离子型超交联聚合物吸附罗丹明B

王科伟; 午赵霞; 刘慧君; 郭永; 崔晓娜; 任斐; 贾治芳

doi:10.14133/j.cnki.1008-9357.20211123001

离子型超交联聚合物吸附罗丹明B

doi: 10.14133/j.cnki.1008-9357.20211123001

山西大同大学化学与化工学院, 化学生物传感山西省重点实验室, 山西大同 037009

基金项目: 国家自然科学基金面上项目(21975146); 山西省省筹资金资助回国留学人员科研项目(2020-134); 山西省应用基础研究计划青年项目(201801D221096); 大同市工业重点研发计划项目(2019028, 2018013)

详细信息

作者简介:
王科伟（1982—），男，博士，副教授，主要研究方向为有机多孔材料的设计及应用。E-mail：wangkewei@sxdtdx.edu.cn

通讯作者:
贾治芳，E-mail：jiazhifang@sxdtdx.edu.cn

中图分类号: O631.5
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- 被引次数: 0
出版历程
- 收稿日期: 2021-11-23
- 录用日期: 2022-04-27
- 网络出版日期: 2022-05-07
- 刊出日期: 2022-09-23

Ionic Hypercrosslinked Polymer for Rhodamine B Adsorption

School of Chemistry and Chemical Engineering, Shanxi Datong University, Datong 037009, Shanxi, China

摘要

摘要: 为了高效吸附废水中的可溶性有机染料，以4-苯胺基苯磺酸钠和苯为单体，二甲氧基甲烷为交联剂，在无水FeCl₃催化下，经过付-克反应一步合成了磺酸钠离子(―SO₃Na)修饰的超交联聚合物(HCP-SO₃Na)。通过元素分析、红外光谱、N₂吸/脱附分析、固态核磁共振波谱和热重分析对HCP-SO₃Na的结构和热性能进行了表征。结果表明，HCP-SO₃Na是一种比表面积大、热稳定性强的无定形微孔有机聚合物，比表面积为587 m²/g，微孔面积为411 m²/g。通过对阳离子染料罗丹明B (RhB)的吸附研究表明，―SO₃Na基团的引入，可增加HCP对RhB的饱和吸附量，最大吸附量达431 mg/g，吸附符合准二级动力学模型和Langmuir 模型，且循环吸附5次之后，吸附性能无明显降低。
- 超交联聚合物 /
- 离子型多孔材料 /
- 罗丹明B /
- 染料吸附
Abstract: Hypercrosslinked polymer (HCP) is a class of microporous organic polymer connected by light elements (C, H, O, and N) through covalent bonds. In order to efficiently adsorb soluble organic dyes in water treatment, here, an ionic HCP (HCP-SO₃Na) was prepared through an efficient Friedel-Crafts reaction from sodium 4-(phenylamino)benzenesulfonate and benzene in the presence of formaldehyde dimethyl acetal and anhydrous FeCl₃. A series of characterizing techniques such as elemental analysis, infrared spectroscopy, N₂ adsorption/desorption analysis, solid-state ¹³C nuclear magnetic resonance spectroscopy and thermogravimetric analysis were employed to characterize the structure and thermal property of the ionic polymer. It was found that HCP-SO₃Na was an amorphous microporous polymer with large specific surface area and high thermostability. The specific surface area and micropore area were 587 m²/g and 411 m²/g, respectively. The adsorption of HCP-SO₃Na for the organic dye of Rhodamine B demonstrated the ―SO₃Na groups distributing uniformly in the polymer could increase the saturation capacity of HCP. The maximum adsorption capacity was up to 431 mg/g. The adsorption process conformed to kinetic pseudo-second-order model and Langmuir model. HCP-SO₃Na can be easily recovered and reused five times without significant loss of activity.
- hypercrosslinked polymer /
- ionic porous material /
- Rhodamine B /
- dye adsorption

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图 1 HCP-SO₃Na的合成

Figure 1. Synthesis of HCP-SO₃Na

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图 2 (a) 4-苯胺基磺酸钠单体和HCP-SO₃Na的FT-IR谱图; (b) HCP-SO₃Na的¹³C-CP/MAS-NMR谱图

Figure 2. (a) FT-IR spectra of sodium 4-(phenylamino)benzenesulfonate and HCP-SO₃Na; (b) Solid state ¹³C-CP/MAS-NMR spectrum of HCP-SO₃Na

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图 3 HCP-SO₃Na的（a）N₂吸/脱附等温曲线，（b）孔径分布曲线和（c）TGA以及DTG曲线图

Figure 3. (a) N₂ adsorption/desorption isotherms, (b) pore size distribution and (c) TGA and DTG curves of HCP-SO₃Na

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图 4 不同时间HCP-SO₃Na对RhB和MO及HCP-SO₃H对RhB的吸附曲线

Figure 4. Adsorption curves of HCP-SO₃Na for RhB and MO, and HCP-SO₃H for RhB at different time

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图 5 HCP-SO₃Na吸附RhB的(a)准一级动力学和(b)准二级动力学拟合曲线

Figure 5. Fitting lines of (a) pseudo-first-order model and (b) pseudo-second-order model of HCP-SO₃Na for RhB

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图 6 HCP-SO₃Na吸附RhB的(a) Langmuir等温方程式和(b) Freundlich等温方程式拟合曲线

Figure 6. Fitting lines of (a) Langmuir and (b) Freundlich isothermal equations of HCP-SO₃Na for RhB

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图 7 HCP-SO₃Na的吸附循环

Figure 7. Adsorption cycle of HCP-SO₃Na

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表 1 HCP-SO₃Na的元素组成

Table 1. Elemental composition of HCP-SO₃Na

Sample	w(C)/%	w(H)/%	w(N)/%	w(S)/%
HCP-SO₃Na	66.8	5.4	1.6	2.5
HCP-SO₃Na¹⁾	67.9	5.0	2.0	2.8
1) After five cycles

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表 2 HCP-SO₃Na的比表面积和微孔参数

Table 2. Surface area and porosity of HCP-SO₃Na

Sample	S_BET¹⁾/(m²·g⁻¹)	S_L²⁾/(m²·g⁻¹)	S_MA³⁾/(m²·g⁻¹)	V⁴⁾/(cm³·g⁻¹)	V_M⁵⁾/(cm³·g⁻¹)
HCP-SO₃Na	587	647	411	0.47	0.17
HCP-SO₃Na⁶⁾	574	642	385	0.41	0.16
1) Surface area calculated from nitrogen adsorption isotherms using BET equation; 2) Surface area calculated from nitrogen adsorption isotherms using Langmuir equation; 3) t-Plot micropore area; 4) Pore volume calculated from nitrogen isotherm at p/p₀ = 0.99; 5) t-Plot micropore volume; 6) The recycled HCP-SO₃Na

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表 3 25 ℃下HCP-SO₃Na吸附RhB的动力学参数

Table 3. Kinetic parameters for RhB adsorption onto HCP-SO₃Na at 25 ℃

Sample	Pseudo-first-order model			Pseudo-second-order model
Sample	q_e/(mg·g⁻¹)	k₁	R²	q_e/(mg·g⁻¹)	k₂	R²
HCP-SO₃Na	31.76	0.0474	0.9602	98.72	0.0049	0.9998

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表 4 25 ℃下HCP-SO₃Na吸附RhB的吸附等温参数

Table 4. Adsorption isotherm parameters for RhB onto HCP-SO₃Na at 25 ℃

Sample	Langmuir			Freundlich
Sample	q_max/(mg·g⁻¹)	K_L	R²	K_F	n	R²
HCP-SO₃Na	431.03	3.467	0.9997	283.27	10.41	0.9446

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