7种胺基键合硅胶的制备及其对重金属Pb2+的吸附

doi:10.3724/SP.J.1123.2019.09030

色谱 ›› 2020, Vol. 38 ›› Issue (3): 341-349.DOI: 10.3724/SP.J.1123.2019.09030

7种胺基键合硅胶的制备及其对重金属Pb²⁺的吸附

李来明, 任芳芳, ASSEFAAschenaki, 刘佳, 张筱菲, 包建民, 李优鑫()

天津市现代药物传递及功能高效化重点实验室, 天津化学化工协同创新中心, 天津大学药物科学与技术学院, 天津 300072

收稿日期:2019-09-29 出版日期:2020-03-08 发布日期:2020-12-10
通讯作者: 李优鑫
作者简介:李优鑫, Tel:(022)27892820, E-mail:lyx@tju.edu.cn
基金资助:
国家自然科学基金(21605112)

Preparation of seven kinds of amino bonded silica gels and their adsorption to heavy metal Pb²⁺

LI Laiming, REN Fangfang, ASSEFA Aschenaki, LIU Jia, ZHANG Xiaofei, BAO Jianmin, LI Youxin()

Tianjin Key Laboratory for Modern Drug Delivery and High-Efficiency, Collaborative Innovation Center of Chemical Science and Engineering, School of Pharmaceutical Science and Technology, Tianjin University, Tianjin 300072, China

Received:2019-09-29 Online:2020-03-08 Published:2020-12-10
Contact: LI Youxin
Supported by:
National Natural Science Foundation of China(21605112)

摘要/Abstract

摘要：

制备了氨丙基键合硅胶（SiO₂-N）、乙二胺-N-丙基键合硅胶（SiO₂-2N）、二乙烯三胺基键合硅胶（SiO₂-3N）、三乙烯四胺基键合硅胶（SiO₂-4N）、四乙烯五胺基键合硅胶（SiO₂-5N）、五乙烯六胺基键合硅胶（SiO₂-6N）和聚乙烯亚胺基键合硅胶（SiO₂-nN），一步法制备的SiO₂-N和SiO₂-2N的胺基键合密度高达2.07 mmol/g和1.71mmol/g，两步法制备的SiO₂-nN的胺基键合密度为0.02mmol/g，其余胺基键合硅胶中胺基密度约为0.50mmol/g。这7种胺基键合硅胶被用于水溶液中常见重金属离子Pb²⁺的吸附研究。结果表明，在30℃条件下，分别加入10 mL 400 mg/L的Pb²⁺溶液（pH 5）和20 mg胺基键合硅胶进行吸附，10 h后，Pb²⁺吸附量达到最大，吸附过程符合Freundlich等温方程。SiO₂-N、SiO₂-2N、SiO₂-3N、SiO₂-4N、SiO₂-5N、SiO₂-6N和SiO₂-nN对Pb²⁺的吸附量依次为131.28、138.98、85.37、75.22、61.87、79.12和114.06 mg/g，这些胺基键合硅胶在吸附Pb²⁺方面均非常具有潜力。

关键词: 胺基键合硅胶, 重金属去除, 铅离子, 吸附量

Abstract:

Seven kinds of amino bonded silica gels were prepared. They were aminopropyl bonded silica gel (SiO₂-N), ethylenediamine-N-propyl bonded silica gel (SiO₂-2N), diethylenetriamine bonded silica gel (SiO₂-3N), triethylenetetramine bonded silica gel (SiO₂-4N), tetraethylene pentamine bonded silica gel (SiO₂-5N), pentaethylene hexamine bonded silica gel (SiO₂-6N) and polyvinylimide bonded silica gel (SiO₂-nN). The densities of the bonded amino groups in SiO₂-N and SiO₂-2N prepared by a one-step method were up to 2.07mmol/g and 1.71mmol/g, respectively. The density of the bonded amino groups in SiO₂-nN with ethylene imine units prepared by a two-step method, was 0.02mmol/g. The densities of the bonded amino groups in the other silica gels were similar, about 0.50mmol/g. The synthesized silica gels were used to investigate the adsorption of the heavy metal ion Pb²⁺ which commonly exists in aqueous solutions. About 20 mg of the silica gel was added to 10 mL of 400 mg/L Pb²⁺, at pH 5 and 30℃. The results indicated that the adsorption capacity reached the maximum value after 10 h. The adsorption process was fit to the Freundlich isothermal equation. The adsorption capacities of SiO₂-N, SiO₂-2N, SiO₂-3N, SiO₂-4N, SiO₂-5N, SiO₂-6N and SiO₂-nN to Pb²⁺were 131.28, 138.98, 85.37, 75.22, 61.87, 79.12 and 114.06 mg/g, respectively, indicating the potential utility of these amino-functionalized silica gels for the adsorption of Pb²⁺.

Key words: amino bonded silica gel, heavy metal removal, lead ion (Pb²⁺), adsorption capacity

李来明, 任芳芳, ASSEFAAschenaki, 刘佳, 张筱菲, 包建民, 李优鑫. 7种胺基键合硅胶的制备及其对重金属Pb²⁺的吸附[J]. 色谱, 2020, 38(3): 341-349.

LI Laiming, REN Fangfang, ASSEFA Aschenaki, LIU Jia, ZHANG Xiaofei, BAO Jianmin, LI Youxin. Preparation of seven kinds of amino bonded silica gels and their adsorption to heavy metal Pb²⁺[J]. Chinese Journal of Chromatography, 2020, 38(3): 341-349.

图/表 9

图1 系列胺基键合硅胶的合成路线

Fig. 1 Synthesis of a series of the amino bonded silica gel SiO2-N: aminopropyl bonded silica gel; SiO2-2N: ethylenediamine-N-propyl bonded silica gel; SiO2-3N: diethylenetriamine bonded silica gel; SiO2-4N: triethlenetetramine bonded silica gel; SiO2-5N: tetraethylenepentamine bonded silica gel; SiO2-6N: pentaethylenehexamide bonded silica gel; SiO2-nN: polyethyleneimine bonded silica gel.

图2 系列胺基键合硅胶的红外光谱图

Fig. 2 IR spectra of a series of the amino bonded silica gel

图3 硅胶和氨丙基键合硅胶扫描电镜图

Fig. 3 Scanning electron microscopes (SEM) of SiO2 and the aminopropyl bonded SiO2 a. SEM of SiO2(×500); b. SEM of SiO2(×50000); c. SEM of the aminopropyl bonded SiO2(×500); d. SEM of the aminopropyl bonded SiO2(×50000).

图4 (a) 硅胶和(b)氨丙基键合硅胶的EDS能谱图

Fig. 4 Energy dspersive spectroscopy (EDS) spectra of (a) SiO2 and (b) the aminopropyl bonded SiO2

表1 硅胶及系列胺基键合硅胶的元素分析结果

Table 1 Elemental analysis results of SiO2 and a series of the amino bonded silica gel

Amino bonded silica gel	C/%	N/%	C/N	N density/(mmol/g)	Number of N	Content of the bonded group/(mmol/g)
SiO₂	0.1	0.1	1.0	0.1	0	0
SiO₂-N	6.87	2.9	2.4	2.1	1	2.07
SiO₂-2N	10.4	4.8	2.1	3.4	2	1.71
SiO₂-3N	4.8	2.1	2.3	1.5	3	0.50
SiO₂-4N	6.4	3.1	2.0	2.2	4	0.55
SiO₂-5N	7.6	3.7	2.3	2.6	5	0.53
SiO₂-6N	8.7	4.3	2.0	3.1	6	0.51
SiO₂-nN	8.5	3.4	2.5	2.4	_~110	0.02

图5 系列胺基键合硅胶的小角XRD图

Fig. 5 Low-angle X-ray diffraction (XRD) patterns of a series of the amino bonded silica gel

图6 Pb2+初始质量浓度对系列胺基键合硅胶吸附量的影响

Fig. 6 Effect of original mass concentrations of Pb2+on adsorptive capacities by a series of the amino bonded silica gel

图7 (a) 溶液pH值、(b)吸附时间和(c)吸附温度对系列胺基键合硅胶吸附量的影响

Fig. 7 Effect of (a) pH value of solution, (b) absorption time and (c) absorption temperature on the adsorption capacities of a series of the amino bonded silica gel

图8 胺基键合硅胶吸附Pb2+的拟合(a)Langmuir和(b)Freundlich等温线

Fig. 8 (a)Langmuir and (b) Freundlich isotherms of absorption of the amino group bonded silica gels to Pb2+

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7种胺基键合硅胶的制备及其对重金属Pb²⁺的吸附

Preparation of seven kinds of amino bonded silica gels and their adsorption to heavy metal Pb²⁺

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