,等.中空结构双模板分子印迹微球的制备及在燃油脱硫中的应用[J].高分子材料科学与工程,2016,32(10):154-159.SI H T,WANG B,SUN Z C,et al.Preparation of hollow structure of dual template molecularly imprinted nanoparticles and its application in desulfurization of fuel oils highpolymer mater[J].Polymer Materials Science and Engineering,2016,32(10):154-159.