CN113583252A - Microporous metal organic framework Cu (Qc)2Preparation method of (1) - Google Patents
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Abstract
The invention relates to the technical field of hybrid materials, in particular to a microporous metal organic framework Cu (Qc)2The preparation method of (1); the invention relates to a microporous metal organic framework Cu (Qc)2The preparation method provides a simple, convenient and efficient room temperature synthesis MOF material Cu (Qc)2The method takes (Zn, Cu) hydroxyl double salt as an intermediate, and successfully synthesizes Cu (Qc) within 1-12 h at room temperature2Obtained Cu (Qc)2Has good carbon dioxide adsorption capacity.
Description
Technical Field
The invention relates toAnd the technical field of hybrid materials, in particular to a microporous metal organic framework Cu (Qc)2The preparation method of (1).
Background
Carbon dioxide is ubiquitous in many chemical, energy production processes or as an impurity in raw materials, and its presence can seriously affect the purity and utilization of products or raw materials, and thus there is an important practical need to separate carbon dioxide from industrial gases. For example, natural gas contains methane as a main component, but carbon dioxide (CO) in an amount of about 10%2) Carbon dioxide is usually removed beforehand to meet transportation standards, where pipeline natural gas is required to be CO2<3%, liquefied natural gas is CO2<50ppm。
In recent years, Metal-Organic Framework Materials (MOFs) have attracted much attention for their abundant topology and applications in gas storage or separation, ion exchange, catalysis, and even chemical sensors. The metal organic framework is a porous material, has the advantages of large specific surface area, adjustable pore diameter, strong adsorption capacity and the like, is assembled by metal ions and organic ligands, and the organic part of the metal organic framework can improve the interaction with a polymer matrix. These features make MOFs better dispersed in mixed matrix membranes.
Application number CN201110131882.1 discloses a microporous metal-organic framework material, a preparation method and applications thereof. In particular to a microporous metal-organic framework material based on isophthalic acid derivatives, a preparation method and application thereof. The chemical formula of the microporous metal-organic framework material is Zn (pybdc), wherein pybdc 2-is deprotonated 5- (1-pyrrolidinyl) -1, 3-phthalic acid, and n represents infinite chain of the structural unit. The metal-organic framework material is crystallized in a trigonal system, the space group is R-3m, and metal Zn is adopted2+In the tetrahedral center, 4 coordinates. The microporous metal-organic framework material has a one-dimensional pore channel structure along the c-axis direction, a methylene group of a five-membered pyrrole ring extends into the pore channel, the pore channel window has a size of about 4A, and the porosity is 18.6%. The material of the invention can be used for gas or solvent due to the pore canal in the structureSafe storage of the molecules.
Publication No. CN201911074884.4 discloses a preparation method of a copper-based microporous metal organic framework material and a gas separation application thereof, and the material is prepared on the basis of an organic ligand 3-hydroxyisonicotinic acid (3-OH-INA) and copper acetate which are simple in structure, cheap and easy to obtain and rich in coordination mode under the solvothermal condition. A unique serrated one-dimensional channel exists in the Cu-MOF structure, and the channel size is slightly larger than the low-carbon hydrocarbon molecular dynamics size, so that a structural basis is provided for the adsorption process of the gas. In addition, ligands regularly distributed in the pore channels provide multiple hydrogen bond action sites, and the action force of ethane gas molecules and the framework is enhanced, so that the effect of preferentially adsorbing ethane gas in ethane-ethylene mixed gas is realized, the ethylene purification task is completed in one adsorption period, and the energy consumption in the separation process is further reduced.
However, common MOFs are prepared under solvothermal conditions, and the pore size of MOFs is microporous and does not have the ability to sieve gases through pore size. The microporous metal organic framework particle filler obtained by direct drying is easy to agglomerate. And the flaky packing is stacked too densely, so that the permeation of gas is not facilitated, and the adsorption effect of the gas can be greatly influenced. Organic objects exist in the unactivated MOF structure, and can occupy the pore channels, reduce the adsorption sites of the gas and reduce the gas adsorption quantity.
Disclosure of Invention
Aiming at the defects in the prior art, the invention discloses a microporous metal organic framework Cu (Qc)2Belonging to the technical field of hybrid materials. Has corresponding excellent performance, large specific surface area, large micropore adsorption capacity, good water vapor stability and excellent carbon dioxide capture performance.
Microporous metal organic framework Cu (Qc)2The structural formula of the preparation method is shown as the following formula:
further, a microporous metalOrganic skeleton Cu (Qc)2The surface area of (A) is 180 to 320m2/g;
Further, a microporous metal organic framework Cu (Qc)2The pore volume of the micropores is 0.09-0.20 cm3/g;
Further, a microporous metal organic framework Cu (Qc)2The diameter of the micropores is 1.0-2.0 nm;
further, a microporous metal organic framework Cu (Qc)2The preparation method comprises the following steps:
s1: mixing the raw material A and the raw material B in an organic solvent, and performing ultrasonic treatment for 10 minutes to obtain an intermediate solution;
s2: mixing and stirring the intermediate solution and DMF containing quinoline-5-carboxylic acid, carrying out synthetic reaction for 10-16 h, adding a synergist, and continuing the reaction for 30-100 min;
s3: washing the product after the synthesis reaction with an organic solvent for 6-9 times to obtain Cu (Qc)2A dispersion liquid;
s4: carrying out suction filtration on the dispersion liquid to obtain purple powder, drying and activating at high temperature under vacuum condition to obtain the microporous metal organic framework Cu (Qc)2。
Further, the raw material A is ZnO;
further, the raw material B is Cu (BF)4)2•6H2O;
In the step one, the mass ratio of the raw material A to the raw material B is 0.15-0.3;
further, the organic solvent is one or a combination of DMF, ethanol or n-butanol;
further, the mass percent content of the quinoline-5-carboxylic acid is 1-10%;
further, the preparation method of the synergist comprises the following steps:
introducing nitrogen into a closed high-pressure reaction kettle according to the parts by weight; adding 12-22 parts of 1-allyl-3-vinylimidazole nitrate, 5-11 parts of mercaptopolyethylene glycol, 0.06-1.5 parts of 3-amino-4-mercaptoquinoline (CAS: 109543-48-8), 100 parts of ethanol, adding 5-11 parts of sodium methoxide, heating and stirring to 50-65 ℃, reacting for 1-4h, and evaporating to remove ethanol to obtain the synergist.
Further, the thiol-polyethylene glycol is represented by formula (I):
HS-(CH2)A-(OCH2CH2)B-C (I);
wherein A is 3-8, B is 2-6, and C is hydrogen, hydroxyl, methoxyl, amino, carboxyl.
Further, the mercapto-polyethylene glycol is (11-mercapto-undecyl) hexa (ethylene glycol).
Further, the mass percent of the synergist is 0.5-2.3%;
further, the vacuum drying temperature is 100-200 DEG CoC, the time is 6-10 h;
further, the microporous metal organic framework material is applied to gas adsorption and/or gas storage.
The reaction mechanism is as follows:
adding ZnO to Cu (BF)4)2·6H2In the O solution, Cu (Qc) is promoted2Key and essential conditions for room temperature synthesis. ZnO and Cu (BF) in solution4)2Will form (Zn, Cu) hydroxyl double salt as intermediate with excellent anion exchange capacity, thus promoting [ (Zn, Cu) (OH) BF4 ]Middle OH—And BF4 —And Qc—The anion exchange capacity reduces the time of the synthesis reaction. In Cu (Qc)2Wherein each cu (ii) atom is coordinated by two quinolinyl groups (with two N atoms) and two carboxylic acid groups (with four O atoms), extending through two linked ligands to four adjacent cu (ii) atoms, providing a square lattice coordination network. The layered network is further packed together by pi-pi interactions.
The technical effects are as follows:
quinoline-5-carboxylic acid copper Cu (Qc)2Can be prepared at room temperature as hydroxy double salt [ (Zn, Cu) (OH) BF)4]The two-dimensional sheet microporous material is formed for intermediate synthesis. Cu (Qc)2The one-dimensional channel size of the crystal is 3.3A, which is similar to that of CO2 Has a (3.3A) equivalent to less than N2 (3.64Å)。
Cu(Qc)2Qc linker pair of (C)2Has adsorption effect on CO2The adsorption capacity is far larger than N2Adsorption amount of, CO2/N2Absorption ratio of 161.3 with CO separation2And N2The potential of (2).
Compared with the method that after the MOF particle filler is obtained by direct drying, n-butyl alcohol is adopted for dispersing, and the dispersion liquid obtained by the solvent replacement method can effectively avoid agglomeration. Finally, Cu (Qc)2Dispersed in n-butanol solution.
Cu (Qc) with synergist2For Cu (Qc)2Can increase Cu (Qc)2To CO2Thereby improving the membrane to CO2The separation performance of (a); can strengthen the interface compatibility between the polymer matrix and the inorganic filler and reduce the phase interface defects.
Drawings
FIG. 1 shows examples Cu (Qc)2SEM image of (d).
FIG. 2 shows examples Cu (Qc)2XRD pattern of (a).
FIG. 3 shows Cu (Qc) in example 12FTIR characterization of (5).
FIG. 4 shows Cu (Qc) in example 12CO of2Adsorption isotherms.
Detailed Description
Synergist preparation example 1
Introducing nitrogen into the closed high-pressure reaction kettle; adding 12g of 1-allyl-3-vinylimidazole nitrate, 5g of mercaptopolyethylene glycol, 0.06g of 3-amino-4-mercaptoquinoline (CAS: 109543-48-8), 10g of ethanol, adding 5g of sodium methoxide, heating and stirring to 50 ℃, reacting for 1h, and evaporating to remove ethanol to obtain the synergist 1.
Synergist preparation example 2
Introducing nitrogen into the closed high-pressure reaction kettle; adding 18g of 1-allyl-3-vinylimidazole nitrate, 8g of mercaptopolyethylene glycol, 0.8g of 3-amino-4-mercaptoquinoline (CAS: 109543-48-8), 110g of ethanol, adding 8g of sodium methoxide, heating and stirring to 60 ℃, reacting for 2.5h, and evaporating to remove ethanol to obtain the synergist 2.
Synergist preparation example 3
Introducing nitrogen into the closed high-pressure reaction kettle; 22g of 1-allyl-3-vinylimidazole nitrate, 11g of mercaptopolyethylene glycol, 1.5g of 3-amino-4-mercaptoquinoline (CAS: 109543-48-8), 120g of alcohol and 11g of sodium methoxide are added, the temperature is raised and the mixture is stirred to 65 ℃, the reaction is carried out for 4 hours, and the ethanol is removed by evaporation, so as to obtain the synergist 3.
Example 1
Microporous metal organic framework Cu (Qc)2The preparation method comprises the following steps:
ZnO (23.49 mg, 0.2 mmol) and Cu (BF) were mixed4)2·6H2O (0.2 g, 0.58 mmol) was dispersed in 12mL of ethanol and sonicated at room temperature for 10 minutes to give the hydroxy double salt [ (Zn, Cu) (OH) BF4]And (4) intermediate solution. Then, a DMF solution (12 mL) of HQC (0.10 g, 0.58 mol) and 0.06g of synergist 1 were added to the previous solution and stirred, and after the synthetic reaction proceeded for 10 hours, each was washed 3 times with DMF, ethanol and n-butanol to finally obtain Cu (Qc)2The n-butanol dispersion. For Cu (Qc) required for characterization2Filling material, filtering the n-butanol dispersion to obtain purple powder, adding 120 oAnd C, drying and activating for 8 hours under a vacuum condition.
In the embodiment, the morphology characteristics of the purple powder crystal obtained after activation are observed by using a Scanning Electron Microscope (SEM), and the purple powder crystal is characterized by an X-ray diffractometer and a Fourier transform infrared spectrometer, as shown in figures 1-4; the SEM and XRD patterns of the crystals obtained in the examples were in agreement with those in the reference, and it was found that the microporous metal organic framework Cu (Qc) was successfully prepared2。
At 298K and 0.1MPa, Cu (Qc)2CO of2Has an adsorption capacity of 47.1cm3g-1Description of Cu (Qc)2Has higher CO2Adsorption capacity.
Example 2
Microporous metal organic framework Cu (Qc)2The preparation method comprises the following steps:
ZnO (29.36 mg, 0.25 mmol) and Cu (BF) were added4)2·6H2O(0.2g,0.58mmol)Dispersing in 15mL ethanol, and performing ultrasonic treatment for 10 minutes at room temperature to obtain hydroxyl double salt [ (Zn, Cu) (OH) BF)4]And (4) intermediate solution. Then, a DMF solution (12 mL) of HQC (0.12 g, 0.696 mol) and 0.12g of synergist 2 were added to the previous solution and stirred, and after the synthetic reaction proceeded for 12 hours, each of DMF, ethanol and n-butanol was washed 3 times to obtain Cu (Qc)2The n-butanol dispersion. For Cu (Qc) required for characterization2Filling material, filtering the n-butanol dispersion to obtain purple powder, adding 120 oAnd C, drying and activating for 8 hours under a vacuum condition.
EXAMPLES the violet powder crystals obtained after activation were observed for morphology by Scanning Electron Microscopy (SEM) and characterized by X-ray diffractometry and Fourier transform infrared spectroscopy, which was substantially the same as that of example 1, and it was found that the microporous metal organic framework Cu (Qc) was successfully prepared2。
At 298K and 0.1MPa, Cu (Qc)2CO of2Has an adsorption capacity of 46.9cm3g-1This example was conducted in substantially the same manner as example 1.
Example 3
ZnO (35.235 mg, 0.3 mmol) and Cu (BF) were mixed4)2·6H2O (0.2 g, 0.58 mmol) was dispersed in 18mL of ethanol and sonicated at room temperature for 10 minutes to give the hydroxy double salt [ (Zn, Cu) (OH) BF4]And (4) intermediate solution. Then, a DMF solution (12 mL) of HQC (0.15 g, 0.87 mol) and 0.18g of synergist 2 were added to the previous solution and stirred, after the synthetic reaction proceeded for 14 h, each was washed 3 times with DMF, ethanol and n-butanol to finally obtain Cu (Qc)2The n-butanol dispersion. For Cu (Qc) required for characterization2Filling material, filtering the n-butanol dispersion to obtain purple powder, adding 120 oAnd C, drying and activating for 8 hours under a vacuum condition.
EXAMPLES the violet powder crystals obtained after activation were observed for morphology by Scanning Electron Microscopy (SEM) and characterized by X-ray diffractometry and Fourier transform infrared spectroscopy, which was substantially the same as that of example 1, and it was found that the microporous metal organic framework Cu (Qc) was successfully prepared2。
At 298K and 0.1MPa, Cu (Qc)2CO of2Has an adsorption capacity of 46.4cm3g-1This example was conducted in substantially the same manner as example 1.
Example 4
Microporous metal organic framework Cu (Qc)2The preparation method comprises the following steps:
ZnO (47.1 mg, 0.4 mmol) and Cu (BF) were added4)2·6H2O (0.2 g, 0.58 mmol) was dispersed in 20mL of ethanol and sonicated at room temperature for 10 minutes to give the hydroxy double salt [ (Zn, Cu) (OH) BF4]And (4) intermediate solution. Then adding HQC (0.15 g, 1.044 mol) in DMF (12 mL) and 0.24g of synergist 3 into the previous solution, stirring, washing with DMF, ethanol and n-butanol respectively for 3 times after the synthetic reaction is carried out for 15 h, and finally obtaining Cu (Qc)2The n-butanol dispersion. For Cu (Qc) required for characterization2Filling material, filtering the n-butanol dispersion to obtain purple powder, adding 120 oAnd C, drying and activating for 8 hours under a vacuum condition.
EXAMPLES the violet powder crystals obtained after activation were observed for morphology by Scanning Electron Microscopy (SEM) and characterized by X-ray diffractometry and Fourier transform infrared spectroscopy, which was substantially the same as that of example 1, and it was found that the microporous metal organic framework Cu (Qc) was successfully prepared2。
At 298K and 0.1MPa, Cu (Qc)2CO of2Has an adsorption capacity of 46.7cm3g-1This example was conducted in substantially the same manner as example 1.
Example 5
Microporous metal organic framework Cu (Qc)2The preparation method comprises the following steps:
ZnO (58.875 mg, 0.5 mmol) and Cu (BF) were mixed4)2·6H2O (0.2 g, 0.58 mmol) was dispersed in 20mL of ethanol and sonicated at room temperature for 10 minutes to give the hydroxy double salt [ (Zn, Cu) (OH) BF4]And (4) intermediate solution. Then, a DMF solution (12 mL) of HQC (0.16 g, 1.114 mol) and 0.276g of synergist 3 were added to the previous solution and stirred, after the synthetic reaction proceeded for 16h, each was washed 3 times with DMF, ethanol and n-butanol to finally obtain Cu (Qc)2The n-butanol dispersion. For Cu (Qc) required for characterization2Filling, dividing n-butanol intoFiltering the obtained powder to obtain purple powder at 120 oAnd C, drying and activating for 8 hours under a vacuum condition.
EXAMPLES the violet powder crystals obtained after activation were observed for morphology by Scanning Electron Microscopy (SEM) and characterized by X-ray diffractometry and Fourier transform infrared spectroscopy, which was substantially the same as that of example 1, and it was found that the microporous metal organic framework Cu (Qc) was successfully prepared2。
At 298K and 0.1MPa, Cu (Qc)2CO of2Has an adsorption amount of 47.0cm3g-1This example was conducted in substantially the same manner as example 1.
Claims (16)
2. a microporous metal organic framework cu (qc) according to claim 12The preparation method is characterized by comprising the following steps: the surface area is 180 to 320m2/g。
3. A microporous metal organic framework cu (qc) according to claim 12The preparation method is characterized by comprising the following steps: the pore volume of the micropores is 0.09-0.20 cm3/g。
4. A microporous metal organic framework cu (qc) according to claim 12The preparation method is characterized by comprising the following steps: the diameter of the micropores is 1.0-2.0 nm.
5. A microporous metal organic framework cu (qc) according to claim 12The preparation method is characterized by comprising the following steps: the method comprises the following steps:
s1: mixing the raw material A and the raw material B in an organic solvent, and performing ultrasonic treatment for 10 minutes to obtain an intermediate solution;
s2: mixing and stirring the intermediate solution and DMF containing quinoline-5-carboxylic acid, carrying out synthetic reaction for 10-16 h, adding a synergist, and continuing the reaction for 30-100 min;
s3: washing the product after the synthesis reaction with an organic solvent for 6-9 times to obtain Cu (Qc)2A dispersion liquid;
s4: carrying out suction filtration on the dispersion liquid to obtain purple powder, drying and activating at high temperature under vacuum condition to obtain the microporous metal organic framework Cu (Qc)2。
6. A microporous metal organic framework Cu (Qc) according to claim 52The preparation method is characterized by comprising the following steps: the raw material A is ZnO.
7. A microporous metal organic framework Cu (Qc) according to claim 52The preparation method is characterized by comprising the following steps: the raw material B is Cu (BF)4)2•6H2O。
8. A microporous metal organic framework Cu (Qc) according to claim 52The preparation method is characterized by comprising the following steps: the mass ratio of the raw material A to the raw material B is 0.15-0.3.
9. A microporous metal organic framework Cu (Qc) according to claim 52The preparation method is characterized by comprising the following steps: the organic solvent is one or more of DMF, ethanol or n-butanol.
10. A microporous metal organic framework Cu (Qc) according to claim 52The preparation method is characterized by comprising the following steps: the mass percentage content of the quinoline-5-carboxylic acid is 1-10%.
11. A microporous metal organic framework Cu (Qc) according to claim 52The preparation method is characterized by comprising the following steps: the preparation method of the synergist comprises the following steps:
introducing nitrogen into a closed high-pressure reaction kettle according to the parts by weight; adding 12-22 parts of 1-allyl-3-vinylimidazole nitrate, 5-11 parts of mercaptopolyethylene glycol, 0.06-1.5 parts of 3-amino-4-mercaptoquinoline (CAS: 109543-48-8), 100 parts of ethanol, adding 5-11 parts of sodium methoxide, heating and stirring to 50-65 ℃, reacting for 1-4h, and evaporating to remove ethanol to obtain the synergist.
12. A microporous metal organic framework cu (qc) according to claim 112The preparation method is characterized by comprising the following steps: the sulfhydryl polyethylene glycol is shown as a formula (I):
HS-(CH2)A-(OCH2CH2)B-C (I);
wherein A is 3-8, B is 2-6, and C is hydrogen, hydroxyl, methoxyl, amino, carboxyl.
13. A microporous metal organic framework cu (qc) according to claim 122The preparation method is characterized by comprising the following steps: the mercapto polyethylene glycol is (11-mercapto undecyl) hexa (ethylene glycol).
14. A microporous metal organic framework Cu (Qc) according to claim 52The preparation method is characterized by comprising the following steps: the mass percentage content of the synergist is 0.5-2.3%.
15. A microporous metal organic framework Cu (Qc) according to claim 52The preparation method is characterized by comprising the following steps: the vacuum drying temperature is 100-200 DEG CoC, the time is 6-10 h.
16. Use of the microporous metal organic framework material according to any one of claims 1 to 5 for gas adsorption and/or gas storage.
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