CO2 capture and separation by ionic liquid-metal organic framework composite materials

doi:10.16085/j.issn.1000-6613.2023-0010

Abstract

Abstract:

Due to the worsening global climate change and the increasing extreme weather events, CO₂ capture and separation has important strategic significance and relates to human survival. In recent years, new materials for CO₂ capture and separation have emerged. Among them, ionic liquids (ILs), as a new alternative to organic solvents, have received tremendous interest due to the tunable chemical structures and unique physicochemical properties, such as low volatility, high thermal stability and excellent solubility. And metal-organic frameworks (MOFs) have also been considered as fascinating porous materials for CO₂ capture and separation. In this paper, the research progress of CO₂ capture and separation by ILs/MOFs composites is summarized. The adsorptive separation via MOFs-supported ILs, ILs-modified MOFs, dispersing MOFs in ILs to form porous liquids, and membrane separation are all discussed, as well as the advantages and disadvantages of each method. In addition, the application prospect and development of ILs/MOFs composites in CO₂ capture and separation are also discussed.

Key words: metal-organic frameworks, ionic liquids, composite materials, CO₂ capture and separation

摘要：

由于全球气候变化加剧和极端天气的增加，CO₂捕集分离已经不单单具有重要的战略意义，更关乎人类的生存。近年来，用于捕集分离CO₂的新型材料层出不穷，其中，离子液体（ionic liquids，ILs）具有可调变的化学结构和独特的物理化学性质，例如低挥发性、高热稳定性和较好的溶解性，从而引起了广泛关注。同时，金属有机框架结构材料（metal-organic frameworks，MOFs）在CO₂捕集分离方面也表现出优异性能。基于此，本文总结了ILs与MOFs相结合的ILs/MOFs复合材料捕集分离CO₂的研究进展，主要包括ILs负载于MOFs材料和对MOFs进行改性的吸附分离、MOFs材料分散于ILs中形成多孔液体的吸收分离、膜分离等方法的研究现状，同时，深入探讨了各方法的优点和不足之处，并对ILs/MOFs复合材料在CO₂捕集分离中的应用前景和发展趋势进行了展望。

关键词: 金属有机骨架材料, 离子液体, 复合材料, CO₂捕集分离

CLC Number:

CAO Mingmin, HAN Chengle, YANG Fang, CHEN Yuhuan. CO₂ capture and separation by ionic liquid-metal organic framework composite materials[J]. Chemical Industry and Engineering Progress, 2023, 42(11): 5831-5841.

曹明敏, 韩铖乐, 杨芳, 陈玉焕. 离子液体/金属有机框架复合材料捕集分离CO₂[J]. 化工进展, 2023, 42(11): 5831-5841.

Figures/Tables 7

References 69

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体系			吸附量	理想选择性α		文献
	ILs	MOFs	吸附量	CO₂/N₂	CO₂/CH₄	文献
MOFs@ILs	30%（质量分数）[BMIm][MeSO₃]	ZIF-8	约12.5mL(STP)/g	约1.5	约2	[8]
	30%（质量分数）[BMIm][CF₃SO₃]	ZIF-8	约11.8mL(STP)/g	约0.7	约3	[8]
	30%（质量分数）[BMIm][MeSO₄]	ZIF-8	约12.7mL(STP)/g	约3.3	约1.8	[8]
	30%（质量分数）[BMIm][OCSO₄]	ZIF-8	约5.5mL(STP)/g	约0.6	约1.4	[8]
	5%（质量分数）[BMIm][AC]	HKUST-1	4.4mmol/g			[10]
	10%（质量分数）[BMIm][AC]	HKUST-1	2.9mmol/g			[10]
	20%（质量分数）[BMIm][AC]	HKUST-1	1.9mmol/g			[10]
	3.44%（质量分数）[BMIm][BF₄]	UiO-66	约32cm³/g	8.1		[21]
	7.8%（质量分数）[BMIm][BF₄]	ZIF-8	约12cm³/g	7.5		[21]
	2.38%（质量分数）[BMIm][BF₄]	CuBTC	约8cm³/g	15.3		[21]
	30%（质量分数）[EMIm][DEP]	CuBTC	约44mL/g		7.4	[22]
	30%（质量分数）[BMIm][SCN]	ZIF-8	约6.5mL/g	约11	约5	[23]
	5%（质量分数）[BMIm][BF₄]	ZIF-8	约250mL/g	15.81	5.57	[24]
	9.3%（摩尔分数）[BMIm]₂[CoCl₄]	ZIF-8	0.43mmol/g	7.5	2.7	[26]
	9.3%（摩尔分数）[BMIm]₂[NiCl₄]	ZIF-8	0.40mmol/g	7.5	2.7	[26]
	9.3%（摩尔分数）[BMIm]₂[FeCl₄]	ZIF-8	0.41mmol/g	7.1	2.8	[26]
	9.3%（摩尔分数）[BMIm]₂[Co(NCS)₄]	ZIF-8	0.30mmol/g	6.4	2.4	[26]
	9.3%（摩尔分数）[BMIm]₂[MnCl₄]	ZIF-8	0.32mmol/g	7.9	3.3	[26]
	50%（质量分数）[EMIm][DCN]	MIL-101(Al)	约3.2mmol/g			[27]
	PIL	MIL-101(Cr)	62cm³/g			[39]
	20%（质量分数）[BMIm][BF₄]	ZIF-8	10.5mL(STP)/g	约8	约3	[40]
IL@MOFs	[C₂OHMIM][DCA]	ZIF-8	3mL(STP)/g		11	[16]
IL@MOFs	[HemIm][DCA]	ZIF-8	8.6cm³/g		30	[16]
IL@MOFs@IL	[TETA]L	ZIF-8	1.53mmol/g	1688^①	260^②	[17]
IL-MOFs	[PMIm][SO₃]-NaCl	UiO-67	47.9cm³/g	44.21^②		[47]
	[NAIm]Br	ZIF-67	24.8cm³/g			[50]
	PIL-NH₂	Cu₃(BTC)₂	19.5cm³/g			[52]

体系			吸附量	理想选择性α		文献
	ILs	MOFs	吸附量	CO₂/N₂	CO₂/CH₄	文献
MOFs@ILs	30%（质量分数）[BMIm][MeSO₃]	ZIF-8	约12.5mL(STP)/g	约1.5	约2	[8]
	30%（质量分数）[BMIm][CF₃SO₃]	ZIF-8	约11.8mL(STP)/g	约0.7	约3	[8]
	30%（质量分数）[BMIm][MeSO₄]	ZIF-8	约12.7mL(STP)/g	约3.3	约1.8	[8]
	30%（质量分数）[BMIm][OCSO₄]	ZIF-8	约5.5mL(STP)/g	约0.6	约1.4	[8]
	5%（质量分数）[BMIm][AC]	HKUST-1	4.4mmol/g			[10]
	10%（质量分数）[BMIm][AC]	HKUST-1	2.9mmol/g			[10]
	20%（质量分数）[BMIm][AC]	HKUST-1	1.9mmol/g			[10]
	3.44%（质量分数）[BMIm][BF₄]	UiO-66	约32cm³/g	8.1		[21]
	7.8%（质量分数）[BMIm][BF₄]	ZIF-8	约12cm³/g	7.5		[21]
	2.38%（质量分数）[BMIm][BF₄]	CuBTC	约8cm³/g	15.3		[21]
	30%（质量分数）[EMIm][DEP]	CuBTC	约44mL/g		7.4	[22]
	30%（质量分数）[BMIm][SCN]	ZIF-8	约6.5mL/g	约11	约5	[23]
	5%（质量分数）[BMIm][BF₄]	ZIF-8	约250mL/g	15.81	5.57	[24]
	9.3%（摩尔分数）[BMIm]₂[CoCl₄]	ZIF-8	0.43mmol/g	7.5	2.7	[26]
	9.3%（摩尔分数）[BMIm]₂[NiCl₄]	ZIF-8	0.40mmol/g	7.5	2.7	[26]
	9.3%（摩尔分数）[BMIm]₂[FeCl₄]	ZIF-8	0.41mmol/g	7.1	2.8	[26]
	9.3%（摩尔分数）[BMIm]₂[Co(NCS)₄]	ZIF-8	0.30mmol/g	6.4	2.4	[26]
	9.3%（摩尔分数）[BMIm]₂[MnCl₄]	ZIF-8	0.32mmol/g	7.9	3.3	[26]
	50%（质量分数）[EMIm][DCN]	MIL-101(Al)	约3.2mmol/g			[27]
	PIL	MIL-101(Cr)	62cm³/g			[39]
	20%（质量分数）[BMIm][BF₄]	ZIF-8	10.5mL(STP)/g	约8	约3	[40]
IL@MOFs	[C₂OHMIM][DCA]	ZIF-8	3mL(STP)/g		11	[16]
IL@MOFs	[HemIm][DCA]	ZIF-8	8.6cm³/g		30	[16]
IL@MOFs@IL	[TETA]L	ZIF-8	1.53mmol/g	1688^①	260^②	[17]
IL-MOFs	[PMIm][SO₃]-NaCl	UiO-67	47.9cm³/g	44.21^②		[47]
	[NAIm]Br	ZIF-67	24.8cm³/g			[50]
	PIL-NH₂	Cu₃(BTC)₂	19.5cm³/g			[52]

填料	聚合物基质	填料质量分数 /%	操作条件		渗透率 /bar	选择性		文献
填料	聚合物基质	填料质量分数 /%	T/K	Δp/bar	渗透率 /bar	CO₂/N₂	CO₂/CH₄	文献
6%（体积分数）[BMIm][Tf₂N]/ZIF-8	PSF		303	6	约312	100	41	[18]
2%（质量分数）[EMIm][C(CN)₃]/Mg-MOF-74	Matrimid®5218	2	303	0.7		36.13		[57]
2%（质量分数）TMGA/MOF-5	Matrimid®5218	2	303	0.7		35.48		[57]
8%（质量分数）[BMIm][PF₆]/ZIF-8	Pebax	25	298	2	117	84.5		[58]
50%（质量分数）[C₃NH₂BIm][Tf₂N]/NH₂-MIL-101(Cr)	PIM-1	5	298	3	2979	37.24		[44]
67%（质量分数）[EMIm][Tf₂N]/HKUST-1	6FDA-Durene Polyimide	30	298	1.985	1101.6	27.1	29.3	[59]
83%（质量分数）[BMIm][Tf₂N]/UiO-66-NH₂	PIM-1	10	293	1	8283.4	12.3	22.5	[60]
5%（质量分数）[BMIm][BF₄]/ZIF-67	6FDA-Durene Polyimide	10	298	2	779.01	18.48	18.76	[61]
5%（质量分数）[BMIm][BF₄]/ZIF-67	6FDA-Durene Polyimide	20	298	2	1254.64	25.70	24.00	[61]
5%（质量分数）[EMIm][Tf₂N]/ZIF-67	6FDA-Durene Polyimide	10	298	2	1030.9	20.87	19.40	[61]
5%（质量分数）[EMIm][Tf₂N]/ZIF-67	6FDA-Durene Polyimide	20	298	2	1426	25.28	25.49	[61]
5%（质量分数）[BMIm][Tf₂N]/ZIF-67	6FDA-Durene Polyimide	10	298	2	672	23.54	22.77	[61]
5%（质量分数）[BMIm][Tf₂N]/ZIF-67	6FDA-Durene/(P)	20	298	2	889	28.09	28.05	[61]
[EMIm][Tf₂N]/ZIF-8	P[VBIm][Tf₂N]	25.8	308	3.5	1062.4	24.2	12.34	[62]
[BMIm][BF₄]/Zr-Fc MOF	Polycarbonate		293	0.49	66.8	216.9	41.7	[67]

填料	聚合物基质	填料质量分数 /%	操作条件		渗透率 /bar	选择性		文献
填料	聚合物基质	填料质量分数 /%	T/K	Δp/bar	渗透率 /bar	CO₂/N₂	CO₂/CH₄	文献
6%（体积分数）[BMIm][Tf₂N]/ZIF-8	PSF		303	6	约312	100	41	[18]
2%（质量分数）[EMIm][C(CN)₃]/Mg-MOF-74	Matrimid®5218	2	303	0.7		36.13		[57]
2%（质量分数）TMGA/MOF-5	Matrimid®5218	2	303	0.7		35.48		[57]
8%（质量分数）[BMIm][PF₆]/ZIF-8	Pebax	25	298	2	117	84.5		[58]
50%（质量分数）[C₃NH₂BIm][Tf₂N]/NH₂-MIL-101(Cr)	PIM-1	5	298	3	2979	37.24		[44]
67%（质量分数）[EMIm][Tf₂N]/HKUST-1	6FDA-Durene Polyimide	30	298	1.985	1101.6	27.1	29.3	[59]
83%（质量分数）[BMIm][Tf₂N]/UiO-66-NH₂	PIM-1	10	293	1	8283.4	12.3	22.5	[60]
5%（质量分数）[BMIm][BF₄]/ZIF-67	6FDA-Durene Polyimide	10	298	2	779.01	18.48	18.76	[61]
5%（质量分数）[BMIm][BF₄]/ZIF-67	6FDA-Durene Polyimide	20	298	2	1254.64	25.70	24.00	[61]
5%（质量分数）[EMIm][Tf₂N]/ZIF-67	6FDA-Durene Polyimide	10	298	2	1030.9	20.87	19.40	[61]
5%（质量分数）[EMIm][Tf₂N]/ZIF-67	6FDA-Durene Polyimide	20	298	2	1426	25.28	25.49	[61]
5%（质量分数）[BMIm][Tf₂N]/ZIF-67	6FDA-Durene Polyimide	10	298	2	672	23.54	22.77	[61]
5%（质量分数）[BMIm][Tf₂N]/ZIF-67	6FDA-Durene/(P)	20	298	2	889	28.09	28.05	[61]
[EMIm][Tf₂N]/ZIF-8	P[VBIm][Tf₂N]	25.8	308	3.5	1062.4	24.2	12.34	[62]
[BMIm][BF₄]/Zr-Fc MOF	Polycarbonate		293	0.49	66.8	216.9	41.7	[67]

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CO₂ capture and separation by ionic liquid-metal organic framework composite materials

离子液体/金属有机框架复合材料捕集分离CO₂

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