Preparation of ZIF-8 based porous liquid and its SO2 adsorption performance

doi:10.11949/0438-1157.20250046

Abstract

Abstract:

Porous liquid (PLs) is a new kind of material with stable permanent pore structure and fluidity. A type Ⅲ porous liquid was synthesized with 2-methylimidazole zinc salt (ZIF-8) nanoparticles as the main body and 1-ethyl-3-methylimidazole bis (trifluoromethanesulfonyl) imide ([EMIm][NTf₂]) as the steric inhibitor. The effects of ZIF-8 loading, SO₂ concentration, SO₂ flow rate and temperature on the adsorption performance of PLs were studied. The results show that PLs has certain fluidity, thermal stability and permanent pore structure. The addition of ZIF-8 can significantly improve the SO₂ adsorption capacity of ionic liquid steric inhibitor. When the loading capacity of ZIF-8 is 25%, the saturation adsorption capacity of PLs for SO₂ (0.41 mmol/g) is much higher than that of pure ionic liquid (0.05 mmol/g), the synergistic effect of ZIF-8 and ionic liquid reaches 61.6%, and the adsorption rate of ZIF-8 is higher (0.37 mmol/(g·min)). The adsorption behavior of PLs for SO₂ conforms to the Avrami adsorption kinetics model. PLs mainly adsorbs SO₂ through the interaction of chemical bond and van der Waals force. PLs still has high adsorption capacity after 4 times of regeneration.

Key words: ZIF-8, porous liquid, SO₂, adsorption, adsorbents, kinetics

摘要：

多孔液体（PLs）是一种具有稳定永久孔隙结构及流动性的新型材料。以2-甲基咪唑锌盐（ZIF-8）纳米粒子为主体，1-乙基-3-甲基咪唑双（三氟甲磺酰基）亚胺（[EMIm][NTf₂]）为位阻剂，合成了一种Ⅲ型多孔液体。研究了ZIF-8负载量、SO₂浓度、SO₂流量和温度对PLs吸附性能的影响。结果表明，PLs具有一定的流动性、热稳定性和永久孔隙结构；ZIF-8的加入能显著提高离子液体位阻剂的SO₂吸附能力，当ZIF-8负载量为25%时，PLs对SO₂的饱和吸附量（0.41 mmol/g）远高于纯离子液体（0.05 mmol/g），ZIF-8与离子液体的协同效应达到61.6%，同时具有较高的吸附速率（0.37 mmol/(g·min)）。PLs对SO₂的吸附行为符合Avrami吸附动力学模型，PLs主要通过化学键和范德华力的共同作用对SO₂进行吸附。PLs经过4次再生后仍具有较高的吸附能力。

关键词: ZIF-8, 多孔液体, SO₂, 吸附, 吸附剂, 动力学

CLC Number:

TQ 028.1

Yuhong TIAN, Zhuangzhuang DU, Huifang XU, Ziqiang ZHU, Yucong WANG. Preparation of ZIF-8 based porous liquid and its SO₂ adsorption performance[J]. CIESC Journal, 2025, 76(8): 4284-4296.

田宇红, 杜壮壮, 徐慧芳, 祝自强, 王宇聪. ZIF-8基多孔液体制备及其SO₂吸附性能[J]. 化工学报, 2025, 76(8): 4284-4296.

Figures/Tables 21

Fig.1 Preparation of porous liquid

Fig.2 SO2 adsorption device diagram

Fig.3 SEM and EDS images of ZIF-8 (a) and ZIF-8 after adsorption of SO2 (b)

Fig.4 XRD patterns of ZIF-8, ZIF-8 after adsorption of SO2, and ZIF-8 separated from porous liquid

Fig.5 IR spectra of ZIF-8 before and after adsorption of SO2

Fig.6 XPS full spectrum of ZIF-8 before and after adsorption of SO2 (a) and high resolution spectra of S 2p (b), Zn 2p (c) and N 1s (d)

Fig.7 N2 adsorption and desorption isotherms (a) and pore size distributions (b) of ZIF-8 and ZIF-8 isolated from porous liquids

Table 1 Pore structure parameters of ZIF-8 and ZIF-8 in porous liquids

材料	比表面积/(m²/g)	孔体积/(cm³/g)	孔径/nm
ZIF-8	1031.02	0.467	0.61
ZIF-8-PLs	911.83	0.383	0.60

Fig.8 TEM and EDS images of ZIF-8-IL

Fig.9 (a) FTIR spectra of porous liquids with different ZIF-8 loads; (b) Thermogravimetric curves of porous liquids with different ZIF-8 loads

Fig.10 Temperature-viscosity diagram of ZIF-8 (25%) –IL (a) and physical diagram (b)

Fig.11 The change curve of adsorption capacity with time (a) and the change relationship between adsorption capacity and adsorption rate (b) of porous liquid with different ZIF-8 loads

Table 2 Comparison of SO2 adsorption data of different porous materials

吸附剂类型	吸附温度/K	饱和吸附量/(mmol/g)	文献
UiO-66-甲酸	298	0.405	[43]
Zr-MOF-NH₂/CTF-Cu²⁺	298	0.614	[44]
Zr-MOF-NH₂/PAN	298	0.297	[45]
MOF-199/PAN	298	0.219	[45]
UiO-66-NH₂@CNTs/PTFE	298	0.6	[46]
ZIF-8(25%)-IL	303	0.41	本研究

Fig.12 Synergistic effect of SO2 adsorption on porous liquids with different ZIF-8 loads

Fig.13 The change curve of adsorption capacity with time (a) and the change relationship between adsorption capacity and adsorption rate (b) of ZIF-8(25%)-IL at different SO2 concentrations; adsorption curve of ZIF-8(25%)-IL with time (c) and relationship between adsorption amount and adsorption rate (d) at different gas flow rates

Fig.14 Change curve of adsorption capacity with time (a) and change relationship between adsorption capacity and adsorption rate (b) of ZIF-8(25%)-IL at different temperatures

Table 3 Kinetic model fitting parameters for adsorption of SO2 by porous liquids with different ZIF-8 loads

样品	伪一级动力学模型			伪二级动力学模型			Avrami 吸附动力学模型
样品	q_e/(mmol/g)	k₁/min^-1	R²	q_e/(mmol/g)	k₂/(g/(min·mmol))	R²	q_e/(mmol/g)	k_A/min^-1	n_A	R²
[EMIm][NTf₂]	0.0471	0.0832	0.991	0.0518	2.4151	0.991	0.0475	0.0090	0.8580	0.997
ZIF-8(5%)-IL	0.1450	0.0597	0.976	0.1661	0.4637	0.928	0.1428	0.0158	1.4573	0.997
ZIF-8(10%)-IL	0.2073	0.0579	0.975	0.2383	0.3085	0.928	0.2039	0.0143	1.4764	0.997
ZIF-8(15%)-IL	0.2732	0.0297	0.967	0.3544	0.0775	0.943	0.2571	0.0044	1.5796	0.996
ZIF-8(20%)-IL	0.5645	0.0089	0.979	0.9439	0.0058	0.977	0.3858	0.0020	1.5110	0.993
ZIF-8(25%)-IL	1.1751	0.0036	0.993	2.1766	0.0009	0.993	0.5799	0.0029	1.2668	0.996
ZIF-8(30%)-IL	1.3981	0.0017	0.997	2.7028	0.0003	0.997	0.4914	0.0026	1.1860	0.998
ZIF-8	0.4941	0.0418	0.998	0.5939	0.0796	0.980	0.4882	0.303	1.1056	0.999

Fig.15 Pseudo-first-order adsorption kinetics model (a), pseudo-second-order adsorption kinetics model (b) and Avrami adsorption kinetics model (c) for different ZIF-8 loads of porous liquids

Fig.16 Cyclic stability of ZIF-8(25%)-IL: (a) cyclic adsorption curve; (b) relationship between cyclic saturation adsorption capacity and efficiency

Fig.17 Cyclic stability: (a) N2 adsorption and desorption isotherm; (b) aperture distribution; (c) XRD pattern, (d) infrared spectrum

Fig.18 Porous liquid adsorption mechanism of SO2

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Preparation of ZIF-8 based porous liquid and its SO₂ adsorption performance

ZIF-8基多孔液体制备及其SO₂吸附性能

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