酰胺基两性分子对二硫化钨吸附铀容量的影响机制

赵家印; 柳玉辉; 王子鸣; 唐梦; 卢雅宁; 张爽; 王英财; 刘云海; 邓圣

doi:10.12153/j.issn.1674-991X.20220498

酰胺基两性分子对二硫化钨吸附铀容量的影响机制

doi: 10.12153/j.issn.1674-991X.20220498

赵家印^{1, 2,},
柳玉辉^{1, 2, ,},
王子鸣^{1, 2},
唐梦^{1, 2},
卢雅宁^{1, 2},
张爽¹,
王英财^{1, 2},
刘云海¹,
邓圣^3, ,

1.
核资源与环境国家重点实验室, 东华理工大学
2.
东华理工大学核科学与工程学院
3.
国家环境保护地下水污染模拟与控制重点实验室, 中国环境科学研究院

基金项目: 国家自然科学基金地区科学基金项目（22266003）；国家自然科学基金青年基金项目（22006013）；江西省主要学科学术和技术带头人培养计划青年人才项目（20225BCJ23020）

详细信息

作者简介:
赵家印（1999—），男，硕士，主要从事核燃料循环与材料研究，zjyecut@163.com

通讯作者:
柳玉辉（1986—），女，副教授，博士，主要从事放射化学与环境化学的研究，liuyuhui@ecut.edu.cn

邓圣(1989—)，男，副研究员，博士，主要从事环境功能材料与技术开发，ds_hit@163.com

中图分类号: X703
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出版历程
- 收稿日期: 2022-05-20

Influence mechanism of amide-based amphoteric molecules on uranium adsorption capacity of WS₂

ZHAO Jiayin^{1, 2
,},
LIU Yuhui^{1, 2
, ,},
WANG Ziming^{1, 2},
TANG Meng^{1, 2},
LU Yaning^{1, 2},
ZHANG Shuang¹,
WANG Yingcai^{1, 2},
LIU Yunhai¹,
DENG Sheng^{3
, ,}

1.
State Key Laboratory of Nuclear Resources and Environment, East China University of Technology
2.
School Nuclear Science and Engineering, East China University of Technology
3.
State Environmental Protection Key Laboratory of Simulation and Control of Groundwater Pollution, Chines Research Academy of Environmental Sciences

摘要

摘要:
含铀废水中铀的回收主要是基于材料与[UO₂(H₂O)₅]²⁺中UO₂ ²⁺之间的络合，但H₂O的电偶极矩对络合有显著弱化作用。采用酰胺基两性分子N,N-二甲基-9-癸烯酰胺（NADA）氢键作用与[UO₂(H₂O)₅]²⁺形成UO₂[(H₂O)_xC₁₂H₂₃NO]_n ^*（x<5，UO₂-Coordination Compound，简称UO₂-CC），选取惰性物质WS₂为吸附材料，通过静态吸附试验（不同pH、接触时间、浓度和温度）分别研究其对UO₂ ²⁺和UO₂-CC的吸附量。动力学拟合结果表明，二者的吸附反应是化学吸附过程，UO₂ ²⁺经NADA重构后，吸附时间从240 min缩短至180 min，准二级动力学吸附常数提高1.35倍。等温吸附研究结果表明，WS₂与UO₂-CC络合过程符合Langmuir吸附等温模型，且NADA的加入使吸附由自发吸热过程转变为自发放热过程，吸附反应过程有序度增加。NADA原位重构[UO₂(H₂O)₅]²⁺后，WS₂对UO₂ ²⁺的平衡吸附量由45.03 mg/g（WS₂/UO₂ ²⁺体系）提高到122.14 mg/g（WS₂/UO₂-CC体系）。采用光谱分析（X射线光电子能谱法）从分子水平深入研究NADA原位重构[UO₂(H₂O)₅]²⁺后在WS₂上的吸附机制，揭示静电、氢键和U—S共价键等作用力对吸附的贡献，特别是NADA的氢键作用。
- 铀酰离子(UO₂ ²⁺) /
- 两性分子 /
- 铀酰活性位点 /
- WS₂纳米片 /
- 络合机理
Abstract:
The recovery of uranium from uranium-containing wastewater is mainly based on the complexation between the material and UO₂ ²⁺ in [UO₂(H₂O)₅]²⁺, but the electric dipole moment of H₂O has a significant weakening effect on the complexation. The amide-based amphoteric molecule N,N-dimethyl-9-decenyl amide (NADA) was used for hydrogen bonding with [UO₂(H₂O)₅]²⁺ to form UO₂[(H₂O)_xC₁₂H₂₃NO]_n ^* (x<5, UO₂-Coordination Compound was named UO₂-CC) ,Inert tungsten disulfide (WS₂) was selected as the adsorption material, and the adsorption capacities of UO₂ ²⁺ and UO₂-CC were studied by static adsorption experiments (different pH, contact time, concentration and temperature). The kinetic fitting results showed that the adsorption reaction was a chemisorption process. After NADA reconstruction, the adsorption time of UO₂ ²⁺ was shortened from 240 min to 180 min, and the quasi-second-order kinetic adsorption constant was increased by 1.35 times. The results of the isothermal adsorption study showed that the complexation process of WS₂ and UO₂-CC conformed to the Langmuir adsorption isothermal model, and the addition of NADA made the adsorption change from spontaneous endothermic process to spontaneous exothermic process, and the order degree of the adsorption reaction process increased. After in situ reconstruction of [UO₂(H₂O)₅]²⁺ by NADA, the equilibrium adsorption capacity of UO₂ ²⁺ by WS₂ increased from 45.03 mg/g (WS₂/UO₂ ²⁺ system) to 122.14 mg/g (WS₂/UO₂-CC system). Spectroscopic analysis by X-ray photoelectron spectroscopy was used to deeply study the adsorption mechanism of NADA on WS₂ after in situ reconstruction of [UO₂(H₂O)₅]²⁺ at the molecular level, and to reveal the contribution of various forces (electrostatic, hydrogen bond and U-S covalent bond) to adsorption, especially the hydrogen bond of NADA.
- uranyl ion (UO₂ ²⁺) /
- amphoteric molecules /
- uranyl active site /
- WS₂ nanosheets /
- complexation mechanism

HTML全文

图 1 WS₂、WS₂/UO₂ ²⁺体系、WS₂/UO₂-CC体系的扫描电镜图

Figure 1. Scanning electron micrographs of WS₂, WS₂/UO₂ ²⁺ system and WS₂/UO₂-CC system

下载: 全尺寸图片幻灯片

图 2 WS₂、WS₂/UO₂ ²⁺体系和WS₂/UO₂-CC体系的XRD谱图

Figure 2. X-ray diffraction pattern of WS₂, WS₂/UO₂ ²⁺ system and WS₂/UO₂-CC system

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图 3 WS₂/UO₂-CC体系的FT-IR谱图

Figure 3. FT-IR spectra of WS₂/UO₂-CC system

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图 4 WS₂、WS₂/UO₂ ²⁺和WS₂/UO₂-CC体系的静态接触角

Figure 4. Static contact angle of WS₂, WS₂/UO₂ ²⁺ and WS₂/UO₂-CC system

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图 5 不同pH下WS₂/UO₂-CC体系的平衡吸附量

Figure 5. Equilibrium adsorption capacity of WS₂/UO₂-CC system at different pH

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图 6 不同NADA添加量下WS₂/UO₂-CC体系的平衡吸附量（pH为5）

Figure 6. Equilibrium adsorption capacity of WS₂/UO₂-CC system by adding different fractions of NADA (pH=5)

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图 7 WS₂/UO₂ ²⁺和WS₂/UO₂-CC体系的动力学曲线

Figure 7. Kinetic curves of WS₂/UO₂ ²⁺ and WS₂/UO₂-CC system

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图 8 不同初始UO₂ ²⁺浓度下WS₂/UO₂ ²⁺和WS₂/UO₂-CC体系的平衡吸附量

Figure 8. Equilibrium adsorption capacity of UO₂ ²⁺ and WS₂/UO₂-CC system at different initial UO₂²⁺ concentrations

下载: 全尺寸图片幻灯片

图 9 不同温度下WS₂/UO₂ ²⁺和WS₂/UO₂-CC体系的平衡吸附量

Figure 9. Equilibrium adsorption capacity of WS₂/UO₂ ²⁺ and WS₂/UO₂-CC system at different temperatures

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图 10 WS₂/UO₂ ²⁺和WS₂/UO₂-CC体系的XPS光谱图及WS₂/UO₂-CC体系的U 4f光谱图

Figure 10. XPS spectra of WS₂/UO₂ ²⁺ and WS₂/UO₂-CC systems and U 4f spectra of WS₂/UO₂-CC system

下载: 全尺寸图片幻灯片

表 1 WS₂、WS₂/UO₂²⁺和WS₂/UO₂-CC体系中各元素含量

Table 1. Contents of elements in WS₂, WS₂/UO₂²⁺ and WS₂/UO₂-CC system %　

体系	C	N	O	S	W	U	合计
WS₂				15.57	84.43		100
WS₂/UO₂²⁺				14.35	84.06	1.59	100
WS₂/UO₂-CC	2.00	0.24	0.74	14.48	79.65	2.89	100

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表 2 WS₂/UO₂ ²⁺和WS₂/UO₂-CC体系的准一级动力学、准二级动力学参数

Table 2. Pseudo-ﬁrst-order and Pseudo-second-order kinetic parameters of WS₂/UO₂ ²⁺ and WS₂/UO₂-CC system

吸附体系	q_e/(mg/g)	准一级动力学			准二级动力学
吸附体系	q_e/(mg/g)	q₁/(mg/g)	k₁/min^-1	R²	q₂/(mg/g)	k₂/〔mg/(g·min)〕	R²
WS₂/UO₂ ²⁺	46.10	28.83	0.009 0	0.961	47.64	0.000 846	0.997 4
WS₂/UO₂-CC	122.20	45.90	0.014 7	0.988	123.94	0.001 140	0.999 7

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表 3 WS₂/UO₂ ²⁺和WS₂/UO₂-CC体系的Langmuir吸附等温模型、Freundlich吸附等温模型参数

Table 3. Langmuir adsorption isothermal model and Freundlich adsorption isothermal model parameters of WS₂/UO₂ ²⁺ and WS₂/UO₂-CC system

吸附体系	Langmuir模型			Freundlich模型
吸附体系	K_L	q_m/(mg/g)	R²	K_F	n	R²
WS₂/UO₂ ²⁺	0.027	37.40	0.985	5.23	1.91	0.974
WS₂/UO₂-CC	0.018	129.86	0.997	20.33	2.21	0.922

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表 4 WS₂/UO₂ ²⁺和WS₂/UO₂-CC体系的D-R吸附等温模型参数

Table 4. D-R adsorption isothermal model parameters of WS₂/UO₂ ²⁺ and WS₂/UO₂-CC system

吸附体系	q_D-R/(mg/g)	β/(mol²/kJ²)	E_D-R/(kJ/mol)	R²
WS₂/UO₂ ²⁺	0.001 3	0.004 8	10.24	0.982
WS₂/UO₂-CC	0.003 5	0.004 6	10.47	0.934
注：E_D-R为吸附平均自由能，kJ/mol。$E_{ {\rm{D} }{\text -}{\rm{R} } }=1/\sqrt{2\beta}$。

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表 5 WS₂/UO₂ ²⁺和WS₂/UO₂-CC体系的热力学参数

Table 5. Thermodynamic parameters of WS₂/UO₂ ²⁺ system and WS₂/UO₂-CC system

吸附体系	ΔG/(kJ/mol)					ΔH/(kJ/mol)	ΔS/〔J/(mol·K)〕
吸附体系	278.15 K	288.15 K	198.15 K	308.15 K	318.15 K	ΔH/(kJ/mol)	ΔS/〔J/(mol·K)〕
WS₂/UO₂ ²⁺	−14.45	−15.47	−16.50	−17.53	−18.55	14.08	102.50
WS₂/UO₂-CC	−18.82	−19.46	−20.09	−20.73	−21.36	−1.16	63.50

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酰胺基两性分子对二硫化钨吸附铀容量的影响机制

doi: 10.12153/j.issn.1674-991X.20220498

作者简介:
赵家印（1999—），男，硕士，主要从事核燃料循环与材料研究，zjyecut@163.com

通讯作者:
柳玉辉（1986—），女，副教授，博士，主要从事放射化学与环境化学的研究，liuyuhui@ecut.edu.cn

邓圣(1989—)，男，副研究员，博士，主要从事环境功能材料与技术开发，ds_hit@163.com

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Influence mechanism of amide-based amphoteric molecules on uranium adsorption capacity of WS₂

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留言板

酰胺基两性分子对二硫化钨吸附铀容量的影响机制

doi: 10.12153/j.issn.1674-991X.20220498

作者简介: 赵家印（1999—），男，硕士，主要从事核燃料循环与材料研究，zjyecut@163.com

通讯作者: 柳玉辉（1986—），女，副教授，博士，主要从事放射化学与环境化学的研究，liuyuhui@ecut.edu.cn 邓圣(1989—)，男，副研究员，博士，主要从事环境功能材料与技术开发，ds_hit@163.com

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出版历程

Influence mechanism of amide-based amphoteric molecules on uranium adsorption capacity of WS2

计量

出版历程

目录

作者简介:
赵家印（1999—），男，硕士，主要从事核燃料循环与材料研究，zjyecut@163.com

通讯作者:
柳玉辉（1986—），女，副教授，博士，主要从事放射化学与环境化学的研究，liuyuhui@ecut.edu.cn

邓圣(1989—)，男，副研究员，博士，主要从事环境功能材料与技术开发，ds_hit@163.com

Influence mechanism of amide-based amphoteric molecules on uranium adsorption capacity of WS₂