桥连双亚胺介孔材料对Cr(Ⅵ)的吸附性能
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摘要
以CTAB/PAANa为混合模板剂,正硅酸乙酯为硅源,自制双亚胺基桥连硅烷偶联剂为改性剂,采用共缩聚法制备了双亚胺桥连介孔硅材料PMOS。利用FTIR、XRD、N2吸附-脱附、固体核磁和TEM对PMOS材料的结构和形貌进行了表征,将其应用于对Cr(Ⅵ)的吸附,并系统考察了pH值、吸附剂用量和吸附时间对PMOS吸附Cr(Ⅵ)的影响,且重点探究了PMOS对Cr(Ⅵ)的吸附行为。结果表明,PMOS具有高度有序的介孔结构,其对Cr(Ⅵ)的最佳吸附条件为:pH=6,初始浓度为200mg/L,吸附时间为8h。PMOS对Cr(Ⅵ)的吸附遵循Langmuir模型,在45℃时,其对Cr(Ⅵ)的饱和吸附量为428.61mg/g。此外,PMOS对Cr(Ⅵ)的吸附行为可用准二级动力学模型来描述,且PMOS与Cr(Ⅵ)之间的作用力主要为静电作用力和配位作用力。
The diimine bridged mesoporous silica(PMOS)was synthesized by copolycondensation method with CTAB/PAANa as mixed template,tetraethyl orthosilicate as silicon source and homemade silane coupling agent as modifier.The structure and morphology of PMOS materials were characterized by FTIR,XRD,BET,solid-state nuclear magnetic and TEM.The effects of pH value,mass rations of adsorbent and absorption time on adsorption for Cr(Ⅵ)were discussed.Besides,the adsorption behavior of PMOS for Cr(Ⅵ)was mainly investigated.The results showed that PMOS was highly ordered mesoporous structure.While pH=6,the concentration of initial solution was 200 mg/L,adsorption time was 8 h,the PMOS showed excellent adsorption for Cr(Ⅵ).The adsorption could be described by Langmuir model and pseudo-second order kinetics model.When the temperature was 45 ℃,the saturated adsorption for Cr(Ⅵ)was 428.61 mg/g.The force between PMOS and Cr(Ⅵ)is mainly electrostatic force and coordination force.
The diimine bridged mesoporous silica(PMOS)was synthesized by copolycondensation method with CTAB/PAANa as mixed template,tetraethyl orthosilicate as silicon source and homemade silane coupling agent as modifier.The structure and morphology of PMOS materials were characterized by FTIR,XRD,BET,solid-state nuclear magnetic and TEM.The effects of pH value,mass rations of adsorbent and absorption time on adsorption for Cr(Ⅵ)were discussed.Besides,the adsorption behavior of PMOS for Cr(Ⅵ)was mainly investigated.The results showed that PMOS was highly ordered mesoporous structure.While pH=6,the concentration of initial solution was 200 mg/L,adsorption time was 8 h,the PMOS showed excellent adsorption for Cr(Ⅵ).The adsorption could be described by Langmuir model and pseudo-second order kinetics model.When the temperature was 45 ℃,the saturated adsorption for Cr(Ⅵ)was 428.61 mg/g.The force between PMOS and Cr(Ⅵ)is mainly electrostatic force and coordination force.
引文
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21 Shi B.Analysis of existing forms of Cr6+in waste water[J].Electroplating Pollution Control,1986,6(4):30(in Chinese).施波.废水中六价铬的存在形态分析[J].电镀与环保,1986,6(4):30.
22 ManjuladeⅥM,Manonmani S.Removal of hexavalent chromium ions from aqueous solution by adsorption using activated carbon prepared from cucumis melo peel activated carbon[J].Oriental J Chem,2015,31(1):531.
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24 Zhang S J,Xing B L,Huang G X,et al.A study on adsorption of Cr(Ⅵ)by hydrothermal carbon from walnut shell[J].Chem Ind Eng Prog,2016,35(3):950(in Chinese).张双杰,邢宝林,黄光许,等.核桃壳水热炭对六价铬的吸附特性[J].化工进展,2016,35(3):950.
25 Zhu W J,Li M M,Ma W H,et al.Synthesis of MCM-41 mesoporous sieves and their adsorption performance of Cu2+[J].Chin J Environmental Eng,2014,8(2):513(in Chinese).朱文杰,李明明,马文会,等.MCM-41介孔分子筛的合成及其对铜离子的吸附性能[J].环境工程学报,2014,8(2):513.
2 Li Z Y,Hu S.Removal of hexavalent chromium from aqueous solutions by ion-exchange resin[J].Adv Mater Res,2012,550-553:2333.
3 Park D,Yun Y,Kim J Y,et al.How to study Cr(Ⅵ)biosorption:Use of fermentation waste for detoxifying Cr(Ⅵ)in aqueous solution[J].Chem Eng J,2008,136(2-3):173.
4 Sanchez J,Rivas B L.Cationic hydrophilic polymers coupled to ultrafiltration membranes to remove chromium(Ⅵ)from aqueous solution[J].Desalination,2011,279(1):338.
5 Goharshadi E K,Moghaddam M B.Adsorption of hexavalent chromium ions from aqueous solution by graphene nanosheets:Kinetic and thermodynamic studies[J].Int J Environmental Sci Technol,2015,12(7):2153.
6 Maleki A,Hayati B,Naghizadeh M,et al.Adsorption of hexavalent chromium by metal organic frameworks from aqueous solution[J].J Ind Eng Chem,2015,28:211.
7 Timin A,Rumyantsev E,Solomonov A.Synthesis and application of amino-modified silicas containing albumin as hemoadsorbents for bilirubin adsorption[J].J Non-Crystalline Solids,2014,385:81.
8 Ge K,Zhang C,Jia G,et al.Defect-related luminescent mesoporous silica nanoparticles employed for novel detectable nanocarrier[J].ACS Appl Mater Interfaces,2015,7(20):10905.
9 Chen T,Wang T,et al.Selective adsorption behavior of Cu(Ⅱ)and Cr(Ⅵ)heavy metal ions by functionalized ordered mesoporous carbon[J].Acta Phys-Chim Sin,2010,26(12):3249(in Chinese).陈田,王涛,等.功能化有序介孔碳对重金属离子Cu(Ⅱ)、Cr(Ⅵ)的选择性吸附行为[J].物理化学学报,2010,26(12):3249.
10 Munoz B,Ramila A,Perez P J,et al.MCM-41organic modification as drug delivery rate regulator[J].Chem Mater,2003,15(2):500.
11 Ozdemir O.Novel symmetric diimine-Schiff bases and asymmetric triimine-Schiff bases as chemosensors for the detection of various metal ions[J].J Molecular Structure,2016,1125:260.
12 Dobrowolski R,Oszust-Cieniuch M,et al.Amino-functionalized SBA-15mesoporous silicas as sorbents of platinum(Ⅳ)ions[J].Colloids Surf A:Physicochem Eng Aspects,2013,435:63.
13 Liu B,Fang M,Jie S,et al.Nickel(Ⅱ)α-diimine catalysts with carboxyl groups for ethylene oligomerization and polymerization[J].Chin J Polym Sci,2016,34(2):221.
14 Meng X J,Xie B,Xiao F S.Organotemplate-free routes for synthesizing zeolites[J].Chin J Catal,2009,30(9):965(in Chinese).孟祥举,谢彬,肖丰收.无有机模板剂条件下合成沸石催化材料[J].催化学报,2009,30(9):965.
15 Liu L,Zhang G Y,Dong J X.Effects of different templating agent on the structure of silica MCM-41mesoporous molecular sieves[J].Acta Phys-Chim Sin,2004,20(1):65(in Chinese).刘雷,张高勇,董晋湘.模板剂对全硅MCM-41介孔分子筛结构的影响[J].物理化学学报,2004,20(1):65.
16 Chandra D,Bhaumik A.Highly active 2Dhexagonal mesoporous titanium silicate synthesized using a cationic-anionic mixed-surfactant assembly[J].Ind Eng Chem Res,2006,45(14):4879.
17 Wang J J,Lu J M,Yang J H,et al.Synthesis of mesoporous MCM-48 molecular sieves with cationic and anionic mixed surfactant system as template[J].Petrochem Technol,2013,42(5):506(in Chinese).王静静,鲁金明,杨建华,等.阴阳离子表面活性剂混合模板剂合成介孔MCM-48分子筛[J].石油化工,2013,42(5):506.
18 Verani C N,et al.Exchange coupling in a bis(heterodinuclear)[CuⅡNiⅡ]2and a linear heterotrinuclear complex CoⅢCuⅡNiⅡ.Synthesis,structures and properties[J].Dalton Trans,2000(3):251.
19 Hao S Y,Xiao Q,Zhong Y J,et al.One-pot synthesis of aminofunctionalized SBA-15and their CO2-adsorption properties[J].Chin J Inorg Chem,2010,26(6):982(in Chinese).郝仕油,肖强,钟依均,等.氨基功能化SBA-15的直接合成及其对CO2的吸附性能研究[J].无机化学学报,2010,26(6):982.
20 Wang X H,Zhu G R,Gao C J.Adsorption of uranium(Ⅵ)on silica mesoporous material SBA-15 with short channels[J].CIESC J,2013,64(7):2480(in Chinese).王兴慧,朱桂茹,高从堦.短孔道介孔二氧化硅SBA-15对铀的吸附性能[J].化工学报,2013,64(7):2480.
21 Shi B.Analysis of existing forms of Cr6+in waste water[J].Electroplating Pollution Control,1986,6(4):30(in Chinese).施波.废水中六价铬的存在形态分析[J].电镀与环保,1986,6(4):30.
22 ManjuladeⅥM,Manonmani S.Removal of hexavalent chromium ions from aqueous solution by adsorption using activated carbon prepared from cucumis melo peel activated carbon[J].Oriental J Chem,2015,31(1):531.
23 Yang J,et al.Adsorption of hexavalent chromium from aqueous solution by activated carbon prepared from longan seed:Kinetics,equilibrium and thermodynamics[J].J Ind Eng Chem,2015,21:414.
24 Zhang S J,Xing B L,Huang G X,et al.A study on adsorption of Cr(Ⅵ)by hydrothermal carbon from walnut shell[J].Chem Ind Eng Prog,2016,35(3):950(in Chinese).张双杰,邢宝林,黄光许,等.核桃壳水热炭对六价铬的吸附特性[J].化工进展,2016,35(3):950.
25 Zhu W J,Li M M,Ma W H,et al.Synthesis of MCM-41 mesoporous sieves and their adsorption performance of Cu2+[J].Chin J Environmental Eng,2014,8(2):513(in Chinese).朱文杰,李明明,马文会,等.MCM-41介孔分子筛的合成及其对铜离子的吸附性能[J].环境工程学报,2014,8(2):513.