Study on magnetically responsive composite materials based on flexible MOFs and their propylene adsorption performance

doi:10.11949/0438-1157.20241125

Abstract

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

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

CLC Number:

TQ 028.8

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.

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.

Figures/Tables 18

Fig.1 Schematic diagram of dynamic adsorption experiment device

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

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)

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

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

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

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

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

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）

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

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

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

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)

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

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]

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

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 ℃

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

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