功能化多孔氮化碳材料对铀的吸附性能研究

doi:10.11949/0438-1157.20231276

化工学报 ›› 2024, Vol. 75 ›› Issue (4): 1616-1629.DOI: 10.11949/0438-1157.20231276

功能化多孔氮化碳材料对铀的吸附性能研究

孟园¹^,²(), 倪善²(), 刘亚锋²^,³, 王文杰²^,³, 赵越²^,³, 朱育丹¹, 杨良嵘²^,³()

^1.南京工业大学化工学院材料化学工程国家重点实验室，江苏南京 211816
^2.中国科学院过程工程研究所盐湖资源绿色高值利用重点实验室，石油化工分子转化与反应工程全国重点实验室，中国科学院绿色过程与工程重点实验室，北京 100190
^3.中国科学院大学化学工程学院，北京 100049

收稿日期:2023-12-04 修回日期:2024-01-12 出版日期:2024-04-25 发布日期:2024-06-06
通讯作者: 倪善,杨良嵘
作者简介:孟园（1998—），男，硕士研究生，mengy925@163.com
基金资助:
国家重点研发计划项目(2021YFC2901500);国家自然科学基金项目(22138012);中国科学院稳定支持基础研究领域青年团队项目(YSBR-038);中国科学院青年创新促进会优秀会员项目(Y202014);中国博士后科学基金项目(2023M733521)

Adsorption properties of functionalized porous carbon nitride materials for uranium

Yuan MENG¹^,²(), Shan NI²(), Yafeng LIU²^,³, Wenjie WANG²^,³, Yue ZHAO²^,³, Yudan ZHU¹, Liangrong YANG²^,³()

^1.State Key Laboratory of Materials-Oriented Chemical Engineering, College of Chemical Engineering, Nanjing Tech University, Nanjing 211816, Jiangsu, China
^2.Key Laboratory of Green and High-end Utilization of Salt Lake Resources, State Key Laboratory of Petroleum Molecular & Process Engineering (RIPP, SINOPEC), CAS Key Laboratory of Green Process and Engineering, Institute of Process Engineering, Chinese Academy of Sciences, Beijing 100190, China
^3.School of Chemical Engineering, University of Chinese Academy of Sciences, Beijing 100049, China

Received:2023-12-04 Revised:2024-01-12 Online:2024-04-25 Published:2024-06-06
Contact: Shan NI, Liangrong YANG

摘要/Abstract

摘要：

从海水和废水中分离和富集铀对能源的可持续发展和保护环境具有重要意义。通过一步碱化和热缩聚三聚氰胺制备了一种富含氰基和羟基的多孔氮化碳吸附剂（d-g-CN），研究其对铀的吸附性能。吸附实验结果表明，在pH=6.0和298 K的条件下，d-g-CN对铀的吸附在3 h达到吸附平衡，饱和吸附容量为2476.23 mg∙g^-1。吸附过程符合拟二级动力学模型和Freundlich等温模型。此外，d-g-CN具有优异的选择性和循环性，在溶液中存在多种竞争离子时，d-g-CN对铀的吸附分配系数达到1.48×10⁴ ml∙g^-1，并且6次循环后吸附效率仍保持在89.5%。由于d-g-CN较大的比表面积提供了更多的吸附位点，同时氰基和羟基等功能基团与铀存在配位作用，因此d-g-CN表现出优异的吸附性能，在低浓度铀的提取方面具有一定的应用潜力。

关键词: 氮化碳, 铀, 海水, 废水, 吸附, 选择性

Abstract:

The separation and enrichment of uranium from seawater and wastewater is of great significance to the sustainable development of energy and environmental protection. A porous carbon nitride adsorbent (d-g-CN) rich in cyano groups and hydroxyl groups was prepared through one-step alkalization and heat-condensation polymerization of melamine, and its adsorption performance for uranium was studied. The results of adsorption experiments showed that under the conditions of pH=6.0 and 298 K, the adsorption of uranium by d-g-CN reached equilibrium in about 3 h, and the saturated adsorption capacity was 2476.23 mg∙g^-1. The adsorption process conformed to the pseudo second order kinetic model and Freundlich isotherm model. In addition, d-g-CN had excellent selectivity and cyclicity. When there were many competitive ions in the solution, the adsorption distribution coefficient of d-g-CN for uranium reached 1.48×10⁴ ml∙g^-1. The adsorption efficiency remained about 89.5% after six cycles. Because the large specific surface area of d-g-CN provided more adsorption sites, and functional groups of cyano and hydroxyl had coordination effect with uranium, d-g-CN showed excellent adsorption performance, and had certain application potential in the extraction of low concentration uranium.

Key words: carbon nitride, uranium, seawater, waste water, adsorption, selectivity

中图分类号:

TQ 424

孟园, 倪善, 刘亚锋, 王文杰, 赵越, 朱育丹, 杨良嵘. 功能化多孔氮化碳材料对铀的吸附性能研究[J]. 化工学报, 2024, 75(4): 1616-1629.

Yuan MENG, Shan NI, Yafeng LIU, Wenjie WANG, Yue ZHAO, Yudan ZHU, Liangrong YANG. Adsorption properties of functionalized porous carbon nitride materials for uranium[J]. CIESC Journal, 2024, 75(4): 1616-1629.

图/表 19

图1 d-g-CN的合成示意图

Fig.1 Schematic diagram of d-g-CN synthesis

图2 HD-CN、HR-CN、d-g-CN的FTIR、XRD和XPS能谱

Fig.2 FTIR, XRD, XPS spectra of HD-CN, HR-CN and d-g-CN

图3 3种吸附剂的SEM图、水接触角和d-g-CN的EDS能谱图

Fig.3 SEM images and water contact angles of three adsorbents and EDS spectra of d-g-CN

图4 HD-CN、HR-CN、d-g-CN的N2吸脱附曲线和孔径分布

Fig.4 N2 adsorption-desorption isotherms and pore size distributions of HD-CN, HR-CN and d-g-CN

表1 HD-CN、HR-CN、d-g-CN的比表面积和孔体积

Table 1 Specific surface area and pore volume of HD-CN， HR-CN and d-g-CN

吸附剂	比表面积/(m²∙g^-1)	孔体积/(cm³∙g^-1)
HD-CN	52.270	0.1587
HR-CN	120.783	0.5427
d-g-CN	131.852	0.4302

图5 不同pH下HD-CN、HR-CN、d-g-CN的吸附容量和Zeta电位

Fig.5 Effect of pH on adsorption capacity and Zeta potential of HD-CN, HR-CN and d-g-CN

图6 不同pH下铀的存在形式

Fig.6 Existing forms of uranium at different pH

图7 吸附动力学数据，d-g-CN的拟一级、拟二级动力学模型和Weber-Morris颗粒内扩散模型

Fig.7 Adsorption kinetics data, pseudo-first-order, pseudo-second-order kinetic models and Weber-Morris intraparticle diffusion model of d-g-CN

表2 d-g-CN的拟一级和拟二级动力学参数

Table 2 Pseudo-first-order and pseudo-second-order kinetic parameters of d-g-CN

拟一级动力学参数			拟二级动力学参数
k₁/min^-1	q_e/(mg∙g^-1)	R²	k₂/(g∙mg^-1∙min^-1)	q_e/(mg∙g^-1)	R²
0.03471	1332.11	0.993	0.00041	1427.96	0.999

图8 不同温度下d-g-CN的吸附等温线

Fig.8 Adsorption isotherms of d-g-CN at different temperatures

表3 Langmuir模型和Freundlich模型拟合参数

Table 3 Fitting parameters of Langmuir model and Freundlich model

温度/K	Langmuir模型			Freundlich模型
温度/K	q_m/(mg∙g^-1)	K_L/(L∙mg^-1)	R²	K_F	1/n	R²
298	2476.23	0.155	0.911	685.893	0.298	0.992
308	2709.41	0.184	0.891	768.055	0.298	0.991
318	3108.57	0.157	0.778	1030.759	0.253	0.993

表4 d-g-CN与已报道的吸附剂的性能比较

Table 4 Performance comparison between d-g-CN and reported adsorbents

吸附剂	实验条件	铀浓度/(mg∙L^-1)	最大吸附容量/(mg∙g^-1)	平衡时间/min	文献
d-g-CN	pH=6.0, m/V= 0.025 g∙L^-1, T=298 K	50	2476.23	180	本文
g-C₃N₄-550	pH=5.0, m/V = 0.2 g∙L^-1, T=298 K	10	149.7	120	[18]
AO/g-C₃N₄	pH=6.8, m/V = 0.1 g∙L^-1, T=298 K	50	312	10	[21]
IIP-g-C₃N₄/β-CD	pH=8.0, m/V = 0.5 g∙L^-1, T=298 K	200	859.66	480	[40]
g-C₃N₄/FeS	pH=6.0, m/V = 0.05 g∙L^-1, T=303 K	100	917.1	60	[41]
P-CS@CN	pH=5.0, m/V = 0.1 g∙L^-1, T=298 K	10	416.7	20	[22]
ZIF-8-CN	pH=6.0, m/V = 0.083 g∙L^-1, T=298 K	200	1000	120	[23]
COF-TpDb-AO	pH=6.0, m/V = 0.5 g∙L^-1, T=298 K	9.25	408	30	[16]
MCP-5	pH=6.0, m/V = 0.02 g∙L^-1, T=298 K	20	950.52	5	[42]

图9 d-g-CN的ln Kd相对于1/T的线性拟合图

Fig.9 Linear fitting graph of ln Kdvs 1/T of d-g-CN

表5 d-g-CN的吸附热力学参数

Table 5 Adsorption thermodynamic parameters of d-g-CN

T /K	ΔG /(kJ∙mol^-1)	ΔH /(kJ∙mol^-1)	ΔS /(J∙mol^-1∙K^-1)
298	-25.75	10.8	122.66
308	-26.98
318	-28.21

图10 d-g-CN对竞争离子的吸附容量和分配系数

Fig.10 Adsorption capacity and distribution coefficient of d-g-CN for competitive ions

图11 d-g-CN的循环吸脱附性能

Fig.11 Cyclic adsorption and desorption performance of d-g-CN

图12 d-g-CN吸附铀后的FTIR、XRD、SEM、TEM、EDS图

Fig.12 FTIR, XRD, SEM, TEM, EDS of uranium adsorbed by d-g-CN

图13 d-g-CN吸附铀前后的XPS能谱

Fig.13 XPS spectra of d-g-CN before and after uranium adsorption

图14 d-g-CN吸附UO22+的可能吸附机理

Fig.14 Possible adsorption mechanism for UO22+ on d-g-CN

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功能化多孔氮化碳材料对铀的吸附性能研究

Adsorption properties of functionalized porous carbon nitride materials for uranium

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