ZIF-8@B-CNF复合气凝胶的制备及其吸附性能研究

doi:10.6023/A23020049

摘要/Abstract

基于“纤维优先”的原则, 采用纤维素纳米纤丝(CNF)与金属有机骨架(MOF)制备复合材料. 采用1,2,3,4-丁烷四羧酸(BTCA)对CNF进行化学交联, 通过冷冻干燥处理制备气凝胶(B-CNF), 接着采用原位生长法在B-CNF表面负载沸石咪唑酯骨架结构材料(ZIF-8), 成功制备ZIF-8@B-CNF复合气凝胶, 并将其用于亚甲基蓝(MB)的吸附. 采用扫描电子显微镜(SEM)、X射线衍射(XRD)、傅里叶变换红外光谱(FT-IR)、X射线光电子能谱(XPS)以及Brunner-Emmet-Teller (BET)等对ZIF-8@B-CNF复合气凝胶进行了表征, 对其吸附机理进行了研究. 结果表明, ZIF-8@B-CNF复合气凝胶具有低密度、高强度等优点, 当ZIF-8负载量为50%时, 其密度低于0.1 g•cm⁻³, 比表面积较CNF增加了14.5倍. 该复合气凝胶对MB表现出优异的吸附能力, 由Langmuir吸附模型得出其理论最大吸附量为352.59 mg•g⁻¹, 吸附过程更符合准二级动力学模型, 属于化学吸附.

关键词: 金属有机骨架, 纤维素纳米纤丝, 复合气凝胶, 吸附性能

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

引用此文

王凯晴, 袁硕, 徐王东, 霍丹, 杨秋林, 侯庆喜, 于得海. ZIF-8@B-CNF复合气凝胶的制备及其吸附性能研究[J]. 化学学报, 2023, 81(6): 604-612.

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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图/表 13

图1. 不同CNF/BTCA质量比的B-CNF气凝胶宏观形貌图(a~e)和微观形貌图(f~j)

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

图2. 不同CNF/BTCA质量比的B-CNF气凝胶的密度图(a)以及FT-IR图(b)

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

图3. (a) 30%-ZIF-8@B-CNF宏观与微观图. (b~d) 10%-ZIF-8@B-CNF、30%-ZIF-8@B-CNF和50%-ZIF-8@B-CNF的微观图

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

图4. (a) ZIF-8不同负载量的复合气凝胶的密度图. CNF、B-CNF、30%-ZIF-8@B-CNF和ZIF-8的XRD光谱图(b)和FT-IR光谱图(c). (d)不同材料的N2吸附-脱附等温线

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

图5. (a) CNF、B-CNF、30%-ZIF-8@B-CNF和ZIF-8的XPS谱图. (b~d) O、Zn、N元素的精细谱图

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

图6. ZIF-8@B-CNF复合气凝胶在不同pH水环境中浸泡24 h的稳定性测试

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

图7. 吸附时间(a)、染料初始浓度(b)以及溶液pH (c)对ZIF-8@B-CNF复合气凝胶吸附性能的影响. (d) ZIF-8@B-CNF复合气凝胶对MB吸附的重复利用性能

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

图8. (a) ZIF-8@B-CNF复合气凝胶吸附MB的Langmuir和Freundlich吸附等温线模型. ZIF-8@B-CNF复合气凝胶吸附MB的准一级动力学拟合曲线(b)和准二级动力学拟合曲线(c)

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

表1. ZIF-8@B-CNF复合气凝胶吸附MB的吸附模型参数

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

表2. 不同材料对MB的最大吸附量比较

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

表3. ZIF-8@B-CNF复合气凝胶吸附MB的动力学参数

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

图9. ZIF-8@B-CNF复合气凝胶吸附MB前后的FT-IR光谱图

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

图10. ZIF-8@B-CNF复合气凝胶对MB的吸附机理

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

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