MnO2/Ti3C2TX复合剂对水中U (VI)的吸附性能与机制

周国霖; 谢水波; 胡恋

MnO₂/Ti₃C₂T_X复合剂对水中U (VI)的吸附性能与机制

周国霖¹,
谢水波^{1, 2, ,},
胡恋³

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
3.
湖南省农林工业勘察设计研究总院, 长沙410007

基金项目: 国家自然科学基金(11475080)；湖南省自然科学基金(2021JJ30579)

详细信息

通讯作者:
谢水波，博士，教授，博士生导师，研究方向为水处理理论与技术、环境模拟与污染控制　E-mail：xiesbmr@263.net

中图分类号: TQ424;X703;TB332
计量
- 文章访问数: 81
- HTML全文浏览量: 62
- 被引次数: 0
出版历程
- 收稿日期: 2023-12-20
- 修回日期: 2024-01-18
- 录用日期: 2024-01-19
- 网络出版日期: 2024-03-02

Adsorption performance and mechanism of MnO₂/Ti₃C₂T_X composite towards U(VI) in water

ZHOU guolin¹,
XIE shuibo^{1, 2
, ,},
HU lian³

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
3.
Hunan prospecting designing & research general institute for agriculture forestry & industry , Changsha 410007, China

Funds: National Natural Science Foundation of China (No.11475080); General program of Hunan Natural Science Foundation (No.2021JJ30579)

摘要

摘要: 针对Ti₃C₂T_X纳米片层易堆叠和吸附位点少的不足，采用水热法制备了MnO₂/Ti₃C₂T_X复合剂。通过单因素试验探讨铀的初始浓度、投加量、pH值、时间和共存离子对其吸附U(VI)的影响，利用现代表征手段分析MnO₂/Ti₃C₂T_X的表面性质及吸附U(VI)的作用机制。试验结果表明：在U(VI)初始浓度5 mg·L⁻¹、MnO₂/Ti₃C₂T_X投加量为0.1 g·L⁻¹、温度303 K、pH值为6时，30 s内U(VI)浓度降至0.41 mg·L⁻¹，30 min后吸附达到平衡，其对U(VI)的吸附率达99.15%，吸附容量为49.58 mg·g⁻¹。经过5次循环后，MnO₂/Ti₃C₂T_X对U(VI)的吸附效率仍保持在96.3%，具有良好的可再生利用性。整个吸附过程为自发吸热过程，符合拟二级动力学模型和Freundlich等温线模型。BET分析表明MnO₂/Ti₃C₂T_X的比表面积达318.3 m²·g⁻¹，较Ti₃C₂T_X高55.9倍。FTIR和XPS分析表明MnO₂/Ti₃C₂T_X对U(VI)吸附主要是表面含氧基团与铀的配位络合。
- Ti₃C₂T_X /
- MXene /
- 二氧化锰 /
- 吸附 /
- 铀
Abstract: To address the shortcomings of Ti₃C₂T_X nanosheets, which tend to stack and have limited adsorption sites, a MnO₂/Ti₃C₂T_X composite was prepared using the hydrothermal method. The influence of uranium initial concentration, dosage, pH, time, and interfering ions on U(VI) adsorption was investigated through single-factor adsorption experiments. Modern characterization techniques were employed to analyze the surface properties of MnO₂/Ti₃C₂T_X and the mechanism of U(VI) adsorption. Experimental results revealed that with an initial U(VI) concentration of 5 mg·L⁻¹, MnO₂/Ti₃C₂T_X dosage of 0.1 g·L⁻¹, and a temperature of 303 K, pH of 6, the U(VI) concentration dropped to 0.41mg·L⁻¹ within 30 seconds. Adsorption equilibrium was reached after 30 minutes, with an adsorption rate of 99.15% and an adsorption capacity of 49.58 mg·g⁻¹. After five cycles, the adsorption efficiency of MnO₂/Ti₃C₂T_X remained at 96.3%, demonstrating its potential for regeneration and reuse.The entire adsorption process was endothermic and spontaneous, fitting the pseudo-second-order kinetic model and the Freundlich isotherm model. BET analysis showed that the specific surface area of MnO₂/Ti₃C₂T_X reached 318.3 m²·g⁻¹, which is 55.9 times higher than that of Ti₃C₂T_X. FTIR and XPS analyses indicated that the primary mechanism of U(VI) adsorption on MnO₂/Ti₃C₂T_X is the coordination complexation between surface oxygen-containing groups and uranium.
- Ti₃C₂T_X /
- MXene /
- MnO₂ /
- adsorption /
- U(VI)

HTML全文

图 2 MnO₂/Ti₃C₂T_X的N₂吸附-解吸等温线和孔径分布图

Figure 2. N₂ adsorption-desorption isothermal curves of MnO₂/Ti₃C₂T_x with inserted BJH pore size distribution

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图 3 Ti₃AlC₂、Ti₃C₂、MnO₂和MnO₂/ Ti₃C₂T_X的XRD光谱图

Figure 3. XRD spectra of Ti₃AlC₂,Ti₃C₂,MnO₂ and MnO₂/ Ti₃C₂T_X

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图 4 Ti₃C₂T_X、MnO₂、MnO₂/ Ti₃C₂T_x和MnO₂/ Ti₃C₂T_X吸附铀后的FTIR光谱图

Figure 4. FTIR spectra of Ti₃C₂T_X, MnO₂, MnO₂/ Ti₃C₂T_X and MnO₂/ Ti₃C₂T_X adsorbed uranium

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图 5 MnO₂/ Ti₃C₂T_X吸附U(VI)前后XPS全谱图(a)、U 4 f光谱图(b)、Mn 2 p光谱图(c)、Mn 3 s光谱图(d)、O 1 s光谱图(e)

Figure 5. MnO₂/ Ti₃C₂T_X and MnO₂/ Ti₃C₂T_x-U (a) full spectrum,(b) U 4 f spectrum,(c) Mn 2 p spectrum,(d) Mn 3 s spectrum,(e) O 1 s spectrum

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图 6 MnO₂/Ti₃C₂T_X不同质量比对U(VI)的吸附效果对比

Figure 6. Comparison of adsorption effects of MnO₂/Ti₃C₂T_X with different mass ratios on U (VI)

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图 7 (a)不同pH值下U(VI)形态分布图，8 (b)不同pH值下MnO₂/Ti₃C₂T_X对U(VI)吸附的影响Fig. 8(a) U(VI) morphology distribution curve at different pH values,8(b) The effect of MnO₂/Ti₃C₂T_X on the adsorption performance of U(VI) at different pH values

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图 8 投加量对MnO₂/Ti₃C₂T_X吸附U(VI)的影响

Figure 8. The influence of different MnO₂/Ti₃C₂T_X dosage on the adsorption of U(VI)

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图 9 共存离子对 MnO₂/Ti₃C₂T_X吸附U(VI)的影响

Figure 9. The effect of coexisting ions on the adsorption of U (VI) by MnO₂/Ti₃C₂T_X

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图 10 (a)吸附时间对MnO₂/Ti₃C₂T_X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 10. (a) Effect of adsorption time on MnO₂/Ti₃C₂T_X adsorption of different concentrations of U (VI); (b) the fitting curve of pseudo-first-order kinetic model; (c) the fitting curve of quasi-second-order kinetic model; (d) the fitting curve of intra-particle diffusion model

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

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图 11 (a)不同温度下MnO₂/Ti₃C₂T_X对U(VI)的吸附等温线；Langmuir和Freundlich吸附等温模型的拟合：(b)293 K，(c)303 K，(d)313 KFig 12(a) Adsorption isotherms of MnO₂/Ti₃C₂T_X for U(VI) at different temperatures. Langmuir and Freundlich fitting curves of MnO₂/Ti₃C₂T_X adsorption of U(VI)：(b)293 K, (c)303 K, (d)313 K

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图 12 MnO₂/Ti₃C₂T_X吸附铀的lnK_d和T⁻¹线性拟合

Figure 12. Linear fitting of lnK_d vs T⁻¹ for MnO₂/Ti₃C₂T_X adsorption of U(VI)

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图 13 循环次数对MnO₂/Ti₃C₂T_X吸附U(VI)的影响

Figure 13. Effect of cycle times on MnO₂/Ti₃C₂T_X adsorption of U(VI)

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表 1 MnO₂/ Ti₃C₂T_x与其他吸附剂比表面积对比

Table 1. Comparison of BET surface area between MnO₂/ Ti₃C₂T_x and other adsorbents

Adsorbent	BET surface area/(m²·g⁻¹)	Pore size/ nm	References
Ti₃C₂T_x	5.6	18.1	Zeng etal^[17] (2021)
MnO₂/TiO₂	73.2	5.7	Ma etal^[18] (2019)
LDHs-Ti₃C₂T_x	49.2	7.4	Gu etal^[19] (2022)
MnO₂/ Ti₃C₂T_x	318.3	6.6	This work
Notes: LDHs-Layered double hydroxides

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表 2 MnO₂/Ti₃C₂T_X吸附U(VI)的动力学模型参数

Table 2. Kinetic model parameters of uranium adsorption by MnO₂/Ti₃C₂T_X

C₀/(mg·L⁻¹)	q_e.exp/(mg·g⁻¹)	Pseudo- first Kinetics model			Pseudo- second Kinetics model
C₀/(mg·L⁻¹)	q_e.exp/(mg·g⁻¹)	K₁	q_e.cal	R²	K₂	q_e.cal	R²
5	49.792	0.085	1.923	0.687	0.020	49.751	1
10	99.112	0.099	8.575	0.893	0.010	99.010	1
15	146.825	0.064	24.016	0.972	0.007	147.059	0.999
Notes: q_e is the adsorption capacity at equilibrium time; K₁ and K₂ are reaction rate constants of pseudo-first-order and pseudo-second-order equations, respectively; R² is the correlation coefficient.

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表 3 MnO₂/Ti₃C₂T_X吸附等温线模型的相关参数

Table 3. Relevant parameters of MnO₂/Ti₃C₂T_X adsorption isotherm model

T/K	Langmuir			Freundlich
T/K	q_max/(mg·g⁻¹)	b	R²	K_F	n	R²
293	372.801	0.853	0.933	162.314	3.058	0.994
303	380.414	1.157	0.941	176.716	3.139	0.994
313	434.837	0.717	0.936	196.977	3.145	0.992
Notes: q_max is Adsorption capacity per unit mass of the adsorbent; b is Langmuir coefficient related to the affinity of binding site; KF , n-Constants that are related to the adsorption capacity and the adsorption intensity, respectively.

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表 4 MnO₂/Ti₃C₂T_X吸附U(VI)性能与其他吸附剂对比

Table 4. Comparison of MnO₂/Ti₃C₂T_X adsorption performance for U (VI) with other adsorbents

Adsorbent	pH	Temperature/K	Equilibrium time/min	Maximum adsorption capacity /(mg·g⁻¹)	References
MnO₂@BBC	5	298	240	97.40	Chen etal^[33](2022)
HPC/POSS-OH modified MXene	5	298	90	307.67	Zhao etal^[34](2022)
Chloroacetic acid modified Ti₃C₂T_X	5	308	150	165.43	Xie etal^[35](2022)
γ-Fe₂O₃/CSS	6	298	120	214.1	Fan etal^[36](2022)
Ti₃C₂@FeS-PDA/PEI	6	298	240	88.5	Liu etal^[37](2023)
MnO₂/ Ti₃C₂T_X	6	303	30	380.41	This work
Notes: MnO₂@BBC-MnO₂ modified bamboo-derived biochar composite;HPC/POSS-OH- hydroxypropyl cellulose (HPC) and polyhedral oligomeric silsesquioxane (POSS-OH);CSS-corn stalk starch; PDA/PEI-polydopamine and polyethyleneimine

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表 5 MnO₂/Ti₃C₂T_X吸附U(VI)的热力学参数

Table 5. Thermodynamic parameters of uranium adsorption by MnO₂/Ti₃C₂T_X

∆G⁰/(kJ·mol⁻¹)			∆H⁰/(kJ·mol⁻¹)	∆S⁰/(kJ·mol⁻¹)
293 K	303 K	313 K	21.073	119.551
−14.014	−15.038	−16.406	21.073	119.551
Notes: ΔG⁰ −Standard free energy change; ΔH⁰ −Standard enthalpy change; ΔS⁰ −Standard entropy change.

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