磁性壳聚糖复合材料的制备及其对铀吸附性能研究

王未然; 何卉

磁性壳聚糖复合材料的制备及其对铀吸附性能研究

王未然^,,
何卉

东华理工大学　核科学与工程学院, 江西南昌 330013

基金项目: 国家自然科学基金 (22006012)

详细信息

通讯作者:
王未然，博士，讲师，硕士生导师，研究方向为核燃料循环与材料研究　E-mail: 626648832@qq.com

中图分类号: X591，TB332
计量
- 文章访问数: 27
- HTML全文浏览量: 14
- 被引次数: 0
出版历程
- 收稿日期: 2024-08-06
- 修回日期: 2024-09-30
- 录用日期: 2024-10-12
- 网络出版日期: 2024-10-28

Preparation of magnetic chitosan composites and their adsorption properties on uranium

WANG Weiran^,,
HE Hui

School of Nuclear Science and Engineering, East China University of Technology, Nanchang, 330013

Funds: National Natural Science Foundation of China (No.22006012)

摘要

摘要: 对于壳聚糖的回收困难问题，通过引入磁性铁酸锌颗粒来构筑核壳结构的复合纳米颗粒。进一步引入两种不同的官能团，接枝到壳聚糖包覆的磁性铁酸锌/二氧化硅纳米颗粒上，制备出新型、高选择性、耐酸、可重复使用的两种功能化磁性壳聚糖基复合材料(ZSC-P和ZSC-D)。通过调节溶液pH、吸附时间、铀溶液初始浓度、吸附温度探究复合材料的吸附性能；通过动力学和热力学模型对复合材料的铀吸附过程进行研究。pH=4时，ZSC-P吸附容量达到122.16 mg/g；pH=5时，ZSC-D吸附容量达到122.76 mg/g。两种吸附材料的吸附过程均符合准二级动力学模型和 Freundlich模型。ZSC-P和ZSC-D材料均展现出较好的对铀酰离子选择性吸附性能和再生性能。
- 壳聚糖 /
- 磁性颗粒 /
- 复合材料 /
- 铀 /
- 吸附
Abstract: For the difficult recycling problem of chitosan, composite nanoparticles with core-shell structure were constructed by introducing magnetic zinc ferrate particles. Two different functional groups were further introduced and grafted onto the chitosan-coated magnetic zinc ferrate/silica nanoparticles to prepare novel, highly selective, acid-resistant and reusable two functionalized magnetic chitosan-based composites (ZSC-P and ZSC-D). The adsorption properties of the composites were investigated by adjusting the solution pH, adsorption time, initial concentration of uranium solution, and adsorption temperature; and the uranium adsorption process of the composites was investigated by kinetic and thermodynamic modelling.The maximum adsorption capacity of the composites was reached by the adsorbent of ZSC-P at 122.16 mg/g for pH=4, and that of ZSC-D was reached by the adsorbent of ZSC-D at 122.76 mg/g for pH=5. The adsorption processes of both adsorbent materials are as follows. The adsorption processes of the two adsorbent materials were in accordance with the quasi-secondary kinetic model and the Freundlich model, and both ZSC-P and ZSC-D materials showed good selective adsorption and regeneration properties for uranyl ions.
- chitosan /
- magnetic nanoparticles /
- composites /
- uranium /
- adsorption

HTML全文

图 1 (a) ZnFe₂O₄@SiO₂@CS-DTPA ZSC-D (ZSC-D)的SEM图、(b) ZnFe₂O₄@SiO₂@CS-DTPA (ZSC-P) 的SEM图

Figure 1. SEM images of (a) ZnFe₂O₄@SiO₂@CS-DTPA(ZSC-D),(b) ZnFe₂O₄@SiO₂@CS-DTPA( ZSC-P)

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图 2 ZSC-D、ZSC-P的XRD光谱图

Figure 2. XRD patterns of ZSC-D and ZSC-P

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图 3 ZSC-D、ZSC-P的红外光谱图

Figure 3. FT-IR spectra of ZSC-D and ZSC-P

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图 4 ZSC-D、ZSC-P的N₂吸附-解析等温线

Figure 4. N₂ adsorption-resolution isotherms of ZSC-D and ZSC-P

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图 5 竞争阳离子对ZSC-D、ZSC-P吸附U (Ⅵ)的影响

Figure 5. Effects of competing cations on the adsorption of U (VI) by ZSC-D and ZSC-P

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图 6 溶液pH对ZSC-D、ZSC-P吸附U (Ⅵ)的影响

Figure 6. Effect of solution pH on the adsorption of U (VI) by ZSC-D and ZSC-P

q_e—Equilibrium adsorption capacity

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图 7 ZSC-D、ZSC-P的Zeta电位

Figure 7. Zeta potential of ZSC-D and ZSC-P

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图 8 ZSC-D、ZSC-P吸附U (Ⅵ)的动力学曲线(a)；ZSC-D、ZSC-P吸附U (Ⅵ)的准一级动力学拟合曲线(b)；ZSC-D、ZSC-P吸附U (Ⅵ)的准二级动力学拟合曲线(c)

Figure 8. Kinetic curves of ZSC-D and ZSC-P adsorption of U (VI) (a); quasi-primary kinetic fitting curves of ZSC-D and ZSC-P adsorption of U (VI) (b); quasi-secondary kinetic fitting curves of ZSC-D and ZSC-P adsorption of U (VI) (c)

t—Adsorption time, q_t—Adsorption capacity at time t

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图 9 温度对ZSC-D、ZSC-P吸附U (Ⅵ)的影响(a)；热力学模型拟合曲线(b)

Figure 9. Effect of temperature on the adsorption of U (Ⅵ) on ZSC-D and ZSC-P (a);thermodynamic model fitting curve (b)

T—temperature

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图 10 ZSC-D、ZSC-P吸附U (Ⅵ)的吸附等温线(a)；ZSC-D、ZSC-P吸附U (Ⅵ)的Freundlich模型拟合曲线(b)；ZSC-D、ZSC-P吸附U (Ⅵ)的Langmuir模型拟合曲线(c)

Figure 10. Adsorption isotherms of ZSC-D and ZSC-P adsorption of U (VI) (a); Freundlich model fitting curves of ZSC-D and ZSC-P adsorption of U (VI) (b); Langmuir model fitting curves of ZSC-D and ZSC-P adsorption of U (VI) (c)

C_e— Equilibrium concentration of the U (Ⅵ) solution

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图 11 ZSC-D、ZSC-P吸附U (Ⅵ)的循环实验

Figure 11. Cycling experiment of U (VI) adsorption by ZSC-D and ZSC-P

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图 12 XPS分析图谱(a) ZSC-P和(b) ZSC-D吸附U (VI)之后的高分辨率U 4f，ZSC-P吸附U (VI)前后的(c)O 1s和(d)N 1s，ZSC-D吸附U (VI)前后的(e) O 1s和(f) N 1s

Figure 12. XPS analysis profiles of (a) high-resolution U 4f after adsorption of U (VI) by ZSC-P and (b) ZSC-D, (c) O 1s and (d) N 1s before and after adsorption of U (VI) by ZSC-P, (e) O 1s and (f) N 1s before and after adsorption of U (VI) by ZSC-D

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图 13 ZSC-D、ZSC-P吸附U (VI)机制图

Figure 13. ZSC-D, ZSC-P adsorption U (VI) mechanism diagrams

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表 1 ZSC-D、ZSC-P的铀吸附准一级和准二级动力学模型拟合参数

Table 1. Parameters for fitting quasi-primary and quasi-secondary kinetic modeling of uranium adsorption on ZSC-D, ZSC-P

Adsored	q_e,exp/(mg·g⁻¹)	Pseudo-first-order model			Pseudo-second-order model
Adsored	q_e,exp/(mg·g⁻¹)	q_1,cal/(mg·g⁻¹)	k₁/(min⁻¹)	R²	q_2,cal/(mg·g⁻¹)	k₂/(g·mg⁻¹·min⁻¹)	R²
ZSC-D	123.37	1.76	0.01	0.82	123.30	0.01	1
ZSC-P	123.11	2.37	0.01	0.8161	123.12	0.01	0.9999
Notes：q_e is the equilibrium adsorption capacity of the adsorption reaction；q_t is the adsorption capacity at time t；k₁、k₂ is Kinetic constants for quasi-primary and quasi-secondary kinetic models

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表 2 复合材料等温吸附模型拟合参数

Table 2. Composite isothermal adsorption model fitting parameters

Adsorbent	Langmuir isotherm			Freundlich isotherm
ZSC-D	K_L/(L·mg⁻¹)	q_m/(mg·g⁻¹)	R²	K_F/(mg·g⁻¹)	n	R²
ZSC-D	−50008	−1149.19	−0.0908	46.5125	0.9422	0.9908
ZSC-D	K_L/(L·mg⁻¹)	q_m/(mg·g⁻¹)	R²	K_F/(mg·g⁻¹)	n	R²
ZSC-D	0.00028	497.51	0.2286	62.1985	1.0834	0.9797
Notes: q_m is theoretical maximum adsorption capacity of adsorbent; K_L is Langmuir adsorption constant; K_F is Freundlich adsorption constant; n is Dimensionless parameter; R² is Correlation coefficients between adsorption processes and models;

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