Preparation and Adsorption Properties of Lithium Chloride Intercalation Carbon Nitride

doi:10.6023/A21120594

Abstract

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

Cite this article

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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Fig. & Tab. 15

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

Figure 2. FTIR spectra of g-C3N4 and 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

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

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

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

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]

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

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

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

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

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

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

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

Figure 12. MB standard curve

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