Preparation and characterization of double imine bridged mesoporous silica

doi:10.16085/j.issn.1000-6613.2017.05.033

Abstract

Abstract: Using self-made double imine silane coupling agent and ethyl silicate as silicon source,cetyl trimethyl ammonium bromide/sodium polyacrylate (CTAB/PAANa) as hybrid template agent,we synthesized double imine bridged functionalized mesoporous materials through copolycondensation method. And the structure of synthesized silicas were characterized by fourier transform infrared spectroscopy (FTIR),N₂ adsorption-desorption,X-ray diffraction assay (XRD),scanning electron microscopy (SEM) and transmission electron microscopy (TEM). Besides,the effects of dosage of sodium polyacrylate (PAANa) on its structure and morphology were emphatically investigated. The silicas were then applied in adsorption of heavy metal ions. The result showed that amount of PAANa had an effect on the specific surface area,pore volume and the degree of order of mesoporous materials. While the dosage of PAANa was 0.01%,mesoporous silicone (PMOS_0.01) showed good morphology and degree of order. Moreover,under acidic condition,the adsorption capacity of Cr (Ⅵ) was 289.24mg/g,while that of Cu (Ⅱ) was 276mg/g under alkaline condition.

Key words: nano-material, double imine bridged, preparation, adsorption, heavy metal, copolymerization

摘要： 以自制双亚胺硅烷偶联剂和正硅酸乙酯为硅源，十六烷基三甲基溴化铵（CTAB）/聚丙烯酸钠（PAANa）为混合模板剂，通过共缩聚法合成桥连双亚胺席夫碱功能化介孔材料。利用红外光谱（FTIR）、氮气吸附-脱附、X射线衍射（XRD）、扫描电子显微镜（SEM）和透射电子显微镜（TEM）对桥连双亚胺介孔材料进行了表征，着重探讨了不同PAANa用量对介孔材料的结构和形貌的影响，并将其应用于重金属离子的吸附。结果表明，PAANa用量对桥连双亚胺介孔材料的比表面积、孔容积和有序度都有一定的影响；当PAANa的加入量为0.01%时，功能化介孔材料（PMOS_0.01）展现出较好的形貌、有序度和比表面积。此外，在酸性条件下，PMOS_0.01对Cr（Ⅵ）的吸附量为289.24mg/g；而在碱性条件下，PMOS_0.01对Cu（Ⅱ）的吸附量为276mg/g。

关键词: 纳米材料, 双亚胺, 制备, 吸附, 重金属, 共缩聚法

CLC Number:

TQ424.3

XIE Huilin, LONG Xiangnan, HU Wenbin, CHEN Xiuying, JIA Zhenyu, LIU Qihai, ZHOU Xinhua. Preparation and characterization of double imine bridged mesoporous silica[J]. Chemical Industry and Engineering Progress, 2017, 36(05): 1825-1830.

谢慧琳, 龙湘南, 胡文斌, 陈秀莹, 贾振宇, 刘其海, 周新华. 桥连双亚胺介孔材料的制备及其表征[J]. 化工进展, 2017, 36(05): 1825-1830.

References

[1] SRIVASTAVA N K,MAJUMDER C B. Novel biofiltration methods for the treatment of heavy metals from industrial wastewater[J]. Journal of Hazardous Materials,2008,151(1):1-8.
[2] KUSVURAN E,YILDIRIM D,SAMIL A,et al. A study:removal of Cu(Ⅱ),Cd(Ⅱ),and Pb(Ⅱ) ions from real industrial water and contaminated water using activated sludge biomass[J]. Clean-Soil Air Water,2012,40(11):1273-1283.
[3] HEIDARI A,YOUNESI H,MEHRABAN Z. Removal of Ni(Ⅱ),Cd(Ⅱ),and Pb(Ⅱ) from a ternary aqueous solution by amino functionalized mesoporous and nano mesoporous silica[J]. Chemical Engineering Journal,2009,153(1/2/3):70-79.
[4] 刘纯,殷恒波,石莉萍,等. 纳米SiO₂空心微球对重金属离子的吸附特性[J]. 中国有色金属学报,2013,23(6):1661-1665. LIU C,YIN H B,SHI L P,et al. Adsorbability characteristic of hollow SiO₂ nanospheres for heavy metal ions[J]. The Chinese Journal of Nonferrous Metals,2013,23(6):1661-1665.
[5] 李小娟,何长发,黄斌,等. 金属有机骨架材料吸附去除环境污染物的进展[J]. 化工进展,2016,35(2):586-594. LI X J,HE C F,HUANG B,et al. Progress in the applications of metal-organic frameworks in adsorption removal of hazardous materials[J]. Chemical Industry and Engineering Progress,2016,35(2):586-594.
[6] 陈田,王涛,王道军,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,2010,12(26):3249-3256. CHEN T,WANG T,WANG D J,et al. Selective adsorption behavior of Cu(Ⅱ) and Cr(Ⅵ) heavy metal ions by functionalized ordered mesoporous carbon[J]. Acta Physico-Chimica Sinica,2010,12(26):3249-3256.
[7] TIMIN A,RUMYANTSEV E,SOLOMONOV A. Synthesis and application of amino-modified silicas containing albumin as hemoadsorbents for bilirubin adsorption[J]. Journal of Non-Crystalline Solids,2014,385:81-88.
[8] 伍宏玉,张友玉,李海涛. 介孔二氧化硅的扩孔及其氨基功能化[J]. 化学研究与应用,2011,23(11):1441-1446. WU H Y,ZHANG Y Y,LI H T. Pore size expansion and amino group functionalization of mesoporous silica [J]. Chemical Research and Application,2011,23(11):1441-1446.
[9] 杨惠,黄超,廖世军. 具有特殊形貌的介孔氧化硅的合成及其应用研究进展[J]. 化工进展,2014,33(8):2089-2095. YANG H,HUANG C,LIAO S J. Progress of synthesis and application of mesoporous silica with special morphology[J]. Chemical Industry and Engineering Progress,2014,33(8):2089-2095.
[10] ZHANG W,HE S,LIU Y,et al. Preparation and characterization of novel functionalized prochloraz microcapsules using silica-alginate-elements as controlled release carrier materials[J]. ACS Applied Materials & Interfaces,2014,6(14):11783-11790.
[11] 孙静静,许利剑,李文,等. APTES改性介孔二氧化硅的制备及其对重金属离子的吸附[J]. 湖南工业大学学报,2013,27(2):16-20. SUN J J,XU L J,LI W,et al.APTES-modified mesoporous silica preparation and its adsorption on heavy metal ions[J]. Journal of Hunan University of Technology,2013,27(2):16-20.
[12] DAI X,QIU F,ZHOU X,et al. Amino-functionalized mesoporous silica modified glassy carbon electrode for ultra-trace copper(Ⅱ) determination[J]. Analytica Chimica Acta,2014,848:25-31.
[13] GE K,ZHANG C,JIA G,et al. Defect-related luminescent mesoporous silica nanoparticles employed for novel detectable nanocarrier[J]. ACS Applied Materials & Interfaces,2015,7(20):10905-10914.
[14] DOBROWOLSKI R,OSZUST-CIENIUCH M,DOBRZYNSKA J,et al. Amino-functionalized SBA-15 mesoporous silicas as sorbents of platinum(IV) ions[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2013,435:63-70.
[15] SANCHEZ C,BOISSIERE C,CASSAIGNON S,et al. Molecular engineering of functional inorganic and hybrid materials[J]. Chemistry of Materials,2014,26(1):221-238.
[16] 吕志卿,吴连斌,蒋剑雄,等. 桥联型有机-无机介孔材料(PMOs)[J]. 化学进展,2010,22(6):1152-1160. LV Z Q,WU L B,JIANG J X,et al. Periodic mesoporous organosilicas(PMOs)[J]. Progress in Chemistry,2010,22(6):1152-1160.
[17] VERANI C N,RENTSCHLET E,WEYHERMULLER T,et al. Exchange coupling in a bis(heterodinuclear) [Cu^ⅡNi^Ⅱ]₂ and a linear heterotrinuclear complex Co^ⅢCu^ⅡNi^Ⅱ. Synthesis,structures and properties[J]. Dalton Transactions,2000(3):251-258.
[18] 李洪玉. 官能化PMOs复合材料的制备、表征及催化性能研究[D]. 太原:太原理工大学,2008. LI H Y. Preparation,characterization and catalytic performance of functionalized PMOs materials[D]. Taiyuan:Taiyuan University of Technology,2008.
[19] 汪雷,焦剑,吕盼盼,等. PMOs/PMMA纳米复合材料的制备及性能研究[J]. 化学与黏合,2013,35(4):1-4.WANG L,JIAO J,LV P P,et al. Study on the synthesis and performance of PMOs/PMMA nano-composite[J]. Chemistry and Adhesion,2013,35(4):1-4.