基于柔性MOFs的磁响应复合材料及其丙烯吸附性能研究

doi:10.11949/0438-1157.20241125

摘要/Abstract

摘要：

磁诱导的变温吸附因其操作便捷、产热速率快以及传热距离短而备受关注，其能源利用效率由吸附材料在磁场中的性能决定。目前的吸附材料性能难以调变，无法在磁诱导变温吸附中充分发挥其分离性能。构筑了磁响应柔性吸附材料MN@CPL-1，并将其应用于丙烯捕获。通过将Fe₃O₄纳米颗粒与柔性MOF材料原位复合实现材料的制备。当交变磁场关闭时，MN@CPL-1具有开放的孔结构，能够有效地捕获丙烯分子。当交变磁场打开时，磁诱导的热量从Fe₃O₄纳米颗粒快速转移至CPL-1，使其框架结构发生局部旋转，促使丙烯分子释放。最优样品在10~30℃变温区间内的工作容量(22.5 cm³·g^-1)优于很多经典的丙烯吸附剂，如MIL-101(14.45 cm³·g^-1)、MAC-4(13.00 cm³·g^-1)和沸石5A(4.14 cm³·g^-1)。在外部磁场调控下，最优样品的吸附量变化率达到了65.9%，并且经过5次交变磁场关闭/打开吸脱附循环后，复合材料依然能保持良好的吸附性能。磁感应产热与吸附材料柔性结构的耦合提升了吸附效率。

关键词: 吸附剂, 吸附, 分离, 磁感应加热, 变温吸附

Abstract:

Magnetic-induced temperature-swing adsorption has attracted much attention due to its convenient operation, fast heat generation, and short heat transfer distance. The energy efficiency of this method is determined by the performance of adsorbents in a magnetic field. The current adsorbent material performance is difficult to adjust and cannot fully exert its separation performance in magnetically induced temperature swing adsorption. In this paper, a magnetically responsive flexible adsorbent material MN@CPL-1 was constructed and applied to propylene capture. These composite adsorbents were obtained by in-situ synthesis of Fe₃O₄ nanoparticles with flexible MOFs. When the alternating magnetic field is turned off, MN@CPL-1 has an open pore structure which can effectively captures propylene molecules. When the alternating magnetic field is turned on, the heat induced by magnetism can be rapidly transferred from Fe₃O₄ nanoparticles to CPL-1, causing local rotation of its framework and promoting the release of propylene molecules. The working capacity of the optimal sample in the temperature range of 10—30℃ (22.5 cm³·g^-1) is superior to various classic propylene adsorbents, such as MIL-101 (14.45 cm³·g^-1), MAC-4 (13.00 cm³·g^-1), and zeolite 5A (4.14 cm³·g^-1). Under the control of an external magnetic field, the uptake swing of the optimal sample reaches 65.9%. After 5 cycles closure/opening of alternating magnetic field for adsorption and desorption, the composite maintained good reusability. The coupling of magnetic-induced heat generation and flexible structure of adsorption materials improves the adsorption efficiency.

Key words: adsorbents, adsorption, separation, magnetic-induced heating, temperature-swing adsorption

中图分类号:

TQ 028.8

谈朋, 李雪梅, 刘晓勤, 孙林兵. 基于柔性MOFs的磁响应复合材料及其丙烯吸附性能研究[J]. 化工学报, 2025, 76(5): 2230-2240.

Peng TAN, Xuemei LI, Xiaoqin LIU, Linbing SUN. Study on magnetically responsive composite materials based on flexible MOFs and their propylene adsorption performance[J]. CIESC Journal, 2025, 76(5): 2230-2240.

图/表 18

图1 动态吸附实验装置示意图

Fig.1 Schematic diagram of dynamic adsorption experiment device

图2 PSS亲水改性的Fe3O4(a)和CPL-1(b)的SEM图像

Fig.2 SEM images of PSS hydrophilically modified Fe3O4 (a)and CPL-1 (b)

图3 MN@CPL-1-1(a)、MN@CPL-1-2(b)、MN@CPL-1-3(c)和MN@CPL-1-4(d)的SEM图像

Fig.3 SEM images of MN@CPL-1-1 (a), MN@CPL-1-2 (b), MN@CPL-1-3 (c) and MN@CPL-1-4 (d)

图4 Fe3O4、CPL-1、MN@CPL-1-1、MN@CPL-1-2、MN@CPL-1-3和MN@CPL-1-4的XRD谱图

Fig.4 XRD patterns of Fe3O4, CPL-1, MN@CPL-1-1, MN@CPL-1-2, MN@CPL-1-3 and MN@CPL-1-4

图5 样品的N2吸附-脱附等温线(a)和NLDFT孔径分布图(b)

Fig.5 N2 adsorption-desorption isotherms (a) and NLDFT pore size distributions of different samples (b)

表1 样品的结构参数

Table 1 Textural properties of different samples

Sample	S_BET/(m²·g^-1)	V_p/(cm³·g^-1)	V_micro/(cm³·g^-1)
CPL-1	247	0.09	0.05
MN@CPL-1-1	172	0.11	0.07
MN@CPL-1-2	216	0.17	0.06
MN@CPL-1-3	246	0.19	0.11
MN@CPL-1-4	229	0.18	0.11

图6 Fe3O4、CPL-1、MN@CPL-1-1、MN@CPL-1-2、MN@CPL-1-3和MN@CPL-1-4的FTIR谱图

Fig.6 FTIR spectra of Fe3O4, CPL-1, MN@CPL-1-1, MN@CPL-1-2, MN@CPL-1-3 and MN@CPL-1-4

图7 Fe3O4、CPL-1、MN@CPL-1-1、MN@CPL-1-2、MN@CPL-1-3和MN@CPL-1-4的TG(a)和DTG曲线(b)

Fig.7 TG (a) and DTG (b) curves of Fe3O4, CPL-1, MN@CPL-1-1, MN@CPL-1-2, MN@CPL-1-3 and MN@CPL-1-4

图8 Fe3O4、MN@CPL-1-1、MN@CPL-1-2、MN@CPL-1-3和MN@CPL-1-4的磁滞回线（1 Oe=79.5774715 A·m-1）

Fig.8 Magnetic hysteretic loops of Fe3O4, MN@CPL-1-1, MN@CPL-1-2, MN@CPL-1-3 and MN@CPL-1-4（1 Oe=79.5774715 A·m-1）

图9 将MN@CPL-1-3置于磁感应加热系统线圈中的示意图

Fig.9 Schematic diagram of MN@CPL-3 is placed in the coils of the magnetic-induced heating system

图10 (a)MN@CPL-1-1、MN@CPL-1-2、MN@CPL-1-3和MN@CPL-1-4暴露在442 mT交变磁场和(b)MN@CPL-1-3暴露在不同强度的交变磁场中的温度变化

Fig.10 Temperature changes of (a) MN@CPL-1-1, MN@CPL-1-2, MN@CPL-1-3 and MN@CPL-1-4 exposed to the alternating magnetic field of 442 mT and (b) MN@CPL-1-3 exposed to alternating magnetic fields of different intensities

图11 CPL-1在不同温度下的C3H6吸附等温线（1 mmHg=133.28 Pa）

Fig.11 C3H6 adsorption isotherms of CPL-1 at different temperatures（1 mmHg=133.28 Pa）

图12 MN@CPL-1-1(a)，MN@CPL-1-2(b)，MN@CPL-1-3(c)，MN@CPL-1-4(d)和CPL-1(e)在10℃和30℃下的C3H6吸附等温线

Fig.12 C2H6 adsorption isotherms of MN@CPL-1-1 (a), MN@CPL-1-2 (b), MN@CPL-1-3 (c), MN@CPL-1-4 (d) and CPL-1 (e) at 10℃ and 30℃ (1 bar=105 Pa)

表2 样品在10℃和30℃下的饱和吸附量和工作容量

Table 2 Saturated adsorption and working capacities of different samples at 10℃ and 30°C

Sample	Adsorption capacity at 10℃/ (cm³·g^-1)	Adsorption capacity at 30℃/ (cm³·g^-1)	Working capacity/ （cm³·g^-1）
CPL-1	36.8	12.0	24.8
MN@CPL-1-1	32.5	10.8	21.7
MN@CPL-1-2	33.4	11.4	22.0
MN@CPL-1-3	34.0	11.5	22.5
MN@CPL-1-4	28.1	10.5	17.6

表3 不同类型的C3H6吸附剂的工作容量

Table 3 Working capacities of different kinds of C3H6 adsorbents

Sample	T_l /℃	T_h/℃	Working capacity/(cm³·g^-1)	References
MN@CPL-1-3	10	30	22.50	This work
MAC-4	0	25	13.00	[31]
HP-Cu-BTC	0	25	6.98	[32]
MIL-101	20	40	14.45	[33]
ZIF-8	0	20	8.58	[33]
Ni-MOF-74	25	50	7.84	[34]
5A	0	20	4.14	[33]
zeolite 4A	150	185	10.30	[35]
SG-1	20	40	3.18	[33]

图13 磁感应加热脱附C3H6机理示意图

Fig.13 Desorption mechanism of C3H6 in magnetic-induced heating

图14 MN@CPL-1-1(a)，MN@CPL-1-2(b)，MN@CPL-1-(c)3和MN@CPL-1-4(d)在打开和关闭交变磁场下的动态吸附曲线；(e)CPL-1在10 ℃和30 ℃下的动态吸附曲线

Fig.14 Dynamic adsorption curves of MN@CPL-1-1 (a), MN@CPL-1-2 (b), MN@CPL-1-3 (c), and MN@CPL-1-4 (d) with the alternating magnetic field on and off; (e) Dynamic adsorption curve of CPL-1 at 10 ℃ and 30 ℃

图15 MN@CPL-1-3的吸附-脱附循环

Fig.15 Adsorption-desorption cycles of MN@CPL-1-3

参考文献 35

1	Cui J Y, Zhang Z Q, Yang L F, et al. A molecular sieve with ultrafast adsorption kinetics for propylene separation[J]. Science, 2024, 383(6679): 179-183.
2	Fu H L, Huang J Y, van der Tol J J B, et al. Supramolecular polymers form tactoids through liquid-liquid phase separation[J]. Nature, 2024, 626(8001): 1011-1018.
3	Mattocks J A, Jung J J, Lin C Y, et al. Enhanced rare-earth separation with a metal-sensitive lanmodulin dimer[J]. Nature, 2023, 618(7963): 87-93.
4	Mensah M A, Niskanen H, Magalhaes A P, et al. Aberrant phase separation and nucleolar dysfunction in rare genetic diseases[J]. Nature, 2023, 614(7948): 564-571.
5	Zhang H L, Li A, Li K, et al. Ultrafiltration separation of Am(Ⅵ)-polyoxometalate from lanthanides[J]. Nature, 2023, 616(7957): 482-487.
6	任其龙, 杨启炜, 鲍宗必. 中国气体分离领域发展现状和未来挑战[J]. 科学观察, 2023, 18(5): 13-16.
	Ren Q L, Yang Q W, Bao Z B. Development status and future challenges in the field of gas separation in China[J]. Science Focus, 2023, 18(5): 13-16.
7	张凯博, 沈佳新, 李玉霞, 等. Y沸石中Cu(Ⅰ)的可控构筑及其乙烯/乙烷吸附分离性能研究[J]. 化工学报, 2024, 75(4): 1607-1615.
	Zhang K B, Shen J X, Li Y X, et al. Controllable construction of Cu(Ⅰ) in Y zeolite for adsorptive separation of ethylene/ethane[J]. CIESC Journal, 2024, 75(4): 1607-1615.
8	郭智芳, 张信伟, 王海洋, 等. 石脑油正异构烷烃吸附分离技术[J]. 当代化工, 2024, 53(7): 1703-1710.
	Guo Z F, Zhang X W, Wang H Y, et al. Technology of adsorption and separation of n/iso-alkanes in naphtha[J]. Contemporary Chemical Industry, 2024, 53(7): 1703-1710.
9	Dai H, Yuan X Z, Jiang L B, et al. Recent advances on ZIF-8 composites for adsorption and photocatalytic wastewater pollutant removal: fabrication, applications and perspective[J]. Coordination Chemistry Reviews, 2021, 441: 213985.
10	Deutz S, Bardow A. Life-cycle assessment of an industrial direct air capture process based on temperature-vacuum swing adsorption[J]. Nature Energy, 2021, 6: 203-213.
11	Saheed I O, Oh W D, Suah F B M. Chitosan modifications for adsorption of pollutants—a review[J]. Journal of Hazardous Materials, 2021, 408: 124889.
12	Verougstraete B, Gholami M, Gomez-Rueda Y, et al. Advancements and challenges in electric heating for enhanced temperature swing adsorption processes[J]. Separation and Purification Technology, 2025, 353: 128522.
13	Li Y C, Delmo E P, Hou G Y, et al. Enhancing local CO₂ adsorption by L-histidine incorporation for selective formate production over the wide potential window[J]. Angewandte Chemie International Edition, 2023, 62(49): e202313522.
14	Zhang Z Q, Chen Y L, Chai K G, et al. Temperature-dependent rearrangement of gas molecules in ultramicroporous materials for tunable adsorption of CO₂ and C₂H₂ [J]. Nature Communications, 2023, 14(1): 3789.
15	Du X D, Cheng Y G, Liu Z J, et al. CO₂ and CH₄ adsorption on different rank coals: a thermodynamics study of surface potential, Gibbs free energy change and entropy loss[J]. Fuel, 2021, 283: 118886.
16	Dang Y X, Tan P, Hu B, et al. Low-energy-consumption temperature swing system for CO₂ capture by combining passive radiative cooling and solar heating[J]. Green Energy & Environment, 2024, 9(3): 507-515.
17	王丽, 王兴杰, 李浩, 等. 葡萄糖基多孔碳材料对CO₂/CH₄的分离性能[J]. 化工学报, 2018, 69(2): 733-740.
	Wang L, Wang X J, Li H, et al. Separation performance of CO₂/CH₄ on porous carbons derived from glucose[J]. CIESC Journal, 2018, 69(2): 733-740.
	王丽, 王兴杰, 李浩, 等. 葡萄糖基多孔碳材料对CO₂/CH₄的分离性能[J]. 化工学报, 2018, 69(2): 733-740.
	Wang L, Wang X J, Li H, et al. Separation performance of CO₂/CH₄ on porous carbons derived from glucose[J]. CIESC Journal, 2018, 69(2): 733-740.
18	阎海宇, 付强, 周言, 等. 真空变压吸附捕集烟道气中二氧化碳的模拟、实验及分析[J]. 化工学报, 2016, 67(6): 2371-2379.
	Yan H Y, Fu Q, Zhou Y, et al. Simulation, experimentation and analyzation of vacuum pressure swing adsorption process for CO₂ capture from dry flue gas[J]. CIESC Journal, 2016, 67(6): 2371-2379.
19	Gu C, Tan P, Jiang T Y, et al. Solar-radiation-induced adsorption/desorption system for carbon dioxide capture[J]. Cell Reports Physical Science, 2022, 3: 101122.
20	Jacobs J H, Deering C E, Sui R H, et al. Degradation of desiccants in temperature swing adsorption processes: the temperature dependent degradation of zeolites 4A, 13X and silica gels[J]. Chemical Engineering Journal, 2023, 451: 139049.
21	Zanco S E, Ambrosetti M, Groppi G, et al. Heat transfer intensification with packed open-cell foams in TSA processes for CO₂ capture[J]. Chemical Engineering Journal, 2022, 430: 131000.
22	Huang G S, Huang C, Tao Y L, et al. Localized heating driven selective growth of metal-organic frameworks (MOFs) in wood: a novel synthetic strategy for significantly enhancing MOF loadings in wood[J]. Applied Surface Science, 2021, 564: 150325.
23	Tao Y L, Li Q Q, Wu Q N, et al. Embedding metal foam into metal-organic framework monoliths for triggering a highly efficient release of adsorbed atmospheric water by localized eddy current heating[J]. Materials Horizons, 2021, 8(5): 1439-1445.
24	Li X M, Tan P, Sun Z, et al. Magnetic MOFs with flexibility for efficient magnetic-induced swing adsorption[J]. Separation and Purification Technology, 2024, 348: 127723.
25	De Belder M, Morais A F, De Vos N, et al. Performance of ferrite nanoparticles in inductive heating swing adsorption (IHSA): how tailoring material properties can circumvent the design limitations of a system[J]. Materials Horizons, 2024, 11(17): 4144-4149.
26	Bellusci M, Masi A, Albino M, et al. Fe₃O₄@HKUST-1 magnetic composites by mechanochemical route for induction triggered release of carbon dioxide[J]. Microporous and Mesoporous Materials, 2021, 328: 111458.
27	Maity R, Gholami M, Peter S A, et al. Strategic fast induction heating to combat hysteresis barriers in a flexible MOF for rapid CO₂ desorption in biogas upgrading[J]. Small, 2023, 19(29): 2302893.
28	Schoukens M, Sharma R, Laha P, et al. Enhancing desorption performance of a compressible hybrid structured adsorbent via localized magnetic induction heating[J]. Advanced Materials Interfaces, 2024, 11(19): 2400105.
29	Zeng H, Xie M, Wang T, et al. Orthogonal-array dynamic molecular sieving of propylene/propane mixtures[J]. Nature, 2021, 595(7868): 542-548.
30	Deng Y H, Cai Y, Sun Z K, et al. Multifunctional mesoporous composite microspheres with well-designed nanostructure: a highly integrated catalyst system[J]. Journal of the American Chemical Society, 2010, 132(24): 8466-8473.
31	Wang G D, Li Y Z, Krishna R, et al. Scalable synthesis of robust MOF for challenging ethylene purification and propylene recovery with record productivity[J]. Angewandte Chemie International Edition, 2024, 63(15): e202319978.
32	Yang P, Li Y X, Liang W B, et al. Prediction of adsorption isotherms of C₃H₆/C₃H₈ on hierarchical porous HP-Cu-BTC[J]. Journal of the Indian Chemical Society, 2022, 99(9): 100657.
33	Su W, Zhang A, Sun Y, et al. Adsorption properties of C₂H₄ and C₃H₆ on 11 adsorbents[J]. Journal of Chemical & Engineering Data, 2017, 62(1): 417-421.
34	Chen D L, Shang H, Zhu W D, et al. Transient breakthroughs of CO₂/CH₄ and C₃H₆/C₃H₈ mixtures in fixed beds packed with Ni-MOF-74[J]. Chemical Engineering Science, 2014, 117: 407-415.
35	Patiño-Iglesias M E, Aguilar-Armenta G, Jiménez-López A, et al. Kinetics of the total and reversible adsorption of propylene and propane on zeolite 4A (CECA) at different temperatures[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2004, 237(1/2/3): 73-77.

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