MXene/SA凝胶微球的制备及对U(VI)的吸附性能

李仕友; 胡俊毅; 贺俊钦; 汪杨; 乔记帅; 王国华

doi:10.13801/j.cnki.fhclxb.20211116.003

MXene/SA凝胶微球的制备及对U(VI)的吸附性能

doi: 10.13801/j.cnki.fhclxb.20211116.003

李仕友^{1, 2},
胡俊毅¹,
贺俊钦¹,
汪杨¹,
乔记帅¹,
王国华^{1, 2, ,}

1.
南华大学　土木工程学院，衡阳 421001
2.
南华大学　污染控制与资源化技术湖南省重点实验室，衡阳 421001

基金项目: 国家自然科学基金(51904155)；湖南省自然科学基金(2022JJ30490)

详细信息

通讯作者:
王国华，博士，副教授，硕士生导师，研究方向为放射性污染治理与资源化　E-mail: wghcsu@163.com

中图分类号: TB333
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- 被引次数: 0
出版历程
- 收稿日期: 2021-09-16
- 修回日期: 2021-10-27
- 录用日期: 2021-10-31
- 网络出版日期: 2021-11-17
- 刊出日期: 2022-08-22

Preparation of MXene/SA gel microspheres and its adsorption performance for U(VI)

LI Shiyou^{1, 2},
HU Junyi¹,
HE Junqin¹,
WANG Yang¹,
QIAO Jishuai¹,
WANG Guohua^{1, 2
, ,}

1.
School of Civil Engineering, University of South China, Hengyang 421001, China
2.
Hunan Provincial Key Laboratory of Pollution Control and Resources Technology, University of South China, Hengyang 421001, China

摘要

摘要: 为了提高纳米材料MXene的吸附能力和可回收性，采用离子交联法将海藻酸钠(SA)和MXene混合，使Ti₃C₂T_xMXene纳米材料固定在SA凝胶基质上，经冷冻干燥后制备了MXene/SA凝胶微球。通过SEM-EDS、FTIR和XPS对凝胶微球结构进行了表征，并考察了不同因素影响下MXene/SA凝胶微球对水溶液中铀(VI)的吸附特性，并探究了其循环再生能力。结果表明，MXene/SA凝胶微球对铀吸附过程遵循拟二级动力学和Langmuir等温吸附模型，说明该吸附主要为单分子层化学吸附，且热力学参数表明其吸附过程是一个自发吸热的过程。在pH为4，温度为298 K时，MXene/SA凝胶微球对铀的最大吸附量为126.82 mg·g⁻¹，其主要吸附机制是离子交换与络合作用。更重要的是该凝胶微球经5次循环后，去除率仍然保持在90%以上，说明吸附剂具有回收再生利用性能，且不会造成水环境的二次污染。因此，MXene/SA凝胶微球吸附剂在修复放射性核素铀废水污染方面表现出巨大潜力。
- MXene /
- 海藻酸钠 /
- 凝胶微球 /
- 铀 /
- 吸附性能
Abstract: In order to improve the adsorption capacity and recyclability of the nanomaterial MXene, sodium alginate (SA) and MXene were mixed by ion cross-linking method to fix the Ti₃C₂T_xMXene nanomaterial on the SA aerogel matrix. After freeze-drying, MXene/SA gel microspheres was prepared. The structure of the gel microspheres was characterized by SEM-EDS, FTIR and XPS, and the adsorption characteristics of MXene/SA gel microspheres to uranium (VI) in aqueous solution were investigated under the influence of different factors, and its recycling ability was explored. The results show that the adsorption of uranium by MXene/SA gel microspheres follows the pseudo-second-order kinetics and Langmuir isotherm adsorption model, indicating that the adsorption is mainly monolayer chemical adsorption, and the thermodynamic parameters indicate that the adsorption process is a spontaneous endothermic. When the pH is 4 and the temperature is 298 K, the maximum adsorption capacity of MXene/SA gel microspheres for uranium is 126.82 mg·g⁻¹. The main adsorption mechanism is ion exchange and complexation. More importantly, after 5 cycles of the gel microspheres, the removal rate remains above 90%, indicating that the adsorbent has the performance of recycling and reuse and will not cause secondary pollution to the water environment. Therefore, MXene/SA gel microsphere adsorbent has shown great potential in repairing the pollution of radionuclide uranium wastewater.
- MXene /
- sodium alginate /
- gel microspheres /
- uranium /
- adsorption performance

HTML全文

图 1 MXene/海藻酸钠(SA)凝胶微球主要制备步骤

Figure 1. Main preparation steps of MXene/sodium alginate (SA) gel microspheres

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图 2 Ti₃C₂T_x(a)、SA凝胶微球 (b)、MXene/SA凝胶微球吸附U(VI)前 (c) 和吸附后 (d) 的SEM图像；MXene/SA凝胶微球吸附U(VI)前 (e) 和吸附后 (f) 的EDS图谱

Figure 2. SEM images of Ti₃C₂T_x (a), SA gel microspheres (b), MXene/SA gel microspheres before (c) and after (d) adsorption; EDS patterns of MXene/SA gel microspheres before (e) and after (f) adsorption

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图 3 Ti₃C₂T_x、SA凝胶微球及MXene/SA凝胶微球吸附前后的FTIR图谱

Figure 3. FTIR spectra of Ti₃C₂T_x, SA gel microspheres and MXene/SA gel microspheres before and after adsorption

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图 4 MXene/SA和MXene/SA-U(VI)的全谱图 (a)、 U4f光谱图 (b)、 Ca2p光谱图 (c)、 C1s光谱图 (d)、 O1s光谱图 (e)

Figure 4. MXene/SA and MXene/SA-U(VI) full spectrum (a), U4f spectrum (b), Ca2p spectrum (c), C1s spectrum (d),O1s spectrum (e)

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图 5 不同配比MXene/SA吸附剂对U(VI)的吸附容量对比

Figure 5. Comparison of MXene/SA adsorption capacity of different ratio adsorbents for U(VI)

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图 6 (a) 不同pH值下U(VI)形态分布曲线图；(b) 不同pH值下MXene/SA对U(VI)吸附性能的影响； (c) 不同硝酸钠离子强度下对MXene/SA吸附U(VI)的影响

Figure 6. (a) U(VI) morphology distribution curves at different pH values; (b) Effect of MXene/SA on the adsorption performance of U(VI) at different pH values; (c) Effect of adsorption U(VI) of MXene/SA adsorbent under different sodium nitrate ionic strength

C₀—Initial U(VI) concentration

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图 7 不同MXene/SA投加量吸附U(VI)的影响

Figure 7. Influence of different MXene/SA dosage on the adsorption of U(VI)

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图 8 (a) 接触时间对MXene/SA凝胶微球吸附不同浓度U(VI)的影响；(b) 拟一级动力学模型拟合曲线； (c) 拟二级动力学模型拟合曲线；(d) 颗粒内扩散模型拟合曲线

Figure 8. (a) Influence of contact time on the adsorption of different concentrations of U(VI) by MXene/SA gel microspheres; (b) Quasi-first-order adsorption kinetic model fitting curves; (c) Quasi-second-order adsorption kinetic model fitting curves; (d) Intra-particle diffusion model fitting curves

q_t—Adsorption capacity at time t; q_e—Equilibrium adsorption capacity; t—Adsorption time

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图 9 (a) MXene/SA吸附 U(VI)的非线性等温模型拟合；(b) lnK_L与 1/T 的关系图

Figure 9. (a) Fitting of nonlinear isothermal model of MXene/SA adsorption of U(VI); (b) Relationship between lnK_L and 1/T

q_e—Equilibrium adsorption capacity; C_e—Uranium concentration at adsorption equilibrium; K_L—Langmuir coefficient related to the affinity of binding site; T—Temperature

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图 10 MXene/SA吸附剂循环再生实验

Figure 10. MXene/SA adsorbent cycle regeneration test

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表 1 MXene/SA凝胶微球对U(VI)的吸附动力学参数

Table 1. The adsorption kinetic parameters of U(VI) on MXene/SA gel microspheres

C₀/(mg·L⁻¹)		5	10	15
q_e,exp/(mg·g⁻¹)		9.7	19.28	28.5
Pseudo-first-order model	k₁/min⁻¹	0.018	0.016	0.014
	q_e,cal/(mg·g⁻¹)	9.851	19.426	28.509
	R²	0.877	0.853	0.975
Pseudo-second-order model	k₂/min⁻¹	0.002	0.001	0.001
	q_e,cal/(mg·g⁻¹)	11.072	21.966	32.783
	R²	0.997	0.995	0.996
Intraparticle diffusion model	k_1p/(mg·(g·min^0.5)⁻¹)	0.872	1.745	2.459
	C₁	−0.774	−2.069	−3.352
	R₁²	0.997	0.942	0.930
	k_2p/(mg·(g·min^0.5)⁻¹)	0.126	0.529	1.010
	C₂	7.746	11.207	11.764
	R₂²	0.720	0.665	0.963
	k_3p/(mg·(g·min^0.5)⁻¹)	0.028	0.020	0.075
	C₃	9.203	18.856	26.896
	R₃²	0.652	0.575	0.590
Notes: q_e,exp—Calculated amount of adsorption equilibrium; q_e,cal—Actual amount of adsorption equilibrium; k₁ and k₂—First order rate constant and second order rate constant, respectively; k_p1, k_p2, k_p3—Particle diffusion constant; R²—Correlation coefficient.

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表 2 Langmuir和Freundlich吸附等温线模型的相关参数

Table 2. Related parameters of Langmuir and Freundlich adsorption isotherm simulation

T/K	Langmuir isotherm			Freundlich isotherm
T/K	q_max/(mg·g⁻¹)	K_L/(L·mg⁻¹)	R²	K_F/(L·mg⁻¹)	n	R²
288	150.382	0.273	0.994	38.123	0.147	0.991
298	154.309	0.373	0.984	43.581	0.241	0.974
308	159.031	0.539	0.975	57.381	0.300	0.963
Notes: q_max—Adsorption capacity per unit mass of the adsorbent; K_L—Langmuir coefficient related to the affinity of binding site; K_F and n—Constants that are related to the adsorption capacity and the adsorption intensity, respectively.

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表 3 MXene/SA吸附U(VI)的热力学参数

Table 3. Thermodynamic parameters of MXene/SA adsorption of U(VI)

T/K	lnK_e	ΔG⁰/(kJ·mol⁻¹)	ΔH⁰/(kJ·mol⁻¹)	ΔS⁰/(J·(mol·K)⁻¹)
288	3.59	−8.60	21.07	103.18
298	3.95	−9.79
308	4.16	−10.65
Notes: T—Thermodynamic temperature; K_e—Equilibrium constant at different temperatures; ΔH⁰—Standard enthalpy change; ΔG⁰—Standard free energy change; ΔS⁰—Standard entropy change.

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