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材料研究学报  2021, Vol. 35 Issue (1): 45-52    DOI: 10.11901/1005.3093.2020.094
  研究论文 本期目录 | 过刊浏览 |
中空介孔SiO2的合成及其对Cr的吸附
张辰, 韩伟豪, 宫玉梅(), 于洋, 曹金城
大连工业大学纺织与材料工程学院 大连 116034
Synthesis of Hollow Mesoporous SiO2 and Its Adsorption Performance of Cr
ZHANG Chen, HAN Weihao, GONG Yumei(), YU Yang, CAO Jincheng
School of Textile and Materials Engineering, Dalian Polytechnic University, Dalian 116034, China
引用本文:

张辰, 韩伟豪, 宫玉梅, 于洋, 曹金城. 中空介孔SiO2的合成及其对Cr的吸附[J]. 材料研究学报, 2021, 35(1): 45-52.
Chen ZHANG, Weihao HAN, Yumei GONG, Yang YU, Jincheng CAO. Synthesis of Hollow Mesoporous SiO2 and Its Adsorption Performance of Cr[J]. Chinese Journal of Materials Research, 2021, 35(1): 45-52.

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摘要: 

以3-氨基苯酚/甲醛(AF)树脂为软模板、正硅酸乙酯(TEOS)为硅源、十六烷基三甲基溴化铵(CTAB)为制孔剂,采用一锅溶胶-凝胶法制备中空介孔二氧化硅(HMS)微球。通过改变反应温度对软模板AF树脂的结构以及TEOS的水解速率进行调控,制备多形貌SiO2微球。使用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、N2吸附-脱附比表面积分析(BET)及傅里叶变换红外光谱(FTIR)等手段对制得的SiO2微球进行表征。结果表明,随着反应温度从0℃提高到100℃,制备的SiO2微球分别为实心微球、蛋黄壳空心球、单层壳空心球和破碎实心球等。其中具有蛋黄壳结构的HMS微球具有较大的比表面积和孔体积,比表面积可达513 m2/g,孔体积达0.432 cm3/g,孔径均匀达3.66 nm。将在30℃下制得的具有蛋黄壳结构的HMS微球表面进行接枝聚丙烯腈并偕胺肟化的改性制备蛋黄壳HMS接枝聚偕胺肟(HMS-g-PAO)。将HMS-g-PAO用于对水中Cr的吸附,在pH = 2时HMS-g-PAO粒子对100 mg/mL的重铬酸钾溶液中Cr有很好的吸附效果,其吸附量达140 mg/g。

关键词 无机非金属材料中空介孔SiO2软模板偕胺肟化Cr吸附    
Abstract

A concise and facile one-pot sol-gel method was proposed by using 3-aminophenol/formaldehyde (AF) resin as soft template, tetraethyl orthosilicate (TEOS) as silicon source, hexadecyl trimethyl ammonium bromide (CTAB) as pore-forming agent for synthesizing silica microparticles. In the synthesis process, modification of soft template 3-aminophenol/formaldehyde (AF) resin structure and hydrolysis rate of TEOS was made by simply changing reaction temperature, a series of SiO2 microspheres with different structures and morphology could be obtained. The microstructure and characteristic of the SiO2 microparticles were characterized by means of scanning electron microscope (SEM), transmission electron microscopy (TEM), N2 adsorption-desorption specific surface areaanalysis (BET) and Fourier transform infrared spectroscopy (FTIR). The results show that as the reaction temperature increases from 0℃to 100℃, SiO2 microparticles presented various type of structures such as solid sphere, yolk-shelled sphere, single-shelled sphere, and broken solid sphere. The HMS microspheres with hollow yolk-shelled morphology possessed a large specific surface area (513 m2/g), large pore volume (0.432 cm3/g), and uniform mesopores (3.66 nm). In addition, the yolk-shelled HMS was subjected to acrylonitrile free radical polymerization, amidoxime treatment to obtain HMS-grafted-polyamidoxime (HMS-g-PAO), which were used in the adsorption test of CrVI in K2Cr2O7 solution at pH=2. The modified HMS microspheres had an excellent adsorption ability to CrVI in K2Cr2O7 solution, and the adsorption amount could reach 140 mg/g when adsorption balanced.

Key wordsinorganic non-metallic materials    hollow mesoporous silica    soft template    polyamidoxime    CrVI adsorption
收稿日期: 2020-03-25     
ZTFLH:  O631  
基金资助:国家自然科学基金(51773024);辽宁省自然科学基金指导计划项目(2019-ZD-0288);辽宁省创新团队项目(LT2017017)
作者简介: 张辰,男,1995年生,硕士生
图1  在不同反应温度下合成SiO2微球的流程
图2  在不同反应温度下制得的SiO2微球的SEM和TEM照片
图3  在不同反应温度下制得的SiO2微球的N2吸附-脱附等温线及相应的孔径分布曲线
图4  具有蛋黄壳结构的HMS、HMS-g-PAN和HMS-g-PAO的红外光谱图
图5  HMS-g-PAO对CrⅥ的吸附和吸附过程的伪一级和伪二级动力学模型
1 Naeimi Z, Miri M. Magnetic and electric hotspots via fractal clusters of hollow silicon nanoparticles [J]. Opt. Lett., 2018, 43: 462
2 Hou C X, Hou Y, Fan Y Q, et al. Oxygen vacancy derived local build-in electric field in mesoporous hollow Co3O4 microspheres promotes high-performance Li-ion batteries [J]. J. Mater. Chem., 2018, 6A: 6967
3 Van De Haar M A, Van De Groep J, Brenny B J M, et al. Controlling magnetic and electric dipole modes in hollow silicon nanocylinders [J]. Opt. Express, 2016, 24: 2047
4 Wang H S, Xiu Y, Chen Y, et al. Electrochemical immunosensor based on an antibody-hierarchical mesoporous SiO2 for the detection of Staphylococcus aureus [J]. RSC Adv., 2019, 9: 16278
5 Tian M, Long Y, Xu D, et al. Hollow mesoporous silica nanotubes modified with palladium nanoparticles for environmental catalytic applications [J]. J. Colloid Interface Sci., 2018, 521: 132
6 Tan X Q, Wan Y F, Huang Y J, et al. Three-dimensional MnO2 porous hollow microspheres for enhanced activity as ozonation catalysts in degradation of bisphenol A [J]. J. Hazard. Mater., 2017, 321: 162
7 Liao K X, Wei H H, Fan J C, et al. Tailoring hollow nanostructures by catalytic strategy for superior lithium and sodium storage [J]. ACS Appl. Mater. Interfaces, 2018, 10: 43953
8 Vaschetto E G, Sicardi M I, Elías V R, et al. Metal modified silica for catalytic wet air oxidation (CWAO) of glyphosate under atmospheric conditions [J]. Adsorption, 2019, 25: 1299
9 Li M M, Gong Y M, Guo J, et al. Polyamidoximation of hollow mesoporous silica and its application in adsorption of Cr(VI) [J]. Chem. J. Chin. Univ., 2017, 38(1): 159
9 李苗苗, 宫玉梅, 郭静等. 中空介孔二氧化硅锚固聚偕胺肟吸附Cr(Ⅵ) [J]. 高等学校化学学报, 2017, 38(1): 159
10 Zhang C, Wu C, Han W H, et al. Controllable synthesis of multi-morphological hollow mesoporous SiO2 and adsorption reduction of Cu2+ by its composites [J]. Chem. J. Chin. Univ., 2019, 40(11): 2412
10 张辰, 吴畅, 韩伟豪等. 多形貌中空介孔SiO2的可控合成及复合物对Cu2+的吸附还原 [J]. 高等学校化学学报, 2019, 40(11): 2412
11 Chang Y F, Li Y Z, Song J C, et al. Formaldehyde controlling the synthesis of multishelled SiO2/FexOy hollow porous spheres [J]. Langmuir, 2018, 34: 8223
12 Momtazan F, Khodadoust S, Zeraatpisheh F, et al. Synthesis of mesoporous silica for adsorption of chlordiazepoxide and its determination by HPLC: Experimental design [J]. J. Separat. Sci., 2019, 42: 3253
13 Xu H L, Shen L, Xu L, et al. Controlled delivery of hollow corn protein nanoparticles via non-toxic crosslinking: in vivo and drug loading study [J]. Biomed Microdevices, 2015, 17: 152
14 Shirkhanloo H, Ahranjani D S. A lead analysis based on amine functionalized bimodal mesoporous silica nanoparticles in human biological samples by ultrasound assisted-ionic liquid trap-micro solid phase extraction [J]. J. Pharm. Biomed. Anal., 2018, 157: 1
15 Hu G F, Yang L L, Li Y N, et al. Continuous and scalable fabrication of stable and biocompatible MOF@SiO2 nanoparticles for drug loading [J]. J. Mater. Chem., 2018, 6B: 7936
16 Yan X B, Zhou Z Y, Ding B F, et al. Superior resistive switching memory and biological synapse properties based on a simple TiN/SiO2/p-Si tunneling junction structure [J]. J. Mater. Chem., 2017, 5C: 2259
17 Chen P H, Hao W, Huang S S, et al. Template synthesis and lithium storage performances of hollow spherical LiMn2O4 cathode materials [J]. Ceram. Int., 2016, 42: 10498
18 Xu X, Chen J, Shen J, et al. Synthesis of hollow structural hydroxyapatite with different morphologies using calcium carbonate as hard template [J]. Adv. Powder Technol., 2018, 29(7): 1562
19 Lin G X, Ma R G, Zhou Y, et al. Three-dimensional interconnected nitrogen-doped mesoporous carbons as active electrode materials for application in electrocatalytic oxygen reduction and supercapacitors [J]. J. Colloid Interface Sci., 2018, 527: 230
20 Su Y, Yan R, Dan M H, et al. Synthesis of hierarchical hollow silica microspheres containing surface nanoparticles employing the quasi-hard template of poly (4-vinylpyridine) microspheres [J]. Langmuir, 2011, 27: 8983
21 Gong P Y, Li B S, Kong X L, et al. A new soft template-oriented method for the preparation of hollow analcime microspheres with nanosheets-assembled shells [J]. J. Mater. Sci., 2017, 52: 9377
22 Meng Q N, Du L L, Ji Y Y, et al. A facile soft template method to synthesize hollow carbon and MnOx composite particles for effective methylene blue degradation [J]. RSC Adv., 2018, 8: 28525
23 Wu X J, Xu D S. Soft template synthesis of yolk/silica shell particles [J]. Adv. Mater., 2010, 22: 1516
24 Chang Y F, Li Y Z, Zhang C, et al. Formaldehyde-controlled synthesis of multishelled hollow mesoporous SiO2 microspheres [J]. Langmuir, 2019, 35: 14517
25 Deng P, Liu Y S, Liu Y, et al. Preparation of phosphorus-containing phenolic resin and its application in epoxy resin as a curing agent and flame retardant [J]. Polym. Adv. Technol., 2018, 29: 1294
26 Li H, Du J H, Wang H X, et al. Research of tribological characteristics of resin matrix composites reinforced by woven fabric of carbon fiber [J]. J. Funct. Mater., 2017, 48: 4100
26 李辉, 杜建华, 王浩旭等. 碳纤维织物增强树脂基摩擦材料摩擦学性能研究 [J]. 功能材料, 2017, 48: 4100
27 Choi M H, Jeon B H, Chun I J. The effect of coupling agent on electrical and mechanical properties of carbon fiber/phenolic resin composites [J]. Polymer, 2000, 41: 3243
28 Yang J P, Shen D K, Zhou L, et al. Spatially confined fabrication of core-shell gold nanocages@mesoporous silica for near-infrared controlled photothermal drug release [J]. Chem. Mater., 2013, 25: 3030
29 Song J C, Xue F F, Lu Z Y, et al. Controllable synthesis of hollow mesoporous silica particles by a facile one-pot sol-gel method [J]. Chem. Commun., 2015, 51: 10517
30 Song J C, Xue F F, Zhang X X, et al. Synthesis of yolk-shell mesoporous silica nanoparticles via a facile one-pot approach [J]. Chem. Commun., 2017, 53: 3761
31 Bin D S, Chi Z X, Li Y T, et al. Controlling the compositional chemistry in single nanoparticles for functional hollow carbon nanospheres [J]. J. Am. Chem. Soc., 2017, 139: 13492
32 Guan J G, Mou F Z, Sun Z G, et al. Preparation of hollow spheres with controllable interior structures by heterogeneous contraction [J]. Chem. Commun., 2010, 46: 6605
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