氯化锂插层氮化碳材料的可控制备及吸附性能

doi:10.6023/A21120594

摘要/Abstract

近年来, 有机废水对环境造成的污染已经引起了广泛的关注. 吸附法操作简单, 已经被广泛用于处理染料废水.通过在类石墨相氮化碳(g-C₃N₄)上用氯化锂(LiCl)插层制备了一系列Li/GCN-x复合材料, 并采用X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、N₂-吸脱附、场发射扫描电子显微镜(SEM)以及X射线光电子能谱(XPS)等对所得吸附剂的形貌和结构进行了表征. 测试结果表明, g-C₃N₄具有明显的层状结构, 使得LiCl在层间能够稳定地生长. LiCl的加入使得g-C₃N₄晶格膨胀, 层间距扩大, 表明LiCl成功插层. 此外, 插层后Li/GCN的比表面积远大于g-C₃N₄, 扩大的比表面积以及形成的 π 共轭体系使得Li/GCN在吸附方面具有较大的潜力. 通过控制实验条件, 研究了Li/GCN对有机染料亚甲基蓝(MB)的吸附性能. 结果表明, Li/GCN-5吸附剂在pH为6时, 5 min吸附量可达704 mg•g^–1. 通过动力学拟合, Li/GCN对MB的吸附过程是由准二级动力学模型占主导地位. 进一步通过Weber-Morris模型探究吸附控制过程, 结果表明MB的吸附由表面扩散和孔内扩散共同作用, 其中表面扩散占主导, 且新增官能团与MB分子间可形成氢键, 并通过π-π键相互作用增强吸附能力. 采用共混热聚合法所制备的Li/GCN吸附剂具有稳定、均一、比表面积大等优点, 且简单快速地实现对MB的吸附, 克服了常用吸附剂动力学缓慢的缺点, 为该材料的工业化应用提供一定的借鉴.

关键词: 氮化碳, 插层, 吸附性能, 氯化锂, 动力学模拟

In recent years, the pollution of organic wastewater to the environment has attracted extensive attention. The adsorption method is simple and has been used for the adsorption of organic dyes in wastewater. In this study, lithium chloride (LiCl) was intercalated on graphite like carbon nitride (g-C₃N₄), a series of Li intercalated g-C₃N₄ adsorbents (Li/GCN-x) were synthesized. And use X-ray diffraction (XRD), field emission scanning electron microscopy (SEM), N₂ adsorption-desorption and other methods to comprehensively test and characterize the phase structure, morphology, and surface area of the prepared samples. At the same time, the influence of the amount of LiCl added on the adsorption of methylene blue (MB) on the intercalation material at room temperature was investigated. The optimal Li content in the intercalation g-C₃N₄ was determined. The research results show that compared with pure g-C₃N₄, the prepared Li/GCN-5 can form fibers with uniform diameters between the layers, XRD results show that the addition of LiCl makes the lattice of g-C₃N₄ expand and the layer spacing expand, indicating the successful intercalation of LiCl. The pH and the binding time between the adsorbent and MB were studied. The new functional groups of the adsorbent can form hydrogen bonds with MB molecules and interact through π-π bonds. When only 50 mg of the adsorbent is added, the maximum adsorption capacity can reach 704 mg•g^–1 in 5 min. In addition, adsorption kinetics simulations have been carried out. The results show that the intercalation adsorbent can adsorb MB. The model conforms to the quasi-second-order kinetic equation. The Weber-Morris model was further used to explore the adsorption control process. The results showed that the adsorption of MB was caused by the combined action of surface diffusion and intrapore diffusion, in which surface diffusion was dominant, and the newly added functional groups could form hydrogen bonds with MB molecules, and the interaction enhances the adsorption capacity through π-π bonds. The as-prepared materials in this study are stable, uniform and have large specific surface area, which can simply and quickly realize the adsorption of MB. It provides a simple, low-cost, and efficient method for the adsorption and removal of organic pollutants, which overcomes the shortcomings of slow kinetics of commonly used adsorbents.

Key words: carbon nitride, intercalation, adsorption property, lithium chloride, kinetics simulations

引用此文

位亚茹, 马晶, 袁婷婷, 姜嘉伟, 段银利, 薛娟琴. 氯化锂插层氮化碳材料的可控制备及吸附性能[J]. 化学学报, 2022, 80(4): 494-502.

Yaru Wei, Jing Ma, Tingting Yuan, Jiawei Jiang, Yinli Duan, Juanqin Xue. Preparation and Adsorption Properties of Lithium Chloride Intercalation Carbon Nitride[J]. Acta Chimica Sinica, 2022, 80(4): 494-502.

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图/表 15

图1. g-C3N4和Li/GCN-x的XRD图谱

Figure 1. XRD patterns of synthesized g-C3N4 and Li/GCN-x

图2. g-C3N4和Li/GCN-5的FTIR图谱

Figure 2. FTIR spectra of g-C3N4 and Li/GCN-5

图3. g-C3N4和Li/GCN-5的N2吸脱附图与孔径分布图: (a) g-C3N4; (b) Li/GCN-5

Figure 3. N2 adsorption-desorption and pore size distribution of g-C3N4 and Li/GCN-5: (a) g-C3N4; (b) Li/GCN-5

Sample	Surface area/ (m²•g^–1)	Pore volume/ (cm³•g^–1)	Pore diameter/ nm
g-C₃N₄	8.30	0.07	33.52
Li/GCN-5	119.3	0.21	7.02

表1. g-C3N4和Li/GCN-5的比表面积、孔体积和平均孔径数据

Table 1. Surface area, pore volume, and average pore diameter data of g-C3N4 and Li/GCN-5

图4. g-C3N4与Li/GCN-5的形貌表征: (a) g-C3N4的SEM图, (b) Li/GCN-5的SEM图

Figure 4. SEM images of g-C3N4 (a) and Li/GCN-5 (b)

图5. g-C3N4和Li/GCN-5的XPS谱图: (a)全谱图; (b) C 1s; (c) N 1s; (d) Li 1s和Cl 2p

Figure 5. XPS spectra of g-C3N4 and Li/GCN-5: (a) survey spectra; (b) C 1s; (c) N 1s; (d) Li 1s and Cl 2p

图6. 不同吸附剂在不同浓度下对溶液的吸附曲线: (a) 20 mg•L–1; (b) 30 mg•L–1 ; (c) 40 mg•L–1

Figure 6. Adsorption curves of different adsorbents at different concentrations: (a) 20 mg•L–1; (b) 30 mg•L–1; (c) 40 mg•L–1

Adsorbent	Adsorbate	Surface area/(m²•g^–1)	q_m/(mg•g^–1)	Reference
Li_0.5-CN	RhB	10.1	—	[57]
50-CN	MB	1.0	360	[58]
NCG-2	MB	432.0	348.2	[48]
LiCl-CN-4h	Pb(II)	36.54	172.41	[17]
g-C₃N₄	Pb(II)	11.0	281.79	[6]
g-C₃N₄	Cd²⁺	52.0	94.4	[3]

表2. 各种氮化碳吸附剂对 MB 吸附性能的比较

Table 2. Comparison of the adsorption performance of various carbon nitride adsorbents on MB

图7. 不同pH下Li/GCN-5对30 mg•L–1 MB溶液的吸附量

Figure 7. Adsorption capacity of Li/GCN-5 to 30 mg•L–1 MB solution under different pH

图8. Li/GCN-5吸附MB溶液的动力学模型: (a)准一级动力学模型; (b)准二级动力学模型

Figure 8. Kinetic model of Li/GCN-5 adsorption of MB solution: (a) Quasi-first-order kinetic model; (b) Quasi-second-order kinetic model

MB/(mg•L^–1)	准一级动力学			准二级动力学
MB/(mg•L^–1)	k₁/(min^–1)	q_e/(mg•g^–1)	R²	k₂/(g•mg^–1•min^–1)	q_e/(mg•g^–1)	R²
20	0.08328	85.26	0.87551	0.00732	383.14	0.99984
30	0.06911	30.28	0.56804	0.00351	598.80	0.99999
40	0.15555	169.02	0.79305	0.00526	704.23	0.99983

表3. Li/GCN-5在不同浓度下吸附MB的最佳拟合模型及动力学参数

Table 3. The best fitting model and kinetic parameters of Li/GCN-5 adsorption of MB at different concentrations

图9. Li/GCN-5吸附不同浓度MB溶液的颗粒内扩散模型: (a) MB浓度为20 mg•L–1; (b) MB浓度为30 mg•L–1

Figure 9. Intra-particle diffusion model of Li/GCN-5 adsorbing MB solutions with different concentrations: (a) 20 mg•L–1; (b) 30 mg•L–1

图10. Li/GCN-5对MB的吸附机理图

Figure 10. Li/GCN-5 adsorption mechanism diagram for MB

图11. Li/GCN-x的制备流程示意图

Figure 11. Schematic diagram of Li/GCN-x preparation process

图12. MB标准曲线

Figure 12. MB standard curve

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