CN112191111A - Ionic liquid/metal organic framework ZIF-8 composite membrane and preparation method and application thereof - Google Patents
Ionic liquid/metal organic framework ZIF-8 composite membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of membrane separation, and provides a preparation method and application of an ionic liquid/ZIF-8 composite membrane. The invention adopts a one-pot method to obtain a compact defect-free ionic liquid/ZIF-8 composite membrane with the thickness of 1 mu m; the obtained composite membrane can be applied to gas separation. The preparation process is simple, and the developed composite membrane has good gas permeation and separation performance and stability, and H is2The permeability reaches 1.5 multiplied by 10–6mol m‑2s‑1Pa‑1，H2/CO2The gas mixture separation factor is 55, exceeding the Robeson upper limit (2008).
Description
Technical Field
The invention belongs to the technical field of membrane separation, and particularly relates to an ionic liquid/metal organic framework ZIF-8 composite membrane, and a preparation method and application thereof
Background
H2、CO2And CH4 gas is often present in the form of a mixed gas in the water gas shift to produce hydrogen (H)2/CO2) Natural gas (CO)2/CH4) And biogas (CO)2/CH4) And in the process of energy gas and industry, the high-efficiency gas separation has great significance to the fields of environment, energy, chemical industry and the like. Film separationThe separation technology has the advantages of small occupied area, easiness in linear amplification, energy conservation, consumption reduction, simplicity in operation and the like, and has attracted high attention in the field of gas separation. The key to membrane separation technology lies in the development of membrane materials with high selectivity, high permeability and high stability.
Metal-organic framework (MOF) is a porous crystalline material with a periodic network structure formed by self-assembly of Metal ions and organic ligands. The rich frame structure, the adjustable pore channel structure and the surface functionalization make the membrane material become a new generation of membrane material. ZIF-8 is a typical material in MOF, and is made of metal ion Zn2+And 2-methylimidazolyl ester, and are widely used in the research of membrane materials. The existing growth method of the ZIF-8 film mainly comprises the following steps: in-situ growth method, secondary growth method, layer-by-layer self-assembly method, counter diffusion method, electrochemical growth method (preparation method of metal organic framework ZIF-8 film [ P ]]Chinese invention patent, CN201210269544, 2012-8-1; metal organic framework film and preparation method and application thereof P]China invention patent, CN201310373159, 2013-8-23) and the like, but the ZIF-8 membrane generally has the problems of large membrane thickness (16-60 mu m) and poor permeation and separation performance. At present, the MOF/ionic liquid related composite membranes have few reports, and O.Tzialla et Al use flaky alpha-Al2O3Preparation of ZIF-69/Ionic liquids [ omim ] for substrates][TCM]A composite membrane (J.Phys.chem.C,2013,117,18434) is prepared by preparing a ZIF-69 membrane layer with the thickness of 60 μm by adopting a seed crystal secondary growth method, and then loading ionic liquid in the ZIF-69 membrane layer and on the surface of the membrane layer by adopting a dip coating method (the thickness of the ionic liquid on the surface is up to 240 μm, and the thickness of the membrane is up to 300 μm, so that CO of the composite membrane is CO2Permeability of only 5.6X 10-11mol m-2s-1Pa-1. At present, the metal organic framework membrane and the ionic liquid/metal organic framework composite membrane generally have the problems of large membrane thickness and improved permeation and separation performance.
Disclosure of Invention
The invention aims to provide an ionic liquid/ZIF-8 composite membrane and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of an ionic liquid/metal organic framework ZIF-8 composite membrane comprises the steps of mixing an ionic liquid, a ZIF-8 sol and a ZIF-8 metal precursor with an organic ligand, wherein the ratio of the ionic liquid to the ZIF-8 sol is 0.2g-0.7g of the ionic liquid to 10mL of the ZIF-8 sol, the mass ratio of the ionic liquid to the ZIF-8 sol is 1:1-2:1, and the mass ratio of the ZIF-8 metal precursor to the organic ligand is 1: 5-2: and 1, injecting the mixed solution into a reaction kettle filled with a carrier, and performing thermal crystallization at least twice through a solvent to obtain the composite membrane.
The method further promotes the interactive growth of ZIF-8 particles, and a continuous nano composite film is formed on the APTES-modified flaky porous alumina substrate.
The ionic liquid is 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt [ Bmim][Tf2N]；
The mixed solution of the metal precursor of the ZIF-8 and the organic ligand is a solution containing zinc ions and a solution containing 2-methylimidazole ligand; wherein the mass ratio of the inorganic zinc salt to the 2-methylimidazole is as follows: 1: 4-1:1.
Further, the following steps are carried out:
(1) preparation of ZIF-8 sol:
1) respectively dissolving inorganic zinc salt and organic ligand 2-methylimidazole in a solvent, then stirring the two solutions dissolved in the solvent at room temperature for reaction, and violently stirring for 10min-24h for later use;
2) centrifuging the reactant, collecting precipitate, washing, and dispersing the precipitate in a solvent; further centrifuging and collecting supernatant to obtain sol with concentration of 0.5-3 mg/mLZIF-8;
(2) solvent thermal crystallization:
1) preparing a reaction mixed solution: adding the imidazole ligand solution into the zinc ion solution, and violently stirring to form a uniform mixture; adding ionic liquid and the ZIF-8 sol into the mixture, and uniformly stirring;
2) and (3) crystallization: and transferring the reaction mixed solution into a reaction kettle fixed with a pretreated substrate for crystallization, cooling to room temperature to obtain primary crystallization, performing crystallization reaction at least twice, taking out, washing with a solvent, and drying to obtain the composite film on the surface of the substrate.
The pretreatment of the substrate comprises the steps of polishing the surface of the substrate until the surface is smooth, washing and drying; after drying, activating by HCl solution, then treating for 1-5h by 3-aminopropyl triethoxysilane (APTES) toluene solution under the action of inert gas, and vacuum drying for 2-5h for later use.
In the step (1), the inorganic zinc salt in the step 1) is one or more of zinc nitrate hexahydrate, zinc nitrate tetrahydrate and zinc acetate; the mass ratio of the inorganic zinc salt to the 2-methylimidazole is as follows: 1: 4-1: 1; the mass ratio of the solvent to the 2-methylimidazole is 20: 1-60: 1.
in the step (2), the imidazole ligand solution 1) is obtained by dissolving 2-methylimidazole in a solvent, and the zinc ion solution is obtained by dissolving inorganic zinc salt in the solvent; the mass ratio of the inorganic zinc salt to the 2-methylimidazole is 1: 4-1: 1; the mass ratio of the solvent to the 2-methylimidazole is 20: 1-60: 1; wherein, the inorganic zinc salt is one or more of zinc nitrate hexahydrate, zinc nitrate tetrahydrate and zinc acetate; the solvent is one or more of water, ethanol and methanol.
In the step (1), the solvent in the steps 1) and 2) is one or a mixture of water, ethanol and methanol.
The crystallization temperature is 100-180 ℃, and the crystallization time is 4-10 h.
The drying temperature is 50-150 ℃, and the drying time is 1-10 h.
The ionic liquid/metal organic framework ZIF-8 composite membrane is prepared by the preparation method.
An application of a nano ionic liquid/ZIF-8 composite membrane in gas separation.
The invention has the following advantages:
the invention adopts a one-pot method to obtain the ionic liquid/ZIF-8 composite membrane with the thickness of 1 mu m; the obtained composite membrane can be applied to gas separation. The preparation method has simple process, and the developed composite membrane has good gas permeation and separation performance and stability; the method specifically comprises the following steps:
(1) the invention prepares and obtains a compact continuous ionic liquid/ZIF-8 composite membrane by a one-pot method, and particularly mixes ionic liquid, ZIF-8 sol and a metal precursor of ZIF-8 with an organic ligand and then carries out solvent thermal crystallization. The method adopts a one-pot method with simple process and convenient operation. The addition of the ionic liquid facilitates the intergrowth between the ZIF-8 particles.
(2) The thickness of the composite membrane obtained by the invention is only 1 mu m, and the ultrathin membrane thickness ensures that the composite membrane has higher gas permeability and separation factor, namely H2The permeability reaches 1.5 multiplied by 10–6mol m-2s-1Pa-1，H2/CO2The gas mixture separation factor is 55, exceeding the Robeson upper limit (2008). Meanwhile, the composite membrane has good running stability, and after the composite membrane runs for 120 hours, the composite membrane has H2/CO2The selective separation performance remains unchanged.
Drawings
FIG. 1 is a TEM picture of a nano ZIF-8 sol according to embodiment 1 of the present invention;
FIG. 2 is an SEM image of a once-crystallized ionic liquid/ZIF-8 composite membrane according to embodiment 1 of the present invention;
fig. 3 is an SEM image of the ionic liquid/ZIF-8 composite film crystallized twice according to embodiment 2 of the present invention.
FIG. 4 is an XRD spectrum of a twice crystallized ionic liquid/ZIF-8 composite membrane according to embodiment 2 of the present invention;
FIG. 5 is a view showing a double-crystallized ionic liquid/ZIF-8 composite membrane vs. a single gas (H) according to embodiment 2 of the present invention2、CO2、N2And CH4) The permeation rate and selectivity of;
FIG. 6 is a ZIF-8/ionic liquid composite membrane pair H crystallized twice in embodiment 2 of the present invention2/CO2Stability of osmotic separation (V)H2：VCO2＝1：1)；
Detailed Description
The preparation method of the composite material comprises the following steps: preparing ZIF-8 sol, pretreating a flaky porous alumina substrate and carrying out solvent thermal crystallization. The composite membrane has good gas permeation and separation performance and stability.
Example 1
(1) Preparation of ZIF-8 sol:
1) zinc nitrate hexahydrate (1.47g) and 2-methylimidazole (3.25g) were dissolved in 100ml of anhydrous methanol to obtain a methanol solution of zinc nitrate and a methanol solution of 2-methylimidazole, respectively, and the methanol solution of zinc nitrate was poured into the methanol solution of 2-methylimidazole and stirred at room temperature for 1 hour.
2) Centrifuging the reactant at least once to completely remove the unreacted precursor, centrifuging for 10min under the centrifugation condition of 8000-10000rpm each time, collecting the precipitate, washing the precipitate with methanol, and dispersing the washed precipitate in the methanol; the supernatant was further centrifuged at 8000-.
As shown in FIG. 1, the ZIF-8 particles in the colloidal solution were substantially in a single crystal dispersion state, and the size of the ZIF-8 particles was about 45 nm.
(2) Pretreatment of the flaky porous alumina substrate:
1) the surface of the substrate is polished by 1000 meshes of sand paper, 2000 meshes of sand paper and 3000 meshes of sand paper in sequence until the surface of the substrate is smooth. Washed with ethanol and deionized water, and dried at 105 ℃ for 10 h.
2) With 1mol L-1The substrate was activated with 2mmol L of HCl solution-1The 3-aminopropyl triethoxysilane (APTES) toluene solution is treated for 2h under the protection of argon at 110 ℃ and dried for 2h in vacuum.
(3) Solvent thermal crystallization:
1) preparing a reaction mixed solution: dissolving 0.3g of zinc nitrate hexahydrate in 11.2g of methanol solution, adding 0.66g of 2-methylimidazole in 11.2g of methanol solution, adding the obtained imidazole ligand solution into the zinc ion solution, stirring for 5min, and uniformly mixing to obtain a mixed solution containing the ligand and metal ions; then 10mL of the solution containing the ionic liquid [ Bmim ]][Tf2N](0.5g) ZIF-8 sol was added to the mixed solution containing the ligand and the metal ion, and stirred uniformly.
2) And (3) crystallization: transferring the reaction mixed solution into a reaction kettle fixed with a substrate, crystallizing for 5 hours at 150 ℃, cooling to room temperature, taking out the crystallized product once, washing with methanol, and drying for 2 hours at 100 ℃ to form the composite membrane on the surface of the substrate.
As shown in FIG. 2, after one-time crystallization, a layer of non-compact ZIF-8 film is formed on the surface of the substrate, and the defect of macropore exists.
Example 2
(1) Preparation of ZIF-8 sol:
1) zinc nitrate hexahydrate (1.47g) and 2-methylimidazole (3.25g) were dissolved in 100ml of anhydrous methanol to obtain a methanol solution of zinc nitrate and a methanol solution of 2-methylimidazole, respectively, and the methanol solution of zinc nitrate was poured into the methanol solution of 2-methylimidazole and stirred at room temperature for 1 hour.
2) Centrifuging the reactant at least once to completely remove the unreacted precursor, centrifuging for 10min under the centrifugation condition of 8000-10000rpm each time, collecting the precipitate, washing the precipitate with methanol, and dispersing the washed precipitate in the methanol; the supernatant was further centrifuged at 8000-.
As shown in FIG. 1, the ZIF-8 particles in the colloidal solution were substantially in a single crystal dispersion state, and the size of the ZIF-8 particles was about 45 nm.
(2) Pretreatment of the flaky porous alumina substrate:
1) the surface of the substrate is polished by 1000 meshes of sand paper, 2000 meshes of sand paper and 3000 meshes of sand paper in sequence until the surface of the substrate is smooth. Washed with ethanol and deionized water, and dried at 105 ℃ for 10 h.
2) With 1mol L-1The substrate was activated with 2mmol L of HCl solution-1The 3-aminopropyl triethoxysilane (APTES) toluene solution is treated for 2h under the protection of argon at 110 ℃ and dried for 2h in vacuum.
(3) Solvent thermal crystallization:
1) preparing a reaction mixed solution: dissolving 0.3g of zinc nitrate hexahydrate in 11.2g of methanol solution, adding 0.66g of 2-methylimidazole in 11.2g of methanol solution, adding the obtained imidazole ligand solution into the zinc ion solution, stirring for 5min, and uniformly mixing to obtain a mixed solution containing the ligand and metal ions; then 10mL of the solution containing the ionic liquid [ Bmim ]][Tf2N](0.5g) of ZIF-8 solutionAdding the glue into the mixed solution containing the ligand and the metal ions, and uniformly stirring.
2) And (3) crystallization: transferring the reaction mixed solution into a reaction kettle fixed with a substrate, crystallizing at 150 ℃ for 5h, cooling to room temperature to obtain primary crystallization, then crystallizing again according to the process, taking out a product obtained after twice crystallization after crystallization, washing with methanol, and drying at 100 ℃ for 2h to obtain the composite film on the surface of the substrate.
FIG. 3 shows that the ionic liquid/metal organic framework ZIF-8 composite film is continuous and compact, the thickness of the composite film is about 1 μm, and no obvious layered interface exists between the film and the substrate.
It is shown from FIG. 4 that ZIF-8 in the composite membrane has very high purity and crystallinity, and the addition of a small amount of ionic liquid has no influence on the crystal structure of ZIF-8.
Single gas (H) is carried out on the ionic liquid/metal organic framework ZIF-8 composite membrane2、CO2、N2Or CH4) The permeation separation performance test of (1), the test conditions are as follows: the temperature was 25 ℃ and the inlet side pressure was 1 bar.
As shown in FIG. 5, the composite film had good H2/CO2Separation Performance composite Membrane vs. H2Has high permeability of 1.43X 10-6mol m-2s-1Pa-1，H2/CO2、H2/N2、H2/CH4The ideal separation factors are 68.6, 25, 25.5, respectively.
H for ionic liquid/metal organic frame ZIF-8 composite membrane2/CO2Testing the operation stability of the mixed gas separation, wherein the testing conditions are as follows: h2/CO2The volume ratio of the mixed gas is 1:1, temperature 25 ℃, inlet side pressure 1 bar.
As shown in FIG. 6, H is observed after the composite membrane is operated for 120H2/CO2The selective separation performance is kept unchanged, and the stability is good.
Claims (10)
1. A preparation method of an ionic liquid/metal organic framework ZIF-8 composite membrane is characterized by comprising the following steps: mixing ionic liquid, ZIF-8 sol and a metal precursor of ZIF-8 with an organic ligand, wherein the ratio of the ionic liquid to the ZIF-8 sol is 0.2g-0.7g of ionic liquid/10 mL of ZIF-8 sol, the mass ratio of the ionic liquid to the ZIF-8 is 1:1-2:1, and the mass ratio of the metal precursor of ZIF-8 to the organic ligand is 1: 5-2: and 1, injecting the mixed solution into a reaction kettle filled with a carrier, and performing thermal crystallization at least twice through a solvent to obtain the composite membrane.
2. The method for preparing the ionic liquid/metal organic framework ZIF-8 composite membrane according to claim 1, which is characterized in that: the ionic liquid is 1-butyl-3-methylimidazolium bistrifluoromethylsulfonyl imide salt [ Bmim][Tf2N]；
The mixed solution of the metal precursor of the ZIF-8 and the organic ligand is a solution containing zinc ions and a solution containing 2-methylimidazole ligand; wherein the mass ratio of the inorganic zinc salt to the 2-methylimidazole is as follows: 1: 4-1:1.
3. The method for preparing the ionic liquid/metal organic framework ZIF-8 composite membrane according to claim 1, which is characterized in that:
(1) preparation of ZIF-8 sol:
1) respectively dissolving inorganic zinc salt and organic ligand 2-methylimidazole in a solvent, and then stirring two solutions dissolved in the solvent at room temperature for reaction for later use;
2) centrifuging the reactant, collecting precipitate, washing, and dispersing the precipitate in a solvent; further centrifuging and collecting supernatant to obtain sol with concentration of 0.5-3 mg/mLZIF-8;
(2) solvent thermal crystallization:
1) preparing a reaction mixed solution: adding the imidazole ligand solution into the zinc ion solution, and violently stirring to form a uniform mixture; adding ionic liquid and the ZIF-8 sol into the mixture, and uniformly stirring;
2) and (3) crystallization: and transferring the reaction mixed solution into a reaction kettle fixed with a pretreated substrate for crystallization, cooling to room temperature to obtain primary crystallization, performing crystallization reaction at least twice, taking out, washing with a solvent, and drying to obtain the composite film on the surface of the substrate.
4. The method for preparing an ionic liquid/metal organic framework ZIF-8 composite membrane according to claim 3, characterized in that: the pretreatment of the substrate comprises the steps of polishing the surface of the substrate until the surface is smooth, washing and drying; after drying, activating by HCl solution, then treating for 1-5h by 3-aminopropyl triethoxysilane (APTES) toluene solution under the action of inert gas, and vacuum drying for 2-5h for later use.
5. The method for preparing an ionic liquid/metal organic framework ZIF-8 composite membrane according to claim 3, characterized in that: in the step (1), the inorganic zinc salt in the step 1) is one or more of zinc nitrate hexahydrate, zinc nitrate tetrahydrate and zinc acetate; the mass ratio of the inorganic zinc salt to the 2-methylimidazole is as follows: 1: 4-1: 1; the mass ratio of the solvent to the 2-methylimidazole is 20: 1-60: 1.
6. the method for preparing an ionic liquid/metal organic framework ZIF-8 composite membrane according to claim 3, characterized in that: in the step (2), the imidazole ligand solution 1) is obtained by dissolving 2-methylimidazole in a solvent, and the zinc ion solution is obtained by dissolving inorganic zinc salt in the solvent; the mass ratio of the inorganic zinc salt to the 2-methylimidazole is 1: 4-1: 1; the mass ratio of the solvent to the 2-methylimidazole is 20: 1-60: 1; wherein, the inorganic zinc salt is one or more of zinc nitrate hexahydrate, zinc nitrate tetrahydrate and zinc acetate; the solvent is one or more of water, ethanol and methanol.
7. The method for preparing the ionic liquid composite membrane supported by the nano metal organic framework ZIF-8 according to claim 3, which is characterized in that: in the step (1), the solvent in the steps 1) and 2) is one or a mixture of water, ethanol and methanol.
8. The method for preparing the ionic liquid composite membrane supported by the nano metal organic framework ZIF-8 according to claim 3, which is characterized in that: the crystallization temperature is 100-180 ℃, and the crystallization time is 4-10 h.
9. The ionic liquid/metal organic framework ZIF-8 composite membrane prepared by the preparation method of claim 1.
10. The use of the nano ionic liquid/ZIF-8 composite membrane of claim 9, wherein: the use of the composite membrane in gas separation.
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Cited By (6)
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| CN113813801A (en) * | 2021-09-28 | 2021-12-21 | 浙江工商大学 | Mixed matrix ultrafiltration membrane doped with ZIFs @ polyion liquid compound and preparation method thereof |
| CN114177788A (en) * | 2021-12-01 | 2022-03-15 | 河北大学 | ZIF-8 tube modified ultrathin nano composite membrane, and preparation method and application thereof |
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| CN116426272A (en) * | 2023-02-23 | 2023-07-14 | 华南理工大学 | Fluorescent Au NCs@ZIF-8 cellulose paper base and preparation method and application thereof |
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| CN114177788A (en) * | 2021-12-01 | 2022-03-15 | 河北大学 | ZIF-8 tube modified ultrathin nano composite membrane, and preparation method and application thereof |
| CN114272726A (en) * | 2021-12-22 | 2022-04-05 | 惠州市绿色能源与新材料研究院 | Method for efficiently separating ammonia-containing gas based on ionic liquid mixed matrix membrane |
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| CN116351265B (en) * | 2022-01-17 | 2024-06-07 | 中国科学院过程工程研究所 | Preparation and application of high-performance mixed matrix gas separation membrane based on ionic liquid coordination |
| CN116426272A (en) * | 2023-02-23 | 2023-07-14 | 华南理工大学 | Fluorescent Au NCs@ZIF-8 cellulose paper base and preparation method and application thereof |
| CN116426272B (en) * | 2023-02-23 | 2024-07-09 | 华南理工大学 | Fluorescent Au NCs@ZIF-8 cellulose paper base and preparation method and application thereof |
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