偕胺肟基螯合氧化硅的合成及其Cu2+亲和性能

doi:10.15541/jim20150483

摘要/Abstract

摘要：

以氯化钾为晶体结构导向剂, 以正硅酸乙酯和2-氰乙基三乙氧基硅烷为硅源, 聚(乙二醇)-聚(丙二醇)-聚(乙二醇)三嵌段共聚物为模板剂, 合成了偕胺肟基螯合氧化硅(AO-SBA-15)。通过X射线衍射(XRD)、低温氮气吸附-脱附、傅里叶红外光谱(FT-IR)、Zeta电位分析和元素分析技术对样品的结构、孔性质和螯合官能团等进行了表征。XRD分析结果表明, 偕胺肟基螯合氧化硅材料具有有序的二维六方结构, 通过氮气物理吸附数据计算得到材料的平均孔径和比表面积分别为3.96 nm和435 m²/g。FT-IR分析表明将氰基成功地引入材料中并转化为偕胺肟基螯合官能团, 元素分析发现材料的偕胺肟基含量约为1.6 mmol/g, 此外, Zeta电位分析表明材料呈现电负性。相对未改性的氧化硅材料(SBA-15), AO-SBA-15对铜离子吸附容量提高了2倍; 相对氰基功能化氧化硅(CN-SBA-15), AO-SBA-15吸附容量提高了3.6倍。这表明通过引入偕胺肟基螯合官能团, SBA-15对铜离子的亲和力得到显著提高。

关键词: Cu2+, SBA-15, 氰基, 偕胺肟, 亲和力

Abstract:

Amidoxime-functionalized mesoporous silica was synthesized with tetraethylorthosilicate and 2-cyanoethyl triethoxysilane as silicon source, potassium chloride as the crystal structure directing agent and poly (ethylene glycol)-poly (propylene glycol)-poly (ethylene glycol) three block copolymers as template. The structure of the samples, pore properties and chelating function groups were characterized by X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), N₂adsorption desorption isotherms and elemental analysis. XRD spectra and N₂ physical adsorption-desorption results indicate that amidoxime functioned mesoporous silica has ordered two-dimensional hexagonal structure with average pore size of 3.96 nm and specific surface area of 435 m²/g. FT-IR spectra shows that cyano is introducted into silica and converted into amidoxime successfully. Amidoxime concentration is about 1.6 mmol/g by elemental analysis and Zeta potential analysis results show that the adsorbent is electronegative. Compared with the Cu²⁺ adsorption capacities of unmodified silica material (SBA-15) and cyano functionalization of porous silicon oxide (CN-SBA-15), the adsorption capacity of AO-SBA-15 increases by 2 fold and 3.6 fold, respectively. This shows that with the introduction of amidoxime chelating function groups, affinity performance of SBA-15 to the copper ions are markedly improved.

Key words: Cu2+, SBA-15, cyano, amidoxime, affinity performance

中图分类号:

X703

魏建文, 王记华, 赵淞盛, 耿琳琳. 偕胺肟基螯合氧化硅的合成及其Cu²⁺亲和性能[J]. 无机材料学报, 2016, 31(5): 449-453.

WEI Jian-Wen, WANG Ji-Hua, ZHAO Song-Sheng, GENG Lin-Lin. Synthesis and Copper(II) Affinity Performance of Amidoxime Functionalized Mesoporous Silica[J]. Journal of Inorganic Materials, 2016, 31(5): 449-453.

图/表 7

图1 AO-SBA-15与SBA-15的粉末XRD图谱

Fig. 1 Powder XRD patterns of AO-SBA-15 and SBA-15

图2 AO-SBA-15的氮气吸脱附等温线

Fig. 2 N2 adsorption/desorption isotherm of AO-SBA-15

图3 AO-SBA-15的孔径分布曲线

Fig. 3 Pore size distribution curve of AO-SBA-15

图4 CN-SBA-15与AO-SBA-15的傅里叶红外光谱图谱

Fig. 4 Fourier transform infrared spectra of AO-SBA-15 and CN-SBA-15

表1 样品的元素分析结果

Table1 Elemental analysis of AO-SBA-15

Samples	Element content/%			C:N	-CN, -AO
Samples	C	N	H	C:N	/(mmol·g^-1)
CN-SBA-15	11.35	2.34	3.43	3.86	2.5
CN-SBA-15	11.24	2.45	3.45	3.80	2.5
AO-SBA-15	8.28	2.71	4.44	2.18	1.6
AO-SBA-15	8.38	2.58	4.48	2.18	1.6

图5 AO-SBA-15吸附Cu2+前后的ζ电位变化

Fig. 5 Zeta potential distribution of AO-SBA-15 before and after adsorbing Cu2+

图6 含不同基团的材料对铜离子的亲和力

Fig. 6 Cu2+ affinity of materials containing different groups

参考文献 23

[1]	JAL P K, PATEL S, MISHRA B K.Chemical modification of silica surface by immobilization of functional groups for extractive concentration of metal ions.Talanta, 2004, 62(5): 1005-1028.
[2]	ZHANG D, LI J H.Ordered SBA-15 mesoporous silica with high amino-functionalization for adsorption of heavy metal ions.Chinese Science Bulletin, 2013, 58(8): 879-883.
[3]	WALCARIUS A, MERCIER L.Mesoporous organosilica adsorbents: nanoengineered materials for removal of organic and inorganic pollutants.Journal of Materials Chemistry, 2010, 20(22): 4478-4511.
[4]	SIERRA I, PEREZ-QUINTANLIIA D.Heavy metal complexation on hybrid mesoporous silicas: an approach to analytical applications.Chemical Society Reviews, 2013, 42(9): 3792-3807.
[5]	ENSHIRAH D, ABDELHAMID S.Adsorption of heavy metals on amine-functionalized SBA-15 prepared by co-condensation: Applications to real water samples.Desalination, 2012, 285(31): 62-67.
[6]	ZHAO D, FENG J, HUO Q, et al.Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores.Science, 1998, 279(5350): 548-552.
[7]	YANG C M, WANG Y Q, BODO Z, et al.Formation of cyanide- functionalized SBA-15 and its transformation to carboxylate- functionalized SBA-15.Physical Chemistry Chemical Physics, 2004, 6(9): 2461-2467.
[8]	YANG C M, ZIBROWIUS B, SCHUTH F.A novel synthetic route for negatively charged ordered mesoporous silica SBA-15.Chemical Communications, 2003, 14(14): 1772-1773.
[9]	WU B H, ZHANG S C, TANG T, et al.Small-angle X-ray scattering studies of carboxyl functionalized SBA-15 type mesoporous molecular sieves.Acta Physico-Chimica Sinica, 2010, 26(8): 2217-2223.
[10]	韩喜江. 固体材料常用表征技术. 哈尔滨: 哈尔滨工业大学出版社, 2011: 263.
[11]	BIAN W, LOU L L, YAN B, et al.Immobilization of papain by carboxyl-modified SBA-15: rechecking the carboxyl after excluding the contribution of H2SO4 treatment. Microporous and Mesoporous Materials, 2011, 143(2): 341-347.
[12]	PAN Y C, WU H Y, LEE L P, et al.Cyanide-and carboxylate-functionalized cubic mesoporous silicas SBA-1: synthesis, characterization and reactivity of organic functional groups.Microporous and Mesoporous Materials, 2009, 123(1): 78-90.
[13]	FIORILLI S, ONIDA B, BONELLI B, et al.In situ infrared study of SBA-15 functionalized with carboxylic groups incorporated by a co-condensation route.The Journal of Physical Chemistry B, 2005, 109(35): 16725-16729.
[14]	KHAYOON M S, HAMEED B H. Synthesis of hybrid SBA-15 functionalized with molybdophosphoric acid as efficient catalyst for glycerol esterification to fuel additives. Applied Catalysis A: General, 2012, 433-434(31): 152-161.
[15]	WANG H B, ZHANG Y H, YANG H L, et al.Palladium immobilized in the nanocages of SBA-16: an efficient and recyclable catalyst for Suzuki coupling reaction.Microporous and Mesoporous Materials, 2013, 168(1): 65-72.
[16]	NILCHI A, BABALOU A A, RAFIEE R, et al.Adsorption properties of amidoxime resins for separation of metal ions from aqueous systems.Reactive and Functional Polymers, 2008, 68(12): 1665-1670.
[17]	SAEED K, HAIDER S, OH T J, et al.Preparation of amidoxime- modified polyacrylonitrile (PAN-oxime) nanofibers and their applications to metal ions adsorption.Journal of Membrane Science, 2008, 322(2): 400-405.
[18]	GAO B J, GAO Y C, LI Y B.Preparation and chelation adsorption property of composite chelating material poly (amidoxime)/SiO2 towards heavy metalions.Chemical Engineering Journal, 2010, 158(3): 542-549.
[19]	GUO F, ZHU G R, GAO C J.Preparation and characterization of cyano-functionalized mesoporous silica. Journal of Inorganic Materials, 2012, 27(2): 134-138.
[20]	MARKIEWICZ M, MROZIK W, REZWAN K, et al.Changes in Zeta potential of imidazolium ionic liquids modified minerals- Implications for determining mechanism of adsorption.Chemosphere, 2013, 90(2): 706-712.
[21]	FERRARI L, KAUFMANN J, WINNEFELD F, et al.Interaction of cement model systems with superplasticizers investigated by atomic force microscopy, Zeta potential, and adsorption measurements.Journal of Colloid and Interface Science, 2010, 347(1): 15-24.
[22]	邓述波, 余刚. 环境吸附材料及应用原理. 北京: 科学出版社, 2012: 23.
[23]	AGUADO J, ARSUAGA J M, ARENCIBIA A, et al.Aqueous heavy metals removal by adsorption on amine-functionalized mesoporous silica. Journal of Hazardous Materials, 2009, 163(1): 213-221.

偕胺肟基螯合氧化硅的合成及其Cu²⁺亲和性能

Synthesis and Copper(II) Affinity Performance of Amidoxime Functionalized Mesoporous Silica

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 23

相关文章 11

编辑推荐

Metrics

本文评价

[1]	蒋丽丽, 徐帅帅, 夏宝凯, 陈胜, 朱俊武. 缺陷调控石墨烯复合催化剂在氧还原反应中的作用[J]. 无机材料学报, 2022, 37(2): 215-222.
[2]	郭宇, 姜晓庆, 吴红梅, 肖昱, 仵大富, 刘鑫. 2-羟基-1-萘甲醛功能化SBA-15吸附剂的制备及其对Cr(III)的吸附性能[J]. 无机材料学报, 2021, 36(11): 1163-1170.
[3]	张志宾, 周润泽, 董志敏, 曹小红, 刘云海. 偕胺肟水热碳对U(VI)-CO₃/Ca-U(VI)-CO₃的吸附性能研究[J]. 无机材料学报, 2020, 35(3): 352-358.
[4]	郭露露, 李立霞, 何鹏程, 袁霞. 介孔材料Co/SBA-15催化环己基过氧化氢分解的研究[J]. 无机材料学报, 2017, 32(5): 543-549.
[5]	于晓磊, 杨军, 冯雪娇, 高鹏飞, 王久林, 努丽燕娜. 多孔硅/碳复合负极材料的制备及电化学性能[J]. 无机材料学报, 2013, 28(9): 937-942.
[6]	郭风, 朱桂茹, 高从堦. 氰基功能化介孔二氧化硅的制备与表征[J]. 无机材料学报, 2012, 27(2): 134-138.
[7]	辛洪川，汤建庭，范峰滔，杨启华，李灿. 缓冲溶液中制备掺杂高度隔离铁物种的介孔氧化硅[J]. 无机材料学报, 2010, 25(1): 107-112.
[8]	张勇,陈之战,施尔畏,严成锋,刘学超. 介孔模板限域法制备SiC纳米颗粒[J]. 无机材料学报, 2009, 24(2): 285-290.
[9]	银建中,张传杰,徐琴琴,王爱琴. Ag/SBA-15纳米复合材料的超临界流体沉积法制备、性能表征和催化特征[J]. 无机材料学报, 2009, 24(1): 129-132.
[10]	翟庆洲,王巍,江天肃,王媛,陈明贵. 镧(Ⅲ)对SBA-15分子筛改性研究[J]. 无机材料学报, 2004, 19(5): 1212-1216.
[11]	张存满,徐政,万克树,刘茜. 高氮含量的有序氮氧化物介孔材料的研究[J]. 无机材料学报, 2004, 19(3): 559-565.