CN113881061A - Metal organic framework porous material and preparation method and application thereof - Google Patents
Metal organic framework porous material and preparation method and application thereof Download PDFInfo
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Abstract
The application discloses a metal organic framework porous material and a preparation method and application thereof. The metal organic framework porous material has a chemical formula shown as a formula I; [ M ] A3L4(QF6)3]nFormula I; m is a positive divalent transition metal ion; l is an organic ligand; QF6Is an anion. The porous material of the metal organic framework changes the pore channel structure of the porous material of the metal organic framework through the selection of the organic ligand, and realizes C2H2And C3H4Ultra-high adsorption of (C)2H2/C2H4And C3H4/C3H6The method effectively solves the problem that the adsorption capacity and the separation selectivity cannot be compatible.
Description
Technical Field
The application relates to a metal organic framework porous material and a preparation method and application thereof, belonging to the technical field of gas separation.
Background
The energy consumed by the gas separation process is a very important part of the total global energy consumption, especially C2-C3Alkyne/alkene separation. C2H4Is a basic chemical raw material for synthetic fibers and rubbers, and is also used to manufacture vinyl chloride, styrene, and ethanol. C3H6Is a second important petrochemical feedstock and is an essential component in the manufacture of various chemicals, including polypropylene. C2H4And C3H6Produced mainly by steam cracking of hydrocarbons or petroleum fractions in the petrochemical industry, often contaminated with traces of C2H2And C3H4。C2H2And C3H4Not only poison the catalyst in the polymerization reaction, but also reduce the quality of the polymer. However, due to their close molecular size and kinetic diameter, C is effectively separated2H2/C2H4And C3H4/C3H6It is very difficult. The traditional separation technology, such as low-temperature distillation, catalytic hydrogenation and the like, has high energy consumption and great environmental pollution. Therefore, it is urgently needed to find an efficient and energy-saving method for realizing C2H2/C2H4And C3H4/C3H6The separation is efficient.
Adsorptive separation is considered an energy efficient method that can drastically change the current energy intensive situation. Metal Organic Frameworks (MOFs) are widely used in gas adsorption separations because of their high porosity, high specific surface area, structural diversity and framework designability. Adsorption separation techniques based on MOFs have made unprecedented progress in the field of gas separation. In recent years, MOFs are at C2H2/CO2、C2H2/C2H4And C3H4/C3H6The separation aspect shows great potential. However, the trade-off between adsorption capacity and separation selectivity of porous MOFs materials remains a major obstacle to achieving efficient separations.
Disclosure of Invention
According to one aspect of the present application, there is provided a metal-organic framework porous material having a metal-organic framework altered by the selection of organic ligandsPore structure of porous material to realize C2H2And C3H4Ultra-high adsorption of (C)2H2/C2H4And C3H4/C3H6The method effectively solves the problem that the adsorption capacity and the separation selectivity cannot be compatible.
A metal organic framework porous material has a chemical formula shown as a formula I;
[M3L4(QF6)3]nformula I;
m is a positive divalent transition metal ion;
l is an organic ligand;
QF6is anion, wherein Q is any one selected from Si, Ti and Zr;
n represents the number of asymmetric structural units and takes infinite value;
the organic ligand is selected from any one of organic matters shown in a formula II;
wherein, R1, R2 and R3 are the same substituent groups and are selected from any one of methyl, hydroxyl, amino, nitro and fluorine.
Optionally, the metal element in the positive divalent transition metal ion is selected from any one of a Cu element, a Co element, a Ni element, a Zn element, a Mn element, and a Cd element.
Optionally, the specific surface area of the metal organic framework porous material is 700-1500 m2/gm2/g。
Optionally, the specific surface area of the metal-organic framework porous material is 700, 900, 1100, 1300, 1500m2/gm2Any value or range of values between any two values in/g.
Optionally, the pore diameter of the metal organic framework porous material is 0.6-1.0 nm.
Optionally, the pore size of the metal-organic framework porous material is any one of 0.6, 0.7, 0.8, 0.9, 1nm or a range between any two values.
Optionally, the metal-organic framework porous material has a chemical formula shown as formula III;
[Cu3(TMTPB)4(SiF6)3]nformula III;
TMTPB is 1,3, 5-trimethyl-2, 4, 6-tri (4-pyridyl) benzene;
n represents the number of asymmetric structural units and takes infinite value.
Optionally, the asymmetric structural unit of the metal organic framework porous material comprises two different proportions of copper ions and two different proportions of SiF6 2-And an organic ligand; two kinds of copper ions both adopt a coordination mode of six coordination, four nitrogen atoms on different ligands are firstly coordinated with the copper ions to form a two-dimensional layered structure, namely SiF6 2-As a column, a two-dimensional layered structure is constructed into a three-dimensional framework, and the outer three pyridine benzene rings are nearly vertical to the central benzene ring due to the existence of methyl on a ligand.
Optionally, the pore channels of the metal organic framework porous material along the c axis are hexagonal.
Optionally, the metal-organic framework porous material is of an orthorhombic system, space group Pbam.
Preferably, the unit cell parameter of the metal-organic framework porous material is
α＝β＝γ＝90°，
Z＝1。
According to another aspect of the present application, there is provided a method of preparing a metal organic framework porous material as defined in any one of the above, the method comprising the steps of:
mixing a solution I containing an organic ligand L and a solution containing a source M and an anion QF6And mixing and diffusing the solution II of the source to obtain the metal organic framework porous material.
Optionally, the source of M is selected from at least one of M-containing salts I.
Optionally, the salt I is at least one selected from M-containing nitrate, M-containing chloride, M-containing sulfate, M-containing tetrafluoroborate and M-containing acetate.
Optionally, the anion QF6The source being selected from the group consisting of anion-containing QF6At least one of salts II of (a).
Optionally, the salt II is selected from (NH)4)2QF6、Na2QF6At least one of (1).
Optionally, the solvent in the solution I is at least one selected from methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, dimethyl sulfoxide, tetrahydrofuran and acetone;
the solvent in the solution II is at least one selected from water and methanol.
Optionally, the concentration of the organic ligand L in the solution I is 1.5-20 mg/ml;
the concentration of the M source in the solution II is 10-50 mg/ml, and the anion QF6The concentration of the source is 6-20 mg/ml.
Optionally, the concentration of the M source is any one of 10, 20, 30, 40, 50mg/ml or a range between any two values, the anion QF6The concentration of the source is any one of 6, 8, 10, 12, 15, 18, 20mg/m or a range between any two values.
Preferably, the volume ratio of the solution I to the solution II is 1: 1-7.
Optionally, the volume ratio of the solution I to the solution II is 1:1, 1:2, 1:4, 1:6, 1: 7 or a range of values between any two values.
Alternatively, the mixing is dropping solution I into solution II.
The dripping is slow dripping, so that the stirring of the liquid level is avoided.
Optionally, the diffusion time is 5-20 d.
Optionally, the diffusion time is any one of 5, 6, 8, 10, 13, 15, 18, 20d or a range between any two values.
Optionally, the method further includes the following steps after the diffusion is finished:
and exchanging the diffusion product with methanol for 3-7 days, and vacuumizing for 5-10 hours at the temperature of 60-100 ℃ under high vacuum.
According to another aspect of the present application, there is provided a use of at least one of the metal-organic framework porous material described in any one of the above, and the metal-organic framework porous material prepared by the preparation method described in any one of the above as a gas adsorbent;
the gas is selected from C2H2、C2H4、C3H4、C3H6At least one of (1).
Optionally, the adsorbent is at 298K and 1bar, and C is2H2The adsorption capacity of the adsorbent is 130-170 cm3/g、C2H4Is 80-120 cm3/g、C3H4Is 140-180 cm3/g、C3H6120-160 cm3/g。
Optionally, the adsorbent is at 298K and 1bar, and C is2H2Has an adsorption capacity of 150cm3/g、C2H4Is 104cm3/g、C3H4Is 159cm3/g、C3H6Is 140cm3/g。
According to another aspect of the application, there is provided a use of at least one of the metal-organic framework porous material described in any one of the above, the metal-organic framework porous material prepared according to the preparation method described in any one of the above, in the separation of C2-C3 alkyne/C2-C3 alkene.
Alternatively, when the mixed gas flow rate is 2mL/min, C2H2/C2H4(1/99, v/v) protectionRetention time of 200-300 min/g, C3H4/C3H6(1/99, v/v) has a retention time of 500-700 min/g.
Alternatively, when the mixed gas flow rate is 2mL/min, C2H2/C2H4(1/99, v/v) a retention time of 230min/g, C3H4/C3H6The retention time of (1/99, v/v) was 590 min/g.
The metal organic framework porous material provided by the application shows ultrahigh water stability and thermal stability, and is compared with other anion porous materials, not only for C2H2And C3H4Has ultrahigh adsorption capacity and is suitable for C2H2/C2H4And C3H4/C3H6Has good separation effect, thereby effectively solving the problem that the adsorption capacity and the separation selectivity can not be compatible.
The metal organic framework porous material provided by the application can realize C2H2And C3H4Ultra-high adsorption of (C)2H2/C2H4And C3H4/C3H6The method effectively solves the problem that the adsorption capacity and the separation selectivity cannot be compatible.
In order to achieve the purpose of the invention, the technical scheme provided by the application is as follows:
the pore size and/or the channel structure of the MOFs are adjusted by changing the ligand and/or the metal ion. Meanwhile, the anion can ensure high binding affinity with the specific gas, thereby remarkably improving the separation performance. Based on the characteristics, the metal organic framework porous material provided by the application is shown in the specification C2H2/C2H4Separation and C3H4/C3H6The separation aspect shows excellent performance. Compared with most of the existing stable fluorine hybrid porous materials which are usually based on linear ligands, the obtained column layer structure has one-dimensional square pore channels. The present application is based on the trigonal ligand TMTPB (TMTPB ═ 1,3, 5-trimethyl)2,4, 6-tri (4-pyridyl) benzene) synthesizes a stable microporous material FJI-W1, and different frameworks with different pore passages can be obtained, thereby being more beneficial to gas separation. Unlike most fluorine hybrid porous materials with pcu topology, the metal organic framework porous materials provided herein exhibit hexagonal channels along the c-axis. Thermogravimetric analysis (TGA) and temperature-variable powder x-ray diffraction (VT-PXRD) experiments show that FJI-W1 has ultrahigh water stability and thermal stability. 77K of N2The adsorption isotherm shows that FJI-W1 has a high specific surface area (1376 m)2In terms of/g). By testing C at different temperatures2H2、C2H4、C3H4And C3H6The adsorption experiment of (3) shows that FJI-W1 is used for C2H2And C3H4Has high adsorption capacity. FJI-W1 was activated at high vacuum for a period of time at temperature and to achieve the best C by varying the flow rates used in the column breakthrough experiments2-C3Alkyne/alkene separation effect.
The structural formula of 1,3, 5-trimethyl-2, 4, 6-tri (4-pyridyl) benzene) is as follows:
the beneficial effects that this application can produce include:
(1) according to the metal organic framework porous material provided by the application, the pore size and/or the pore channel structure of the porous material MOFs are adjusted by changing the ligand and/or the metal ion. Meanwhile, the anion can ensure high binding affinity with the specific gas, thereby remarkably improving the separation performance.
(2) The metal organic framework porous material provided by the application has a large specific surface area, and the adsorption capacity of the material is improved.
(3) The metal organic framework porous material provided by the application can realize C2H2、C3H4、C3H4、C3H6Ultra-high adsorption of (C)2H2/C2H4And C3H4/C3H6The method effectively solves the problem that the prior adsorption capacity and separation selectivity can not be compatible.
(4) The metal organic framework porous material provided by the application has good water stability and thermal stability.
Drawings
FIG. 1 shows a coordination environment of FJI-W1 (a) and a three-dimensional framework structure along the c-axis direction (b);
FIG. 2 shows the adsorption isotherms of FJI-W1 at 298K for a single component gas, where (a) is C2H2And C2H4And (b) is C3H4And C3H6。
FIG. 3 shows a penetration cycle test curve for FJI-W1 column, where (a) C3H4/C3H6(1/99)；(b)C2H2/C2H4(1/99)；(c)C3H4/C3H6(50/50)；(d)C2H2/C2H4(50/50)。
FIG. 4 shows FJI-W1 vs. other MOFs (a) C at 298K, 1bar2H2Breakthrough time and C2H2The amount of adsorption; (b) c at 298K, 0.1bar3H4Breakthrough time and C3H4The adsorbed amount, wherein sample FJI-W1 of the present application corresponds to "This work" in the figure.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
The raw materials in the examples of the present application were all purchased commercially, unless otherwise specified.
In the examples of the present application, the structural data of the crystal is represented by
Collected by the Synergy Custom (Liquid MetalJet D2+) diffractometer. C. Analysis of H and N Trace elements an ElementarVario MICRO element analyzer was used.Powder X-ray diffraction data were collected using a Rigaku MiniFlex 600X-ray diffractometer using Cu-Ka (λ ═ 0.154 nm). Thermogravimetric analysis (TGA) was performed on a NETZSCH STA 449C apparatus at a heating rate of 10 ℃/min measured at 900 ℃ from room temperature under a nitrogen atmosphere. Temperature-variable powder X-ray diffraction (VT-PXRD) was measured by heating a sample to the desired temperature in air and holding for 20 minutes.
All reagents and solvents used were purchased from commercial sources and used without further purification.
TMTPB is 1,3, 5-trimethyl-2, 4, 6-tri (4-pyridyl) benzene) and has the following structural formula:
example 1
First, 3ml of a methanol solution containing 10mg of TMTPB was slowly added dropwise to a solution containing 18mg of (NH)4)2SiF6And 30mg Cu (NO)3)2·6H2Diffusion of O in 3ml of an aqueous solution at room temperature for two weeks gave dark blue rod-like crystals FJI-W1. Exchanging the fresh sample with methanol for 7 days, and vacuumizing at 80 ℃ for 10 hours to obtain a metal organic framework porous material FJI-W1, which belongs to an orthorhombic system and a space group Pbam with a single-cell parameter of
α＝β＝γ＝90°，
Z is 1, the coordination environment and the three-dimensional framework structure along the c-axis direction are respectively shown in FIGS. 1(a) and 1(b), the asymmetric structural unit comprises two copper ions with different proportions, and two SiFs with different proportions6 2-And an organic ligand. Two kinds of copper ions both adopt a coordination mode of six coordination, four nitrogen atoms on different ligands are firstly coordinated with the copper ions to form a twoMaintaining the layered structure, then SiF6 2-The two-dimensional layered structure is constructed into a three-dimensional framework as a column, and the existence of methyl on the ligand enables the three pyridine benzene rings at the outer part to be nearly vertical to the central benzene ring, so that hexagonal pore channels are presented along the c axis.
The experimental result shows that FJI-W1 has ultrahigh water stability and thermal stability.
N at 77K was collected in a liquid nitrogen bath using a Micromeritics 3Flex specific surface area and pore size analyzer2The saturated adsorption capacity of the adsorbent can reach 350cm3(iv)/g, corresponding FJI-W1 specific surface area of 1376m2G, pore diameter of 0.8 nm. C at 298K was collected in a water bath2H2、C2H4、C3H4And C3H6Adsorption isotherm of (1). As can be seen from FIG. 2, C was measured at 298K, 1bar2H2Has an adsorption capacity of 150cm3/g，C2H4Is 104cm3/g，C3H4Is 159cm3/g，C3H6Is 140cm3/g。
Column breakthrough experiments were performed on a fixed bed. A sample of activated FJI-W1 (0.7084g) was first packed into a stainless steel column (5mm (inside diameter). times.180 mm (length)) and the column ends were capped with quartz wool. The column was activated with He gas at 90 ℃ for 10 hours, and during the test, the mixed gas was allowed to flow through the packed bed at a constant flow rate, and the gas flowing out of the column was monitored by a Gas Chromatography (GC) detector. After each breakthrough, the samples were activated with He gas for 2 hours at 90 ℃. As a result, as shown in FIG. 3, C was obtained when the mixed gas flow rate was 2mL/min2H2/C2H4(1/99, v/v) a retention time of 230min/g, C3H4/C3H6The retention time of (1/99, v/v) was 590 min/g. The experimental result shows that FJI-W1 can effectively separate (a) C3H4/C3H6(1/99) and (b) C2H2/C2H4(1/99) a mixed gas of two components, and (C) C3H4/C3H6(50/50) and (d) C2H2/C2H4(50/50) in equal proportionThe mixed gas also has good separation effect. Three repeated experiments show that FJI-W1 has excellent separation stability.
Comparing the above-mentioned characterization and/or performance test results of FJI-W1 with MOF materials already reported in the prior art, it can be seen that:
1. FJI-W1 has a specific surface area of 1376m2/g, much higher than most fluorine-hybridized MOFs, e.g. SIFIX-Cu-TPA (1330 m)2/g)1，SIFSIX-1-Cu(1178m2/g)2，UTSA-200a(612m2/g)3，SIFSIX-2-Cu-i(503m2/g)2And SIFSIX-3-Ni (368 m)2/g)2。
2. At 298K, 1bar, FJI-W1 pairs of C2H2The adsorption capacity of (2) is up to 150cm3/g，C2H2/C2H4(1/99, v/v) has a retention time of about 230min/g, higher than UTSA-100a (96 cm) under the same conditions3/g，15min/g)4、SIFSIX-3-Zn(82cm3/g，36min/g)2And ZU-62-Ni (67 cm)3/g，167min/g)5。
3. Under the condition of 298K, 0.1bar, C3H4The adsorption capacity of (2) is up to 130cm3(ii) in terms of/g. Under the condition of 298K, 1bar, C3H4/C3H6The retention time of (1/99, v/v) was about 600 min/g. Higher than ZIF-8(32 cm) under the same conditions3/g，15min/g)6、ZJUT-1(24cm3/g，110min/g)7、JXNU-6a(57cm3/g，100min/g)8、ELM-12(57cm3/g，190min/g)9、SIFSIX-3-Ni(61cm3/g，230min/g)6And SIFSIX-2-Cu-i (72 cm)3/g，290min/g)6。
FIG. 4 shows FJI-W1 vs. other MOFs (a) C at 298K, 1bar2H2Breakthrough time and C2H2The amount of adsorption; (b) c at 298K, 0.1bar3H4Breakthrough time and C3H4The adsorbed amount, wherein sample FJI-W1 of the present application corresponds to "This work" in the figure.
From the above, the present inventionThe application can ensure that the metal organic framework porous material has a more reasonable pore channel structure by selecting the triangular ligand TMTPB, and can realize C2H2、C3H4、C3H4、C3H6Ultra-high adsorption of (C)2H2/C2H4And C3H4/C3H6The method effectively solves the problem that the prior adsorption capacity and separation selectivity can not be compatible.
Corresponding reports on the above prior art MOF materials are as follows:
1.Li,H.；Liu,C.；Chen,C.；Di,Z.；Yuan,D.；Pang,J.；Wei,W.；Wu,M.；Hong,M.,An Unprecedented Pillar-Cage Fluorinated Hybrid Porous Framework with Highly Efficient Acetylene Storage and Separation.AngewChemInt Ed2021,60,7547-7552.
2.Cui,X.；Chen,K.；Xing,H.；Yang,Q.；Krishna,R.；Bao,Z.；Wu,H.；Zhou,W.；Dong,X.；Han,Y.；Li,B.；Ren,Q.；Zaworotko,M.J.；Chen,B.,Pore chemistry and size control in hybrid porous materials for acetylene capture from ethylene.Science2016,353(6295),141-144.
3.Li,B.；Cui,X.；O'Nolan,D.；Wen,H.M.；Jiang,M.；Krishna,R.；Wu,H.；Lin,R.B.；Chen,Y.S.；Yuan,D.；Xing,H.；Zhou,W.；Ren,Q.；Qian,G.；Zaworotko,M.J.；Chen,B.,An Ideal Molecular Sieve for Acetylene Removal from Ethylene with Record Selectivity and Productivity.Adv Mater2017,29(47),1704210.
4.Hu,T.-L.；Wang,H.；Li,B.；Krishna,R.；Wu,H.；Zhou,W.；Zhao,Y.；Han,Y.；Wang,X.；Zhu,W.；Yao,Z.；Xiang,S.；Chen,B.,Microporous metal-organic framework with dual functionalities for highly efficient removal of acetylene from ethylene/acetylene mixtures.Nat Commun2015,6,7328.
5.Yang,L.；Jin,A.；Ge,L.；Cui,X.；Xing,H.,A novel interpenetrated anion-pillared porous material with high water tolerance afforded efficient C2H2/C2H4 separation.ChemCommun2019,55(34),5001-5004.
6.Li,L.；Wen,H.M.；He,C.；Lin,R.B.；Krishna,R.；Wu,H.；Zhou,W.；Li,J.；Li,B.；Chen,B.,A Metal-Organic Framework with Suitable Pore Size and Specific Functional Sites for the Removal of Trace Propyne from Propylene.AngewChemInt Ed2018,57(46),15183-15188.
7.Wen,H.-M.；Li,L.；Lin,R.-B.；Li,B.；Hu,B.；Zhou,W.；Hu,J.；Chen,B.,Fine-tuning of nano-traps in a stable metal-organic framework for highly efficient removal of propyne from propylene.J Mater Chem A2018,6(16),6931-6937.
8.Lin,Z.-T.；Liu,Q.-Y.；Yang,L.；He,C.-T.；Li,L.；Wang,Y.-L.,Fluorinated Biphenyldicarboxylate-Based Metal-Organic Framework Exhibiting Efficient Propyne/Propylene Separation.InorgChem2020,59(6),4030-4036.
9.Li,L.；Lin,R.-B.；Krishna,R.；Wang,X.；Li,B.；Wu,H.；Li,J.；Zhou,W.；Chen,B.,Flexible-Robust Metal-Organic Framework for Efficient Removal of Propyne from Propylene.J Am ChemSoc2017,139(23),7733-7736.
although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. A metal organic framework porous material is characterized in that the metal organic framework porous material has a chemical formula shown as a formula I;
[M3L4(QF6)3]nformula I;
m is a positive divalent transition metal ion;
l is an organic ligand;
QF6is anion, wherein Q is any one selected from Si, Ti and Zr;
n represents the number of asymmetric structural units and takes infinite value;
the organic ligand is selected from any one of organic matters shown in a formula II;
wherein, R1, R2 and R3 are the same substituent groups and are selected from any one of methyl, hydroxyl, amino, nitro and fluorine.
2. The metal-organic framework porous material according to claim 1, wherein the metal element in the positive divalent transition metal ion is selected from any one of a Cu element, a Co element, a Ni element, a Zn element, a Mn element, and a Cd element.
3. The metal-organic framework porous material as claimed in claim 1, wherein the specific surface area of the metal-organic framework porous material is 700-1500 m2/g；
Preferably, the pore diameter of the metal organic framework porous material is 0.6-1.0 nm.
4. The metal-organic framework porous material of claim 1, wherein the metal-organic framework porous material has a chemical formula as shown in formula III;
[Cu3(TMTPB)4(SiF6)3]nformula III;
TMTPB is 1,3, 5-trimethyl-2, 4, 6-tri (4-pyridyl) benzene;
n represents the number of asymmetric structural units and takes infinite value;
preferably, the pore channels of the metal organic framework porous material along the c axis are hexagonal;
preferably, the metal-organic framework porous material belongs to the orthorhombic system, space group Pbam;
preferably, the unit cell parameter of the metal-organic framework porous material is
Z＝1。
5. The method for preparing a metal organic framework porous material according to any one of claims 1 to 4, characterized by comprising the following steps:
mixing a solution I containing an organic ligand L and a solution containing a source M and an anion QF6And mixing and diffusing the solution II of the source to obtain the metal organic framework porous material.
6. The method according to claim 5, wherein the M source is at least one selected from M-containing salts I;
preferably, the salt I is at least one selected from nitrate containing M, chloride containing M, sulfate containing M, tetrafluoroborate containing M and acetate containing M;
preferably, the anion QF6The source being selected from the group consisting of anion-containing QF6At least one of salts II of (a);
preferably, said salt II is selected from (NH)4)2QF6、Na2QF6At least one of;
preferably, the solvent in the solution I is at least one selected from methanol, ethanol, N-dimethylformamide, N-dimethylacetamide, N-diethylformamide, dimethyl sulfoxide, tetrahydrofuran and acetone;
the solvent in the solution II is at least one selected from water and methanol;
preferably, the concentration of the organic ligand L in the solution I is 1.5-20 mg/ml;
the concentration of the M source in the solution II is 10-50 mg/ml, and the anion QF6The concentration of the source is 6-20 mg/ml;
preferably, the volume ratio of the solution I to the solution II is 1: 1-7;
preferably, the diffusion time is 5-20 d.
7. Use of at least one of the metal organic framework porous material according to any one of claims 1 to 4, the metal organic framework porous material prepared by the preparation method according to any one of claims 5 to 6 as a gas adsorbent;
the gas is selected from C2H2、C2H4、C3H4、C3H6At least one of (1).
8. The use according to claim 7, wherein the adsorbent is at 298K, 1bar, C2H2The adsorption capacity of the adsorbent is 130-170 cm3/g、C2H4Is 80-120 cm3/g、C3H4Is 140-180 cm3/g、C3H6120-160 cm3/g。
9. Use of at least one of the metal-organic framework porous materials of any one of claims 1 to 4, the metal-organic framework porous materials prepared by the preparation method of any one of claims 5 to 6 in the separation of C2-C3 alkyne/C2-C3 alkene.
10. Use according to claim 9, wherein C is the flow rate of the mixed gas at 2mL/min2H2/C2H4(1/99, v/v) has a retention time of 200-300 min/g, C3H4/C3H6(1/99, v/v) has a retention time of 500-700 min/g.
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