线性温敏性聚合物嵌段调控的ReO4-智能离子印迹聚合物的设计制备及其吸附分离性能研究

doi:10.11949/0438-1157.20221291

化工学报 ›› 2023, Vol. 74 ›› Issue (2): 941-952.DOI: 10.11949/0438-1157.20221291

• 材料化学工程与纳米技术 • 上一篇下一篇

线性温敏性聚合物嵌段调控的 $R e O 4 -$ 智能离子印迹聚合物的设计制备及其吸附分离性能研究

许万¹^,²(), 陈振斌¹^,²(), 张慧娟¹^,², 牛昉昉¹^,², 火婷¹^,², 刘兴盛¹^,²

^1.兰州理工大学材料科学与工程学院，甘肃兰州 730050
^2.兰州理工大学省部共建有色金属先进加工与再利用国家重点实验室，甘肃兰州 730050

收稿日期:2022-09-26 修回日期:2022-12-31 出版日期:2023-02-05 发布日期:2023-03-21
通讯作者: 陈振斌
作者简介:许万（1998—），男，硕士研究生，xuwanzong@163.com
基金资助:
甘肃省自然科学基金项目(22JR5RA227);沈阳材料科学国家实验室与有色金属先进加工与再利用国家重点实验室联合基金项目(18LHZD003)

Study on synthesis, adsorption and desorption performance of linear temperature-sensitive segment polymer regulated intelligent $R e O 4 -$ ion-imprinted polymer

Wan XU¹^,²(), Zhenbin CHEN¹^,²(), Huijuan ZHANG¹^,², Fangfang NIU¹^,², Ting HUO¹^,², Xingsheng LIU¹^,²

^1.School of Materials Science and Engineering, Lanzhou University of Technology, Lanzhou 730050, Gansu, China
^2.State Key Laboratory of Advanced Processing and Recycling of Nonferrous Metals, Lanzhou University of Technology, Lanzhou 730050, Gansu, China

Received:2022-09-26 Revised:2022-12-31 Online:2023-02-05 Published:2023-03-21
Contact: Zhenbin CHEN

摘要/Abstract

摘要：

首先采用可逆加成断裂聚合法（RAFT），合成了线性温敏性聚合物聚N,N-二乙基丙烯酰胺（PDEA），之后将其引入到以丙烯酸（AA）、丙烯酰胺（AM）、N,N-二乙基丙烯酰胺（DEA）为功能单体， $R e O 4 -$ 为模板离子，N,N-亚甲基双丙烯酰胺（NMBA）为交联剂，甲醇和水混合溶液（V_甲醇∶V_蒸馏水=3∶7）为溶剂的离子印迹聚合物制备体系，自组装完成后，用Vc-H₂O₂引发聚合，制备出一种线性温敏性聚合物嵌段调控的智能离子印迹聚合物—— $R e O 4 -$ -IIP。用傅里叶变换红外光谱（FTIR）和扫描电子显微镜（SEM）对 $R e O 4 -$ -IIP的结构和形貌进行了表征，以电感耦合等离子体发射光源（ICP-AES）为表征手段对 $R e O 4 -$ -IIP的吸附分离性能进行了评价。结果表明： $R e O 4 -$ -IIP被成功制备， $R e O 4 -$ -IIP的饱和吸附量为0.1126 mmol/g，解吸率为75%，在二元混合溶液中具有良好的选择性，在经过7次吸附/解吸循环后， $R e O 4 -$ -IIP依旧保持良好的吸附解吸能力，表明 $R e O 4 -$ -IIP具有巨大的工业应用前景。

关键词: 智能离子印迹聚合物, 线性温敏性嵌段, 铼分离回收, 选择性吸附, $R e O 4 -$ -IIP

Abstract:

The linear temperature-sensitive polymer poly(N,N-dimethyl acrylamide) (PDEA) was firstly synthesized by reversible addition-fragmentation chain transfer (RAFT). Subsequently, it was introduced into the ion-imprinted polymer preparation system using acrylic acid (AA), acrylamide (AM), and N,N-diethylacrylamide (DEA) as functional monomers, $R e O 4 -$ as template ion, N,N-methylenebisacrylamide (NMBA) as crosslinker, and a mixture of methanol and water (V_methanol∶V_water=3∶7) as solvent. After the self-assembly was completed, polymerization was initiated by Vc-H₂O₂ to prepare an intelligent ion-imprinted polymer $R e O 4 -$ -IIP with linear temperature-sensitive polymer block regulation. The structure and morphology of $R e O 4 -$ -IIP were characterized by Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), and the adsorption and separation performance of $R e O 4 -$ -IIP was evaluated by inductively coupled plasma atomic emission spectroscopy (ICP-AES). The results showed that $R e O 4 -$ -IIP was successfully prepared, the saturated adsorption capacity of $R e O 4 -$ -IIP was 0.1126 mmol/g, the desorption rate was 75%, and it had good selectivity in the binary mixed solution. After 7 adsorption/desorption cycles, $R e O 4 -$ -IIP still maintains good adsorption-desorption capacity, indicating that $R e O 4 -$ -IIP has great industrial application prospects.

Key words: smart ion-imprinted polymer, linear temperature-sensitive block, rhenium separation and recovery, selective adsorption, $R e O 4 -$ -IIP

中图分类号:

O 647.33

许万, 陈振斌, 张慧娟, 牛昉昉, 火婷, 刘兴盛. 线性温敏性聚合物嵌段调控的 $R e O 4 -$ 智能离子印迹聚合物的设计制备及其吸附分离性能研究[J]. 化工学报, 2023, 74(2): 941-952.

Wan XU, Zhenbin CHEN, Huijuan ZHANG, Fangfang NIU, Ting HUO, Xingsheng LIU. Study on synthesis, adsorption and desorption performance of linear temperature-sensitive segment polymer regulated intelligent $R e O 4 -$ ion-imprinted polymer[J]. CIESC Journal, 2023, 74(2): 941-952.

图/表 12

图1 ReO4--IIP制备过程

Fig.1 The preparation process of ReO4--IIP

图2 PDEA溶液透过率与温度的关系

Fig.2 Relationship between transmittance of PDEA solution and temperature

图3 ReO4--IIP和ReO4--NIIP的红外光谱图

Fig.3 The FTIR spectra of ReO4--IIP and ReO4--NIIP

图4 ReO4--IIP和ReO4--NIIP的SEM图

Fig.4 SEM images of ReO4--IIP and ReO4--NIIP

图5 ReO4--IIP在不同温度下的吸附动力学曲线(a)、零级动力学模型(b)、准一级动力学模型(c)和准二级动力学模型(d)

Fig.5 The adsorption kinetics (a), zero-order model (b), pseudo-first-order model (c) and pseudo-second-order model (d) of ReO4--IIP at different temperatures

表1 动力学模型模拟结果

Table 1 Kinetic model simulation results

温度/℃	零级动力学模型	R²	准一级动力学模型	R²	准二级动力学模型	R²
25	y₁=8.1258×10^-4x+0.0110	0.9984	y₁=-0.0131x-0.1170	0.9971	y₁=01312x-0.0880	0.9731
	y₂=4.4343×10^-4x+0.0245	0.9633	y₂=-0.0164x+0.0271	0.9768	y₂=05887x-32.9030	0.9473
	y₃=8.9601×10^-4x+0.0677	0.7951	y₃=-0.02x+0.3146	0.9987	y₃=7.4285x-13331.5783	0.8545
35	y₁=0.0011×10^-4x+0.0215	0.9814	y₁=-0.0160x-0.1906	0.9984	y₁=0.1441x+0.0575	0.9621
	y₂=4.6000×10^-4x+0.0410	0.9999	y₂=-0.0138x-0.1767	0.9708	y₂=0.3684x-16.9263	0.9645
	y₃=1.4100×10^-4x+0.0702	0.6980	y₃=-0.0175x+0.1533	0.9971	y₃=3.6028x-625.8839	0.9395
40	y₁=9.8874×10^-4x+0.0161	0.9836	y₁=-0.0143x-0.1516	0.9999	y₁=0.1310x+0.0077	0.9669
	y₂=4.2630×10^-4x+0.033	0.9849	y₂=-0.0124x-0.1649	0.9637	y₂=0.3166x-13.5943	0.9640
	y₃=1.4100×10^-4x+0.0702	0.6980	y₃=-0.0222x+0.8245	0.9831	y₃=6.1036x-1099.847	0.9439

图6 ReO4--IIP在35℃下的吸附等温曲线(a)、Scatchard 模型(b)、Langumuir 模型(c)和Freundlich 模型(d)

Fig.6 The adsorption thermodynamic curves (a), Scatchard model (b), Langmuir model (c) and Freundlich model (d) of ReO4--IIP at 35℃

图7 不同浓度氨水的解吸率

Fig.7 The influence of different concentrations of ammonia on desorption rate

图8 解吸时间和解吸率之间的关系

Fig.8 The relationship between desorption time and desorption rate

表2 ReO4--IIP和ReO4--NIIP的选择性参数

Table 2 Selectivity parameters of ReO4--IIP and ReO4--NIIP

Type	$R e O 4 -$ -IIP			$R e O 4 -$ -NIIP			k′
Type	k_d(Re)/(L/g)	k_d/(L/g)	k	k_d(Re)/(L/g)	k_d/(L/g)	k	k′
Re/Mn	0.258	0.068(Mn)	3.794	0.043	0.042(Mn)	1.024	3.705
Re/Ni	0.225	0.047(Ni)	4.787	0.060	0.049(Ni)	1.224	3.911
Re/Co	0.265	0.056(Co)	4.732	0.051	0.043(Co)	1.186	3.990

表2 ReO4--IIP和ReO4--NIIP的选择性参数

Table 2 Selectivity parameters of ReO4--IIP and ReO4--NIIP

Type	$R e O 4 -$ -IIP			$R e O 4 -$ -NIIP			k′
Type	k_d(Re)/(L/g)	k_d/(L/g)	k	k_d(Re)/(L/g)	k_d/(L/g)	k	k′
Re/Mn	0.258	0.068(Mn)	3.794	0.043	0.042(Mn)	1.024	3.705
Re/Ni	0.225	0.047(Ni)	4.787	0.060	0.049(Ni)	1.224	3.911
Re/Co	0.265	0.056(Co)	4.732	0.051	0.043(Co)	1.186	3.990

图9 n(AA)/n(AM）(a)，n(DEA)/n(AM) (b)，n(ReO4-)/n(AM) (c)，n(NMBA)/n(AM) (d)，聚合温度(e)和聚合时间(f)对ReO4--IIP吸附性能的影响

Fig.9 Effect of n(AA)/n(AM) (a), n(DEA)/n(AM) (b), n(ReO4-)/n(AM) (c), n(NMBA)/n(AM) (d), polymerization temperature (e) and polymerization time (f) on the adsorption performance of ReO4--IIP

图10 ReO4--IIP的重复使用性

Fig.10 Reusability of ReO4--IIP

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线性温敏性聚合物嵌段调控的 $R e O 4 -$ 智能离子印迹聚合物的设计制备及其吸附分离性能研究

Study on synthesis, adsorption and desorption performance of linear temperature-sensitive segment polymer regulated intelligent $R e O 4 -$ ion-imprinted polymer

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