多形貌中空介孔SiO2的可控合成及复合物对Cu 2+的吸附还原

doi:10.7503/cjcu20190244

高等学校化学学报 ›› 2019, Vol. 40 ›› Issue (11): 2412.doi: 10.7503/cjcu20190244

多形貌中空介孔SiO₂的可控合成及复合物对Cu ²⁺的吸附还原

张辰¹,吴畅¹,韩伟豪¹,宫玉梅^1,^*(),石强^2,^*()

^1. 大连工业大学纺织与材料工程学院, 大连 116034
^2. 中国科学院长春应用化学研究所高分子物理与化学国家重点实验室, 长春 130022

收稿日期:2019-04-26 出版日期:2019-11-10 发布日期:2019-10-15
通讯作者: 宫玉梅,石强 E-mail:ymgong@dlpu.edu.cn;shiqiang@ciac.ac.cn
基金资助:
国家自然科学基金(51773024);辽宁省自然科学指导计划(2019-ZD-0288);中国科学院长春应用化学研究所高分子化学与物理国家重点实验室开放课题基金资助.(201715)

Controllable Synthesis of Multi-morphological Hollow Mesoporous SiO₂ and Adsorption Reduction of Cu ²⁺ by Its Composites ^†

ZHANG Chen¹,WU Chang¹,HAN Weihao¹,GONG Yumei^1,^*(),SHI Qiang^2,^*()

^1. School of Textile and Material Engineering, Dalian Polytechnic University, Dalian 116034, China
^2. State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China

Received:2019-04-26 Online:2019-11-10 Published:2019-10-15
Contact: GONG Yumei,SHI Qiang E-mail:ymgong@dlpu.edu.cn;shiqiang@ciac.ac.cn
Supported by:
? Supported by the National Natural Science Foundation of China(51773024);The Liaoning Provincial Natural Science Guidance Program, China(2019-ZD-0288);The Open Research Fund of State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences(201715)

摘要/Abstract

摘要：

以间苯二酚/甲醛(RF)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-凝胶法制备了多形貌中空介孔二氧化硅微球(HMSM). 通过改变甲醛用量调控软模板RF树脂的结构, 可以获得一系列不同形貌及结构的HMSM, 随着甲醛用量的增加, HMSM结构表现为单层壳空心球、蛋黄壳空心球、双层壳空心球等结构. 其中具有蛋黄壳空心球结构的HMSM比表面积可达691 m ²/g, 孔体积达2.23 cm ³/g, 孔径均匀(3.5 nm). 以硝酸铈铵为引发剂, 在具有蛋黄壳空心球结构的HMSM中引发丙烯腈自由基聚合, 并将支链聚丙烯腈上的氰基偕胺肟化, 制得HMSM接枝聚偕胺肟(HMSM-g-PAO). 以100 mg/L的CuCl₂溶液为目标溶液, 在pH=4.0时测试合成的HMSM-g-PAO对Cu ²⁺的吸附效果, 发现吸附平衡时Cu ²⁺吸附量达134 mg/g.

关键词: 中空介孔二氧化硅, 软模板, 聚偕胺肟, Cu ²⁺吸附

Abstract:

A concise and facile one-pot sol-gel method was proposed by using resorcinol/formaldehyde(RF) resin as soft template, tetraethyl orthosilicate(TEOS) as silicon source, hexadecyl trimethyl ammonium bromide(CTAB) as pore-forming agent to fabricate hollow mesoporous silica microspheres(HMSM). A series of HMSM with different structures and topography was obtained by simply adjusting the formaldehyde amount. As the formaldehyde amount increased, the morphology of the as-prepared hollow spheres changed from single-shelled, to yolk-shelled, double-shelled and then turned back. The yolk-shelled HMSM possessed a large specific surface area(691 m ²/g), large pore volume(2.23 cm ³/g), and uniform mesopores(3.5 nm). HMSM-g-PAO(PAO=polyamidoximation) was prepared by tranforming the cyano groups in polyacrylonitrile(PAN) of 6-HMSM-g-PAN, which was prepared from yolk-shelled HMSM through polymerization of acrylonitrile initiated by ceric ammonium nitrate. As 100 mg/L CuCl₂ solution was used as the target solution, the adsorption and reduction effect of HMSM-g-PAO was tested at pH=4.0, and the adsorption amount could reach 134 mg/g when adsorption balanced.

Key words: Hollow mesoporous silica, Soft template, Polyamidoxime, Cu ²⁺ adsorption

中图分类号:

O631

TrendMD:

张辰,吴畅,韩伟豪,宫玉梅,石强. 多形貌中空介孔SiO₂的可控合成及复合物对Cu ²⁺的吸附还原. 高等学校化学学报, 2019, 40(11): 2412.

ZHANG Chen,WU Chang,HAN Weihao,GONG Yumei,SHI Qiang. Controllable Synthesis of Multi-morphological Hollow Mesoporous SiO₂ and Adsorption Reduction of Cu ²⁺ by Its Composites ^†. Chem. J. Chinese Universities, 2019, 40(11): 2412.

图/表 7

Scheme 1 Synthesis strategy of HMSM with different shell numbers tuned by formaldehyde

Fig.1 SEM(A—E) and TEM(F—J) images of the 2-HMSM(A, F), 4-HMSM(B, G), 6-HMSM(C, H), 8-HMSM(D, I) and 10-HMSM(E, J)

Fig.2 N2 adsorption-desorption isotherms and the corresponding pore-size distribution curves(insets) of 2-HMSM(A), 4-HMSM(B), 6-HMSM(C), 8-HMSM(D) and 10-HMSM(E)

Fig.3 FTIR spectra of the synthesized 6-HMSM(a), 6-HMSM-g-PAN(b) and 6-HMSM-g-PAO(c)

Fig.4 XRD patterns of 6-HMSM(a), 6-HMSM-g- PAN(b), and 6-HMSM-g-PAO(c)

Fig.5 Amount of copper adsorbed by 6-HMSM-g-PAO(A), pseudo-primary(B) and pseudo-secondary(C) dynamics models established for the adsorption process Inset of (A): Cu2+ solution before(a) and after adsorbed(b) by 6-HMSM-g-PAO.

Fig.6 Typical XPS survey spectra for 6-HMSM-g-PAO-Cu(A) and high resolution XPS spectra of Cu for 6-HMSM-g-PAO-Cu(B)

参考文献 29

[1]	Huang B. Y., Liu Y. G., Li B., Liu S. B., Zeng G. M., Zeng Z. W., Wang X. H., Ning Q. M., Zheng B. H., Yang C. P., Carbohydrate Polymers, 2017,157, 576— 585
[2]	Vargas V., Castillo J., Ocampo-Torres R., Lienemann C. P., Bouyssiere B., Petroleum Science & Technology, 2018,36(8), 618— 624
[3]	Yuan F., Pascale S. J., Salen R., Andrew T., Vicki H., Chemical Science, 2019,10, 1— 25
[4]	Lee E. L., Wachs I. E., Journal of Physical Chemistry C, 2017,112(51), 20418— 20428
[5]	Quincoces C. E., Vargas S. P. D., González M. G., Diaz A., Montes M., Journal of Materials Engineering & Performance, 2018,119(5), 1— 10
[6]	Chen J., Wang D. W., Qi J., Li G. D., Zheng F. Y., Li S. X., Small, 2015,11(4), 420— 425
[7]	Ma J. Z., Xu Q. N., Zhou J. H., Zhang J., Zhang L. M., Tang H. R., Chen L. H., Colloids & Surfaces B Biointerfaces, 2013,111, 257— 263
[8]	Hu G., Yang L., Li Y., Wang L ., Journal of Materials Chemistry B, 2009,3(4), 835— 843
[9]	Hu X., Wang Y., Zhang L., Xu M., Dong W ., International Journal of Biological Macromolecules, 2017,107(Pt B), 1811— 1820
[10]	Han Y. Y., Liu X. Y., Lu Z. D., Applied Sciences, 2018,8(8), 1— 9
[11]	Lee G., Kim S., Kim S., Choi J ., Advanced Functional Materials, 2017,27(39), 1— 8
[12]	Wei M., Zeng L., Liu R., Han L., Luo F., Chen X ., Chemistry, 2017,24(19), 4841— 4848
[13]	Xu Y. J., Wang Q., Cao Y. F., Wei X. F., Huang B. Q., RSC Advances, 2017,7(29), 18172— 18177
[14]	Panwar K., Jassal M., Agrawal A. K., Particuology, 2015,19(2), 107— 112
[15]	Guo M., Dong Y., Xiao J., Gu R., Ding M., Huang T., Li J., Zhao N., Liao H ., Journal of Biomedical Materials Research, Part A, 2018,29(1), 1223— 1235
[16]	Yan H. Q., Li J. C., Feng Y. H., Hu W. T., Liu R. L., Lin Q., Chem. J. Chinese Universities, 2013,34(9), 2164— 2170 doi: 10.7503/cjcu20130299
	( 颜慧琼, 李嘉诚, 冯玉红, 胡文涛, 刘若林, 林强 . 高等学校化学学报, 2013,34(9), 2164— 2170) doi: 10.7503/cjcu20130299
[17]	Lu W. D., Wang Q. N., He L., Li W. C., Lu A. H., Chemnanomat, 2018,4(5), 505— 509
[18]	Chang Y. F,, Li Y. Z., Song J. C., Zhao M., Guo J., An Q. D., Gong Y. M., Guo Q. P., Langmuir the Acs Journal of Surfaces & Colloids, 2018,34(28), 8223— 8229
[19]	Liu F., Shen J., Zhou W. Y., Zhang S. Y., Wan L., RSC Advances, 2017,7(26), 15992— 15996
[20]	Bian S. W., Liu S., Chang L., Journal of Materials Science, 2016,51(7), 3643— 3649
[21]	Simioni A. R., Jesus P. C. C. D., Tedesco A. C., Photodiagnosis & Photodynamic Therapy, 2018,22, 169— 177
[22]	Chu X. F., Wang H., Chi Y. D., Wang C., Lei L., Zhang W. T., Yang X. T., RSC Advances, 2018,8(4), 2072— 2076
[23]	Örnek A ., J. Colloid Interface Sci., 2017,504, 468— 478
[24]	Song J. C., Xue F. F., Lu Z. Y., Sun Z. Y., Chemical Communications, 2015,51(52), 10517— 10520
[25]	Bin D. S., Chi Z. X., Li Y., Zhang K., Yang X., Sun Y. G., Piao J. Y., Cao A. M., Wan L. J., Journal of the American Chemical Society, 2017,139(38), 13492— 13498
[26]	Yang J., Wang Y., Li W., Wang L., Fan Y., Jiang W., Luo W., Wang Y., Kong B., Selomulya C ., Advanced Materials, 2017,29(48), 1— 7
[27]	Guan J. G., Mou F. Z., Sun Z. G., Shi W. D., Chemical Communications, 2010,46(35), 6605— 6607
[28]	Li M. M., Gong Y. M., Lyu A., Liu Y. F., Zhang H., Applied Surface Science, 2016,383, 133— 141
[29]	Li M. M., Gong Y. M., Guo J., Yu Y., Zhang S., Zhao M., Chem. J. Chinese Universities, 2017,38(1), 159— 164
	( 李苗苗, 宫玉梅, 郭静, 于跃, 张森, 赵秒 . 高等学校化学学报, 2017,38(1), 159— 164)

多形貌中空介孔SiO₂的可控合成及复合物对Cu ²⁺的吸附还原

Controllable Synthesis of Multi-morphological Hollow Mesoporous SiO₂ and Adsorption Reduction of Cu ²⁺ by Its Composites ^†

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 7

参考文献 29

相关文章 8

编辑推荐

Metrics

本文评价

[1]	徐安琪, 李彬, 杜芳林. 有序介孔TiO₂的合成及光解水产氢应用[J]. 高等学校化学学报, 2021, 42(4): 978.
[2]	佘沛鸿, 徐文洲, 关卜源. 大孔道介孔氧化硅/碳基纳米材料的设计合成与应用[J]. 高等学校化学学报, 2021, 42(3): 671.
[3]	李苗苗, 宫玉梅, 郭静, 于跃, 张森, 赵秒. 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.
[4]	杨年旺, 陈涛, 傅佳骏. 智能纳米容器对缓蚀剂酸/碱双刺激的响应释放性能[J]. 高等学校化学学报, 2014, 35(5): 971.
[5]	焦鹏伟, 王建明, 周洁, 王丹, 冯琳, 江雷. 碳酸钙在天然木浆-聚酯纤维复合膜上的仿生合成[J]. 高等学校化学学报, 2009, 30(7): 1268.
[6]	王哲, 邢汝博, 韩艳春, 李滨耀. 聚合物三维微图案加工的转移微模塑新方法[J]. 高等学校化学学报, 2003, 24(5): 946.
[7]	杨超雄, 吴锦远. 纤维素基磁性聚偕胺肟树脂的研究——CuCl₂的吸附行为[J]. 高等学校化学学报, 1998, 19(3): 419.
[8]	吴锦远, 杨超雄. 纤维素基磁性聚偕胺肟树脂的研究——溴在树脂上的吸附动力学[J]. 高等学校化学学报, 1998, 19(2): 265.