中空介孔二氧化硅锚固聚偕胺肟吸附Cr(Ⅵ)

doi:10.7503/cjcu20160398

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (1): 159.doi: 10.7503/cjcu20160398

中空介孔二氧化硅锚固聚偕胺肟吸附Cr(Ⅵ)

李苗苗, 宫玉梅(), 郭静(), 于跃, 张森, 赵秒

大连工业大学纺织与材料工程学院, 大连 116034

收稿日期:2016-06-01 出版日期:2017-01-10 发布日期:2016-12-06
作者简介:联系人简介: 宫玉梅, 女, 博士, 教授, 主要从事生物质基复合材料与功能高分子研究. E-mail: ymgong@dlpu.edu.cn; 郭静, 女, 博士, 教授, 博士生导师, 主要从事高分子材料成型加工与改性研究. E-mail: guojing@dlpu.edu.cn
基金资助:
国家留学基金(批准号: 20163035)、辽宁省自然科学基金(批准号: 2016102048)和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(批准号: 201513)资助.

Polyamidoximation of Hollow Mesoporous Silica and Its Application in Adsorption of Cr(Ⅵ)^†

LI Miaomiao, GONG Yumei^*(), GUO Jing^*(), YU Yue, ZHANG Sen, ZHAO Miao

School of Textile and Material Engineering, Dalian Polytechnic University, Dalian 116034, China

Received:2016-06-01 Online:2017-01-10 Published:2016-12-06
Contact: GONG Yumei,GUO Jing E-mail:ymgong@dlpu.edu.cn;guojing@dlpu.edu.cn
Supported by:
† Supported by the Fund of China Scholarship Council(No.20163035), the Natural Science Foundation of Liaoning Province, China(No.201602048) and the Open Research Fund of the State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences(No.201513).

摘要/Abstract

摘要：

以硝酸铈铵为引发剂, 在自制的中空介孔二氧化硅(HMS)的空腔和通道内引发丙烯腈自由基聚合, 并将其氰基偕胺肟化, 用于制备具有吸附Cr(Ⅵ)的廉价有机无机复合吸附材料—中空介孔二氧化硅锚固聚偕胺肟. 通过傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)及N₂吸附-脱附比表面分析对中空介孔二氧化硅锚固聚偕胺肟进行表征. 结果表明, 制备的中空微球直径约为400 nm, 其壁上孔径约为11.0 nm, 比表面积约为431 m²/g, 锚固聚偕胺肟后中空微球壁上孔道直径约为4.6 nm, 比表面积降低为347 m²/g. HMS锚固的聚偕胺肟对重铬酸钾溶液中铬的吸附量高达0.46 mmol/g, 吸附过程中伴随化学反应, 符合伪二级动力学模型, 可用作废水处理中重金属离子的高效廉价吸附材料.

关键词: 中空介孔二氧化硅, 聚偕胺肟, Cr(Ⅵ)吸附, 锚固

Abstract:

Polyamidoximation of hollow mesoporous silica(HMS/PAO) was prepared by tranforming the cyano groups in polyacrylonitrile grafted from hollow mesoporous silica(HMS) through polymerization of acrylonitrile initiated by ceric ammonium nitrate. The hollow mesoporous silica was prepared by a facile one-pot sol-gel method. The microstructure and characteristic of the HMS and HMS/PAO were examined by Fourier transform Infrared spectra(FTIR), X-ray diffraction, scanning electron microscope(SEM), N₂ adsorption desorption isotherm. The results showed that the diameter of the HMS was about 400 nm, and the size of the mesoporous was ca. 11.0 nm. The size of the mesoporous was ca. 4.6 nm and more uniform and smaller. As potassium dichromate solution(K₂Cr₂O₇) was used as a target solution for detecting adsorption capacity of the prepared HMS/PAO, the adsorption chromium kinetics was consistent with the pseudo-second-order kinetics model by analyzing the adsorption amount as a function of the sorbent dispersed duration in solution at pH=2.0. The adsorption capacity of HMS/PAO for chromium was as much as 0.46 mmol/g. Therefore, it is an adsorbent with high efficiency.

Key words: Hollow mesoporous silica, Amidoximation, Cr(Ⅵ) adsorption, Anchor

中图分类号:

O631

TrendMD:

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). 高等学校化学学报, 2017, 38(1): 159.

LI Miaomiao, GONG Yumei, GUO Jing, YU Yue, ZHANG Sen, ZHAO Miao. Polyamidoximation of Hollow Mesoporous Silica and Its Application in Adsorption of Cr(Ⅵ)^†. Chem. J. Chinese Universities, 2017, 38(1): 159.

图/表 10

Scheme 1 Schematic illustration of the HMS/PAO preparation

Fig.1 Typical SEM images of HMS Insert: a collapsed HMS sphere.

Fig.2 FTIR spectra of HMS(a), HMS/PAN(b) and HMS/PAO(c)

Fig.3 N2 adsorption and desorption profiles of HMS(A) and HMS/PAO(B)

Table 1 Characteristics of the synthesized HMS and HMS/PAO

Sample	Specific surface area/(m²·g^-1)	Total pore volume, V/(cm³·g^-1)	Average pore diameter/nm
HMS	431	1.16	11.0
HMS/PAO	347	0.55	4.6

Fig.4 Color of the K2Cr2O7 solutions at pH=2.0(A) Original HMS; (B) dispersing HMS/PAO; (C) dispersing HMS.

Scheme 2 Adsorption mechanism of Cr(Ⅵ) and Cr(Ⅲ) on HMS/PAO

Fig.5 Amount of chromium(mg) adsorbed by per gram HMS/PAO(A), the plot of lg(qe-qt) vs. t(B) and the plot of t/qt vs. t(C)(A) m=50 mg, c0=1 mg/mL, T=298.15 K, pH=2.0, V=50 mL.

Table 2 Adsorption kinetic parameters of HMS/PAO for Cr(Ⅵ)

Model	q_e,exp/(mg·g^-1)	q_e,cal/(mg·g^-1)	k₁/min	R²
Pseudo-first-order	23.68	10.99	0.014	0.731
Pseudo-second-order	23.68	31.53	0.002	0.965

Table 3 Comparation of the adsorption capacity of synthesized HMS, HMS/PAN, and HMS/PAO on Cr(Ⅵ) with that of amino group and amidoxime group modified mesoporous silica on Zn(Ⅱ), Cu(Ⅱ) and Pb(Ⅱ) in literatures

Adsorbent	Ion	Capacity/(mmol·g^-1)	Ref.	Adsorbent	Ion	Capacity/(mmol·g^-1)	Ref.
AD-2-SiO₂-CN400	Pb(Ⅱ)	0.45	[22]	HMS	Cr(Ⅵ)	0.04	This paper
MCM-NH₂	Zn(Ⅱ)	0.22	[17]	HMS/PAN	Cr(Ⅵ)	0.14	This paper
MCM-NH₂	Cu(Ⅱ)	0.18	[17]	HMS/PAO	Cr(Ⅵ)	0.46	This paper

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中空介孔二氧化硅锚固聚偕胺肟吸附Cr(Ⅵ)

Polyamidoximation of Hollow Mesoporous Silica and Its Application in Adsorption of Cr(Ⅵ)^†

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中空介孔二氧化硅锚固聚偕胺肟吸附Cr(Ⅵ)

Polyamidoximation of Hollow Mesoporous Silica and Its Application in Adsorption of Cr(Ⅵ)†

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Polyamidoximation of Hollow Mesoporous Silica and Its Application in Adsorption of Cr(Ⅵ)^†