金属有机框架材料对非二氧化碳温室气体捕捉研究进展

doi:10.11949/0438-1157.20221183

摘要/Abstract

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

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

中图分类号:

TQ 028.1⁺5

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.

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.

图/表 12

表1 温室气体的GWP值/GTP值及寿命［8］

Table 1 Global warming potential （GWP）， global temperature potential （GTP） and lifetime of green house gases［8］

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

表2 MOFs对CH4/N2的分离性能

Table 2 MOFs separation performance for CH4/N2

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]

图1 ATC-Cu的晶体结构(a)；ATC-Cu对CH4和N2的吸附等温线(b)；在298 K、1 bar下各材料与ATC-Cu的吸附容量与选择性对比(c)；普通CH4吸附剂与纳米阱的对比(d)[33]

Fig.1 Illustration of the crystal structure of ATC-Cu (a)； The methane and nitrogen adsorption isotherm for ATC-Cu at 273 and 298 K (b)； The CH4/N2 selectivity for high-performance materials at 1 bar and 298 K (c)； The comparison of traditional methane adsorbent and nano-trap (d)[33]

图 2 Ni(ina)2的配体与结构模型(a)；在298 K、1 bar下各材料与Al-CDC的吸附容量与选择性对比(b) [27]

Fig.2 Illustration of the crystal structure of Ni(ina)2 (a)； Comparison of IAST selectivity of CH4 uptake for previously reported MOFs with Al-CDC (b)[27]

表3 N2O排放组分的物理性质［56］

Table 3 Physical properties of N2O emission components［56］

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

表4 MOFs对N2O/CO2的分离性能

Table 4 MOFs separation performance for N2O/CO2

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]

图3 DFT计算的CO2与N2O在Fe3+-F-，开放Fe3+位点和开放Fe2+位点上的作用模型[60]紫色—三价铁; 绿色—二价铁; 灰色—碳; 深蓝色—氮; 红色—氧; 浅蓝色—氟

Fig.3 The DFT-calculated adsorption configurations of CO2 and N2O on the Fe3+-F–, open-Fe3+ site and open Fe2+ sites in MIL-100(Fe), using a cluster model[60]

图4 在298 K和1 bar时，NU-1000-PhTz中吸附的CO2和N2的质量中心概率密度等值线图[57]

Fig.4 Contour plots of the center-of-mass probability densities of adsorbed CO2 and N2O in NU-1000-PhTz at 298 K and 1 bar[57]

图5 通过pcu拓扑基本单元的孔径和关键参数的变化来说明LIFM-W2中骨架的3D变化对不同芳香族客体的响应(a)；R22和R134a在273 K和298 K时的吸附等温线[(b)、(c)]；使用LIFM-W2在298 K时N2/R22/R134a混合气体（99.8∶0.01∶0.01，体积比）的柱穿透曲线(d)[23]

Fig.5 Representative 3D variations of the framework in LIFM-W2 responsive to different aromatic guests, illustrated by the changes of pore size and key parameters of the basic unit of the topologically simplified pcu net (a)；R22 and R134a uptakes at 273 K and 298 K [(b),(c)]；Column breakthrough curves of N2/R22/R134a mixed gases (99.8 : 0.01 : 0.01, volume ratio) at 298 K by using LIFM-W2 (d) [23]

表5 MOFs对SF6/N2分离性能

Table 5 MOFs separation performance for SF6/N2

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]

图6 Cu-MOF-NH2的结构模型，金属桨轮单元[Cu2(CO2)4]和弯曲的NH2-TPTC连接器组成(a)；Cu-MOF-NH2空腔中杯芳烃类似微环境的表征(b)；0.1 bar下SF6吸附容量及298 K和1.0 bar下预测的气体混合物(SF6∶N2=10∶90)的选择性(c)[87]

Fig.6 Illustration of the identified top-performers MOF hereafter labeled Cu-MOF-NH2 consisting of dimeric metal-paddlewheel units [Cu2(CO2)4] and bent NH2-TPTC linkers (a)；Representation of the calix arene-analogous microenvironments present in the cavity of Cu-MOF-NH2 (b)； The SF6 uptake as a single component at 0.1 bar and the IAST selectivity predicted at 298 K and 1.0 bar for the gas mixture (SF6∶N2=10∶90), respectively (c)[87]

图7 Cu(peba)2、Ni(pba)2和Ni(ina)2的结构模型(a)；三种材料在298 K下的SF6和N2吸附等温线[(b)~(d)]；使用IAST计算三种MOF在298 K下(SF6/N2体积比1/9)的SF6/N2选择性(e); 比较298 K和1 bar下的SF6/N2 (1/9) IAST选择性，以及Ni(ina)2、Ni(pba)2、Cu(peba)2和其他高性能材料在298 K和0.1 bar下的SF6吸附容量(f)； Ni(ina)2中SF6吸附结合位点的计算(g) [79]

Fig.7 The pore structures of Cu(peba)2, Ni(pba)2 and Ni(ina)2 (a); SF6 and N2 adsorption isotherms of the three materials at 298 K [(b)-(d)]; SF6/N2 selectivity of the three MOFs calculated at 298 K (SF6/N2 volume ratio 1/9) using IAST (e); Comparison of SF6/N2 (1/9) IAST selectivities at 298 K and 1 bar and SF6 uptakes at 298 K and 0.1 bar in Ni(ina)2, Ni(pba)2, Cu(peba)2 and other top-performance materials (f); The calculated adsorption binding sites of SF6 in Ni(ina)2 (g)[79]

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