The progress of metal-organic frameworks for non-CO2 greenhouse gases capture

doi:10.11949/0438-1157.20221183

Abstract

Abstract:

Along with the extensive research of global warming, non-carbon dioxide greenhouse gases have gained increasing attention recently. Because of their large temperature-rising effect and long lifetime, they can generate huge greenhouse effect, so they have become a research hotspot. Especially, efficient capture of non-carbon dioxide greenhouse gases is a new challenge. Adsorptive separation is an energy efficient technology which relies on advanced porous sorbents. Metal organic framework (MOFs) provide new opportunities for the capture of non-carbon dioxide greenhouse gases because of their diverse structures, controllable pore features, and open metal sites. In this review article, the research results of MOF materials for non-carbon dioxide greenhouse gas separation in recent years are summarized, and the separation mechanism of each material is analyzed. The challenges and opportunities of the future research on MOFs for non-carbon dioxide greenhouse gas separation has been discussed.

Key words: metal organic frameworks, non-CO₂ greenhouse gases, adsorption, adsorption capacity, selectivity

摘要：

随着全球暖化研究的深入，非二氧化碳温室气体（非二气体）日益受到重视，其温升效应大，寿命长，能够带来巨大的温室效应，因而成为近年来的研究热点。其中对非二气体的高效捕捉是目前面临的难点和新挑战。多孔材料吸附捕捉是一种低能耗的气体捕集分离技术，关键在于高效的吸附剂开发。金属-有机框架材料（MOFs）因其结构多样，孔道的高度可调控性能，以及具有丰富的开放金属位点等特点为非二气体的分离和捕捉提供了新的机遇。以此为主题，总结了近年来MOF材料在非二气体分离方面的研究成果，分析了各材料的分离机理与性能，展望了未来MOFs材料在非二气体分离领域的挑战与机遇。

关键词: 金属有机框架材料, 非二氧化碳温室气体, 吸附捕集, 吸附容量, 选择性

CLC Number:

TQ 028.1⁺5

Muzi LI, Guowei JIA, Yanlong ZHAO, Xin ZHANG, Jianrong LI. The progress of metal-organic frameworks for non-CO₂ greenhouse gases capture[J]. CIESC Journal, 2023, 74(1): 365-379.

李沐紫, 贾国伟, 赵砚珑, 张鑫, 李建荣. 金属有机框架材料对非二氧化碳温室气体捕捉研究进展[J]. 化工学报, 2023, 74(1): 365-379.

Figures/Tables 12

References 87

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气体名称	分子式	寿命/a	GWP 20	GWP 100	GWP 500	GTP 50	GTP 100
二氧化碳	CO₂	—	1	1	1	1	1
甲烷	CH₄	11.8	81.2	27.9	7.95	11	5.38
氧化亚氮	N₂O	109	273	273	130	290	233
氢氟化碳(HFCs)
HFC-23	CHF₃	228	12400	14600	10500	15400	15100
HFC-32	CH₂F₂	5.4	2690	771	220	181	142
HFC-125	CHF₂CF₃	30	6740	3740	1110	3300	1300
HFC-134a	CH₂FCF₃	147	4140	1530	436	733	306
HFC-143a	CH₃CF₃	51	7840	5810	1940	5910	3250
HFC-152a	CH₃CHF₂	1.6	591	164	46.8	36.5	29.8
HFC-227ea	CF₃CHFCF₃	36	5850	3600	1100	3400	1490
HFC-236fa	CF₃CH₂CF₃	213	7450	8690	6040	9200	88700
HFC-245fa	CHF₂CH₂CF₃	7.9	3170	962	274	262	180
全氟化碳(PFCs)
PFC-14	CF₄	50000	5300	7380	34100	7660	9050
PFC-116	C₂F₆	10000	8940	12400	10600	12900	15200
六氟化硫	SF₆	3200	18300	25200	17500	26200	30600
三氟化氮	NF₃	569	13400	17400	18200	18200	20000

气体名称	分子式	寿命/a	GWP 20	GWP 100	GWP 500	GTP 50	GTP 100
二氧化碳	CO₂	—	1	1	1	1	1
甲烷	CH₄	11.8	81.2	27.9	7.95	11	5.38
氧化亚氮	N₂O	109	273	273	130	290	233
氢氟化碳(HFCs)
HFC-23	CHF₃	228	12400	14600	10500	15400	15100
HFC-32	CH₂F₂	5.4	2690	771	220	181	142
HFC-125	CHF₂CF₃	30	6740	3740	1110	3300	1300
HFC-134a	CH₂FCF₃	147	4140	1530	436	733	306
HFC-143a	CH₃CF₃	51	7840	5810	1940	5910	3250
HFC-152a	CH₃CHF₂	1.6	591	164	46.8	36.5	29.8
HFC-227ea	CF₃CHFCF₃	36	5850	3600	1100	3400	1490
HFC-236fa	CF₃CH₂CF₃	213	7450	8690	6040	9200	88700
HFC-245fa	CHF₂CH₂CF₃	7.9	3170	962	274	262	180
全氟化碳(PFCs)
PFC-14	CF₄	50000	5300	7380	34100	7660	9050
PFC-116	C₂F₆	10000	8940	12400	10600	12900	15200
六氟化硫	SF₆	3200	18300	25200	17500	26200	30600
三氟化氮	NF₃	569	13400	17400	18200	18200	20000

材料	选择性	吸附容量/ (cm³ CH₄/g)	压力/bar	温度/ K	文献
Ni(ina)₂	15.8^①	40.8	1	298	[27]
Al-CDC	13.0^①	29.24	1	298	[28]
Co(C₄O₂)₂(OH)₂	12.5^①	8.26	1	298	[29]
Al-Fum	11.7^①	25.54	1	298	[30]
SB-MOF	11.5^①	26.15	1	298	[31]
Cu-MOF	11.0^①	13.70	1	298	[32]
ATC-Cu	9.0^①	62.5	1	298	[33]
Ni(3-ain)₂	9.0^①	46.7	1	298	[27,34]
MIL-160	8.9^①	10.53	1	298	[30，35]
Cu(INA)₂	8.3^①	16.07	1	298	[34]
CAU-10-H	7.2^①	16.58	1	298	[30]
MIL-53	7.1^①	12.77	1	298	[30]
Zn(CH₃COO)₂·H₂O	7.0^①	24.64	1	298	[36]
Ni-BPZ	6.6^①	34.94	1	298	[37]
[Ni(HCOO)₆]	6.1^①	17.47	1	298	[38]
ZIF-8	5.2	90.05	1	196	[39]
UiO-66-Br₂	5.1^①	11.41	1	298	[35]
[Co(HCOO)₆]	5.1^①	10.98	1	298	[38]
Cu(OTf) 2D	4.8^①	5.7	1	298	[40]
Ni(2-ain)₂	4.2^①	6.8	1	298	[27]
MOF-177	4.0^①	12.28	1	298	[41]
Ni-MOF-74	3.8^①	31.74	1	298	[42]
HKUST-1	3.7^①	18.35	1	298	[43]
Cu(OTf) 3D	3.2^①	7.9	1	298	[39-40]
MIL-100(Cr)	3^①	12.32	1	298	[42]
MIL-100(V)	3^①	4.98	1	298	[44]
Co-MOF-74	3^①	28.57	1	298	[31, 42]
Mg-MOF-74	1.5^①	33.86	1	298	[42]
Ni(pba)₂	1.6^①	17.1	1	298	[27]
MOF-5	1.1^①	1.72	1	298	[41]
V₂Cl_2.8(btdd)	>20^②	42.56	1	298	[45]
MIL-101(Cr)	5~10^②	21.28(1 bar)	0.1~10	283	[46]
MIL-100(Cr)	8^②	35.84	1	293	[47]
TYUT-96Cr	4.6^②	约25	1	298	[48]

材料	选择性	吸附容量/ (cm³ CH₄/g)	压力/bar	温度/ K	文献
Ni(ina)₂	15.8^①	40.8	1	298	[27]
Al-CDC	13.0^①	29.24	1	298	[28]
Co(C₄O₂)₂(OH)₂	12.5^①	8.26	1	298	[29]
Al-Fum	11.7^①	25.54	1	298	[30]
SB-MOF	11.5^①	26.15	1	298	[31]
Cu-MOF	11.0^①	13.70	1	298	[32]
ATC-Cu	9.0^①	62.5	1	298	[33]
Ni(3-ain)₂	9.0^①	46.7	1	298	[27,34]
MIL-160	8.9^①	10.53	1	298	[30，35]
Cu(INA)₂	8.3^①	16.07	1	298	[34]
CAU-10-H	7.2^①	16.58	1	298	[30]
MIL-53	7.1^①	12.77	1	298	[30]
Zn(CH₃COO)₂·H₂O	7.0^①	24.64	1	298	[36]
Ni-BPZ	6.6^①	34.94	1	298	[37]
[Ni(HCOO)₆]	6.1^①	17.47	1	298	[38]
ZIF-8	5.2	90.05	1	196	[39]
UiO-66-Br₂	5.1^①	11.41	1	298	[35]
[Co(HCOO)₆]	5.1^①	10.98	1	298	[38]
Cu(OTf) 2D	4.8^①	5.7	1	298	[40]
Ni(2-ain)₂	4.2^①	6.8	1	298	[27]
MOF-177	4.0^①	12.28	1	298	[41]
Ni-MOF-74	3.8^①	31.74	1	298	[42]
HKUST-1	3.7^①	18.35	1	298	[43]
Cu(OTf) 3D	3.2^①	7.9	1	298	[39-40]
MIL-100(Cr)	3^①	12.32	1	298	[42]
MIL-100(V)	3^①	4.98	1	298	[44]
Co-MOF-74	3^①	28.57	1	298	[31, 42]
Mg-MOF-74	1.5^①	33.86	1	298	[42]
Ni(pba)₂	1.6^①	17.1	1	298	[27]
MOF-5	1.1^①	1.72	1	298	[41]
V₂Cl_2.8(btdd)	>20^②	42.56	1	298	[45]
MIL-101(Cr)	5~10^②	21.28(1 bar)	0.1~10	283	[46]
MIL-100(Cr)	8^②	35.84	1	293	[47]
TYUT-96Cr	4.6^②	约25	1	298	[48]

分子	动力学直径/Å	偶极矩/D^①	极化率/(C·m²/V)	四极矩/m²
N₂O	3.30	0.17	3.08	3
CO₂	3.30	0	2.93	4.3
N₂	3.64	0	1.74	1.4

The progress of metal-organic frameworks for non-CO₂ greenhouse gases capture

金属有机框架材料对非二氧化碳温室气体捕捉研究进展

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材料	N₂O/CO₂选择性	N₂O吸附容量/(ml/g)	压力/bar	温度/K	文献
MIL-101(Cr)-NH₂	1.91	113.76	1	298	[58]
MIL-100(Fe)	1.84	105.27	1	298	[60]
ZIF-7	1.4~1.7	56	1	298	[61]
MIL-101(Cr)	1.49	122	1	298	[58]
ZIF-8	1.30	31.1	1	298	[62]
MIL-101(Cr)-Br	1.30	57.78	1	298	[58]
UiO-66	1.29	96.9	1	298	[62]
HKUST-1	1.20	87.6	1	298	[62]
NU-1000-PhTz	1.10	35.8	1	298	[57]
MIL-101(Cr)-NO₂	1.02	53.31	1	298	[58]
MIL-100(Cr)	1	129.4	1	298	[59]
MOF-5	—	20.4	1	298	[41]
Ni-MOF	—	63	1	298	[63]
ELM-11	—	1.46	1	298	[64]
ELM-12	—	19.26	1	298	[64]
MIL-53(Al)	—	60.48	1	298	[64]

材料	SF₆/N₂选择性	SF₆吸附容量/(cm³/g)	压力/bar	温度/K	文献
Ni(NDC)(TED)_0.5	750	61.86	1	298	[77]
SBMOF-1	727	22.8	1	298	[78]
Ni(ina)₂	375.1	63.7	1	298	[79]
Zn-MOF-74	313	85.12	1	298	[80]
Cu-MOF-NH₂	266	176.51	1	298	[81]
Ni(pba)₂	200.6	78.5	1	298	[79]
Co-MOF-74	52.9	116.48	1	298	[80]
UU-200	44.81	24.69	1	298	[82]
UiO-67	37	133.6	1	298	[83]
Mg-MOF-74	32.9	134.4	1	298	[80]
Cu(peba)₂	18.2	52.8	1	298	[79]
MIL-101	—	276	18	298	[84]
Cu₃(BTC)₂	—	107.07	1	298	[84]
Co₂(1,4-bdc)₂(dabco)	—	75.94	1	298	[84]
Zn₄O(btb)	—	69.89	1	298	[84]
MIL-100(Fe)	—	65.86	1	298	[84]
Zn₄O(dmcpz)₃	—	56.9	1	298	[84]
DUT-9	—	52	18	298	[84]

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