Preparation and Adsorption Properties of ZIF-8@B-CNF Composite Aerogel

doi:10.6023/A23020049

Abstract

Based on the principle of “fiber first”, cellulose nanofibrils (CNF) and metal-organic framework (MOF) are utilized to prepare composite material. The CNF with high dispersibility was prepared via MgCl₂/succinic acid hydrolysis, sodium chlorite oxidation and high-pressure homogenization, then it was chemically cross-linked with 1,2,3,4-butane tetracarboxylic acid (BTCA) and freeze-dried in a mold for 4 h to obtain the aerogel. The aerogel was fully esterified at 170 ℃ for 2~3 min to obtain aerogel B-CNF, then Zn²⁺ and 2-methylimidazole were synthesized in-situ on its surface, finally, ZIF-8@B-CNF composite aerogel was successfully prepared. After that, the composite aerogel was used for the adsorption of methylene blue (MB), and the effects of adsorption conditions including adsorption time, MB concentration, pH values of the solution were discussed. The ZIF-8@B-CNF composite aerogel was characterized by SEM (scanning electron microscope), XRD (X-ray diffraction), FT-IR (Fourier transform infrared spectroscopy), XPS (X-ray photoelectron spectroscopy), BET (Brunner-Emmet-Teller), etc., and the adsorption behavior and adsorption mechanism of MB were researched. The results showed that the ZIF-8@B-CNF composite aerogel had the advantages of low density and high surface area. When the loading capacity of ZIF-8 came up to 50%, the density of the ZIF-8@B-CNF was as low as less than 0.1 g•cm⁻³, and its surface area were increased by 14.5 times compared with that of the CNF aerogel. The ZIF-8@B-CNF composite aerogel showed excellent adsorption capacity for the MB, its theoretical maximum adsorption capacity was as high as 352.59 mg•g⁻¹ based on the Langmuir adsorption model, demonstrating that the composite aerogel had excellent adsorption capacity. The adsorption process was in accordance with the quasi-second-order kinetic model, which belonged to the chemisorption. In addition, the adsorption behavior of MB on the composite aerogel mainly depended on the effects of electrostatic interaction, π-π stacking and hydrogen bonding.

Key words: metal-organic framework, cellulose nanofibril, composite aerogel, adsorption property

Cite this article

Kaiqing Wang, Shuo Yuan, Wangdong Xu, Dan Huo, Qiulin Yang, Qingxi Hou, Dehai Yu. Preparation and Adsorption Properties of ZIF-8@B-CNF Composite Aerogel[J]. Acta Chimica Sinica, 2023, 81(6): 604-612.

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Fig. & Tab. 13

Figure 1. Macroscopic morphology (a~e) and microscopic morphology (f~j) of the B-CNF aerogel with different CNF/BTCA mass ratios

Figure 2. The density diagram (a) and FT-IR diagram (b) of B-CNF aerogels with different CNF/BTCA mass ratios

Figure 3. (a) The macroscopic and microscopic images of 30%-ZIF-8@B-CNF. (b~d) Microstructures of 10%-ZIF-8@B-CNF, 30%-ZIF-8@B-CNF and 50%-ZIF-8@B-CNF

Figure 4. (a) The density diagram of ZIF-8 composite aerogels with different loadings. The XRD spectra (b) and FT-IR spectra (c) of CNF, B-CNF, 30%-ZIF-8@B-CNF and ZIF-8. (d) The N2 adsorption-desorption isotherms of different materials

Figure 5. (a) XPS spectra of CNF, B-CNF, 30%-ZIF-8@B-CNF and ZIF-8 samples. (b~d) Fine spectra of O, Zn, N elements

Figure 6. The stability of ZIF-8@B-CNF composite aerogels immersed in different pH water environments for 24 h

Figure 7. Effects of adsorption time (a), initial dye concentration (b) and solution pH (c) on the adsorption properties of ZIF-8@B-CNF composite aerogel. (d) The reusability of ZIF-8@B-CNF composite aerogel for MB adsorption

Figure 8. (a) Langmuir and Freundlich adsorption isotherm models for MB adsorption by ZIF-8@B-CNF composite aerogel. Quasi-first-order kinetic fitting curve (b) and quasi-second-order kinetic fitting curve (c) for ZIF-8@B-CNF composite aerogel adsorption of MB

Langmuir model				Freundlich model
Q_m/(mg•g⁻¹)	K_L/(L•mg⁻¹)	R²		1/n	K_F/(mg•g⁻¹)	R²
352.59	0.0118	0.9784		0.3976	28.4781	0.9183

Table 1. Parameters of adsorption model for ZIF-8@B-CNF composite aerogel adsorption of MB

Adsorption material	T/℃	pH	C₀/(mg•L⁻¹)	Q_e/(mg•g⁻¹)	Reference
Magnetic activated carbon	25	10	50	169.49	[44]
Graphene oxide-chitosan composite aerogel	25	11	50	110.90	[45]
Ni-MOFs@GO composites	25	—	25	235.37	[46]
TiO₂-MIL-101 nano-composite	30	—	20	20.70	[47]
MIL-53(Fe)@montmorillonite	—	—	200	313.70	[48]
Waste cellulose/ZIF-8 aerogel	25	—	50	10.31	[49]
ZIF-8@B-CNF composite aerogel	25	—	60	352.59	This study

Table 2. Comparison of the maximum adsorption capacity of different materials for the MB

Q_e,exp/(mg•g⁻¹)	Quasi-first-order kinetic				Quasi-second-order kinetic
Q_e,exp/(mg•g⁻¹)	Q_e,cal/(mg•g⁻¹)	k₁/min⁻¹	R²		Q_e,cal/(mg•g⁻¹)	k₂/(g•mg⁻¹•min⁻¹)	R²
124.59	89.12	-0.0211	0.8468		139.86	0.0185	0.9956

Table 3. Kinetic parameters of MB adsorption on ZIF-8@B-CNF composite aerogels

Figure 9. FT-IR spectra of ZIF-8@B-CNF composite aerogel before and after adsorption of MB

Figure 10. Adsorption mechanism of ZIF-8@B-CNF composite aerogel for the MB

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ZIF-8@B-CNF复合气凝胶的制备及其吸附性能研究