CN112973456B - Two-dimensional metal organic framework nanosheet film, and preparation method and application thereof - Google Patents
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Abstract
The invention discloses a two-dimensional metal organic framework nanosheet membrane, and a preparation method and application thereof. By controllably modulating the organic ligand, functional groups with different contents are introduced, and the separation performance of hydrogen/carbon dioxide is improved. The preparation method comprises the steps of synthesizing a layered precursor by a one-pot method, peeling layers from top to bottom to obtain a two-dimensional layered nanosheet material, and finally assembling the two-dimensional layered nanosheet film on the surface of the porous carrier. The invention can controllably modify the two-dimensional metal organic framework nanosheet and realize the optimization of the performance of the corresponding two-dimensional ultrathin film.
Description
Technical Field
The invention belongs to the field of membrane separation, and relates to a two-dimensional metal organic framework nanosheet membrane, a preparation method and application thereof.
Background
Compared with the traditional separation technology, the membrane separation has the advantages of simple operation process, low energy consumption, high efficiency and the like, and is widely applied to the fields of chemical industry, wastewater treatment, biological medicine and the like. With the increasing severity of the global warming problem, energy conservation and emission reduction become important topics in the current era, and the membrane material has the advantages of high separation efficiency and simple and convenient operation, and has wide application prospect in the field of gas separation. The membrane gas separation is a high-efficiency separation method which utilizes the difference of the transmission rates of mixed gas permeating a membrane under the action of pressure drive so as to achieve the separation purpose. However, it has been difficult to break through the limitation of robinson's upper line in membrane separation, i.e., increasing the selectivity decreases permeability and increasing the selectivity decreases permeability. Since the discovery of graphene, the development of two-dimensional materials has attracted considerable attention. The two-dimensional material has the thickness of molecular level and an ordered pore structure, can effectively reduce the mass transfer resistance, and provides possibility for breaking through the bottleneck. In addition to graphene and its derivatives, the two-dimensional nanoplatelets currently used in the separation field include transition metal sulfides, zeolites, metal organic framework materials, and the like. The two-dimensional metal organic framework nanosheet has the advantages of being rich in structure, wide in pore size range distribution and capable of modifying functional groups on the surface, and can be used as an ideal membrane construction unit. Therefore, the research on the two-dimensional metal organic framework nanosheet membrane is focused on, and the more excellent separation performance is achieved through further modification and optimization.
Disclosure of Invention
The invention aims to provide a two-dimensional metal organic framework nanosheet, a preparation method and application thereof, and relates to a controllable modification method for a layered material and a gas separation performance test for the obtained ultrathin layered material.
A preparation method of a two-dimensional metal organic framework nanosheet is used for realizing controllable modification of the two-dimensional metal organic framework nanosheet, firstly synthesizing a two-dimensional layered metal organic framework precursor material through controllable modification, then stripping the precursor from top to bottom to obtain a two-dimensional nanosheet material, and then forming a film from the two-dimensional nanosheet material, wherein the specific preparation process comprises the following steps:
(1) one-pot synthesis of layered precursor materials: the metal source is divalent zinc salt, and divalent zinc salt, an organic ligand, sodium formate and an organic solvent are mixed and react for 24-168 hours at 0-200 ℃ to obtain a precursor of the two-dimensional layered metal organic framework;
wherein the molar ratio of each raw material is Zn2+: organic ligand: sodium formate: organic solvent ═ 1: 0-1.0: 0-1.0: 150, and the organic ligand cannot be 0;
(2) and (2) carrying out ball milling from top to bottom to strip to obtain two-dimensional layered nanosheets, mixing the precursor material of the two-dimensional layered metal organic framework obtained in the step (1) with an organic solvent, and carrying out ball milling from top to bottom to strip to obtain the two-dimensional layered nanosheets. Dispersing the two-dimensional layered nanosheets in an organic solvent to obtain a two-dimensional layered metal organic framework material (nanosheet) dispersion liquid, and standing and settling for 1-730 d;
wherein the mass concentration of the two-dimensional layered nanosheet in the nanosheet dispersion liquid is 0.001-1%;
(3) dripping the nano sheet dispersion liquid obtained in the step (2) on the surface of a porous carrier to form a film at room temperature to 200 ℃, namely assembling the nano sheets on the surface of the porous carrier in parallel to form a film, and drying to obtain a two-dimensional metal organic framework nano sheet film;
wherein, when the nano-sheet film is prepared, the dropping amount of the nano-sheet dispersion liquid is 1-50 mL/cm based on the carrier in unit area2And (3) a carrier.
Based on the technical scheme, preferably, the organic ligand is one or a mixture of more of benzimidazole, 3H-imidazo [4,5-c ] pyridine, methylimidazole, 5-methoxy-2-benzimidazole, 2-mercaptoimidazole, 2-mercaptobenzimidazole, cysteine and the like. The aminobenzimidazole includes 5-amino-2-benzimidazole and 2-aminobenzimidazole.
Based on the above technical scheme, preferably, in the step (1), when the organic ligand is benzimidazole or aminobenzimidazole, the molar ratio of each raw material is Zn2+: benzimidazole: aminobenzimidazole: sodium formate: organic solvent ═ 1: 0-0.5: 0-0.5: 0-1: 150, and the benzimidazole and the aminobenzimidazole cannot be 0 at the same time, and the sodium formate cannot be 0.
Based on the technical scheme, preferably, in the step (1), the amount of the sodium formate and the organic ligand are the same.
Based on the above technical scheme, preferably, in the step (1), the divalent zinc salt is Zn (NO)3)2、ZnCl2And the like.
Based on the above technical scheme, preferably, in the step (1) and the step (2), the organic solvent is anhydrous methanol, anhydrous ethanol, N-dimethylformamide, or the like.
Based on the above technical solution, preferably, in the step (2), the ball milling conditions are as follows: the rotating speed is 50-100r/min, and the ball milling time is 1-24 hours.
Based on the technical scheme, preferably, in the step (2), the method for dispersing the two-dimensional layered nanosheets in the organic solvent is ultrasonic dispersion, wherein the ultrasonic dispersion is carried out for 0-1h, and the power is 300-600W.
Based on the above technical solution, preferably, in the step (2), the standing and settling is performed for 14 days or more and 365 days or less.
The two-dimensional layered precursor material of the present invention is Zn2(BIM)4And modified derivatives of similar structure having amino functional groups. The controllable modification preparation of the two-dimensional layered metal organic framework nanosheet material is realized by regulating and controlling the type and the amount of the ligand.
Based on the above technical solution, preferably, in the step (3), the film forming method includes a hot drop method, a vacuum filtration method, an interface self-assembly method, a Langmuir-shaefer (ls) method, and the like.
Wherein the hot-drop method is a hot-drop method for forming a film at 120 ℃; vacuum filtration method is used for forming the film at room temperature of 0-minus 0.1 MPa. When the nano-sheet film is prepared, the nano-sheet dispersion liquid is dripped by 1-20 mL in unit area of the carrier, and the liquid of the interfacial self-assembly method and the LS method is water, C1-C8 alcohol and derivatives thereof, or a mixture of at least two substances.
Based on the above technical solution, preferably, in the step (3), the porous carrier (base film) is a silica carrier or α -Al2O3Support, gamma-Al2O3Support, TiO2One of a carrier, an anodic alumina carrier and a stainless steel carrier; the pore size of the porous carrier is 5 nm-1 μm.
Based on the above technical solution, preferably, in the step (3), the porous carrier has a sheet structure, a fiber structure, or a tubular structure.
Based on the above technical solution, preferably, in the step (3), the drying conditions are as follows: the temperature is 0-200 ℃, and the time is 1-24 h.
When the organic ligand is benzimidazole, the two-dimensional layered precursor material Zn is prepared by controllable modification through a one-pot method2(BIM)4(ii) a When the organic ligand is benzimidazole or 5-aminobenzimidazole, the two-dimensional layered precursor material NH is prepared by controllable modification by a one-pot method2-Zn2(BIM)4。
The invention also relates to two-dimensional metal organic framework nanosheets prepared by the method described above.
The invention also relates to the application of the two-dimensional metal organic framework nanosheet membrane in gas separation, in particular hydrogen/carbon dioxide separation.
Has the advantages that: the invention firstly synthesizes a layered precursor by a one-pot method, then strips the layers from top to bottom to obtain a two-dimensional layered nanosheet material, and finally assembles the two-dimensional layered nanosheet film on the surface of a porous carrier. By controllably modulating the organic ligand, functional groups with different contents are introduced, and the separation performance of hydrogen/carbon dioxide is improved. By using the preparation method provided by the invention, the two-dimensional metal organic framework nanosheet can be controllably modified, the optimization of the performance of the corresponding two-dimensional ultrathin film is realized, the two-dimensional metal organic framework nanosheet film material with excellent performance can be obtained, and the preparation method has a good application prospect in the separation field.
Drawings
The invention is shown in figure 11, which is respectively:
FIG. 1 shows Zn synthesized in example 12(bim)4An X-ray diffraction pattern of a nanoplate precursor material;
FIG. 2 shows Zn synthesized in example 12(bim)4Scanning electron microscope photographs of the nanoplatelet precursor materials;
FIG. 3 shows 5% -NH synthesized in example 22-Zn2(bim)4An X-ray diffraction pattern of a nanoplate precursor material;
FIG. 4 shows 5% -NH synthesized in example 22-Zn2(bim)4Scanning electron microscope photographs of the nanosheet precursor material;
FIG. 5 shows 10% -NH synthesized in example 32-Zn2(bim)4An X-ray diffraction pattern of a nanoplate precursor material;
FIG. 6 shows 10% -NH synthesized in example 32-Zn2(bim)4Scanning electron microscope photographs of the nanoplatelet precursor materials;
FIG. 7 shows 15% -NH synthesized in example 22-Zn2(bim)4An X-ray diffraction pattern of a nanoplate precursor material;
FIG. 8 shows 15% -NH synthesized in example 22-Zn2(bim)4Scanning electron microscope photographs of the nanoplatelet precursor materials;
FIG. 9 is an ultrathin 5% -NH film prepared in example 62-Zn2(bim)4A scanning electron microscope photograph of the nanosheet supporting film;
FIG. 10 is an ultra-thin 10% -NH film made in example 62-Zn2(bim)4A scanning electron microscope photograph of the nanosheet supporting film;
FIG. 11 is an ultra-thin 15% -NH film made in example 62-Zn2(bim)4A scanning electron microscope photograph of the nanosheet supporting film;
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Example 1 Zn2(bim)4Preparation of the precursor
1.5 g of zinc nitrate hexahydrate, 0.298 g of benzimidazole and 0.174 g of sodium formate were added to 30 ml of anhydrous methanol and stirred for 20 minutes. Transferring the mixed solution into a 100 ml reaction kettle, placing the reaction kettle in an oven, reacting for 72 hours at 100 ℃, taking out the reaction kettle and cooling to room temperature. Repeatedly cleaning the ZIF-7 nano particles obtained by centrifugation with methanol, drying the product in a 60 ℃ oven overnight, and collecting Zn2(bim)4A precursor.
X-ray diffraction confirmed that the product had Zn2(bim)4Structure (figure 1) demonstrates the successful synthesis of the precursor material. The scanning electron microscope picture shows that the product has obvious step-like layered morphology (as shown in figure 2).
Example 25% -NH2-Zn2(bim)4Preparation of
1.5 g of zinc nitrate hexahydrate, 0.283 g of benzimidazole, 0.0168 g of 5-aminobenzimidazole and 0.174 g of sodium formate were added to 30 ml of methanol and stirred for 20 minutes. Transferring the mixed solution into a 100 ml reaction kettle, placing the reaction kettle in an oven, reacting for 72 hours at 100 ℃, taking out the reaction kettle and cooling to room temperature. Repeatedly cleaning the ZIF-7 nano particles obtained by centrifugation with methanol, drying the product in an oven at 60 ℃ overnight, and collecting the product to obtain 5% -NH2-Zn2(bim)4A precursor.
X-ray diffraction confirms that the product also has Zn2(bim)4Structure (see fig. 3), demonstrating the successful synthesis of the precursor material. The scanning electron microscope picture shows that the product has obvious step-like layered morphology (as shown in figure 4).
Example 310% -NH2-Zn2(bim)4Preparation of
1.5 grams of zinc nitrate hexahydrate, 0.268 grams of benzimidazole,0.0336 g of 5-aminobenzimidazole, 0.174 g of sodium formate, 30 ml of methanol were added and stirred for 20 minutes. Transferring the mixed solution into a 100 ml reaction kettle, placing the reaction kettle in an oven, reacting for 72 hours at 100 ℃, taking out the reaction kettle and cooling to room temperature. Repeatedly cleaning the ZIF-7 nano particles obtained by centrifugation with methanol, drying the product in an oven at 60 ℃ overnight, and collecting the product to obtain 5% -NH2-Zn2(bim)4A precursor.
X-ray diffraction confirms that the product also has Zn2(bim)4Structure (see fig. 5), demonstrating the successful synthesis of the precursor material. The scanning electron microscope picture shows that the product has obvious step-like layered morphology (as shown in figure 6).
Example 415% -NH2-Zn2(bim)4Preparation of
1.5 g of zinc nitrate hexahydrate, 0.283 g of benzimidazole, 0.0168 g of 5-aminobenzimidazole and 0.174 g of sodium formate were added to 30 ml of methanol and stirred for 20 minutes. Transferring the mixed solution into a 100 ml reaction kettle, placing the reaction kettle in an oven, reacting for 72 hours at 100 ℃, taking out the reaction kettle and cooling to room temperature. Repeatedly cleaning the ZIF-7 nano particles obtained by centrifugation with methanol, drying the product in an oven at 60 ℃ overnight, and collecting the product to obtain 5% -NH2-Zn2(bim)4A precursor.
X-ray diffraction confirms that the product also has Zn2(bim)4Structure (see fig. 7), demonstrating the successful synthesis of the precursor material. The scanning electron microscope picture shows that the product has obvious step-like layered morphology (as shown in FIG. 8).
EXAMPLE 5 ultrathin two-dimensional layered Zn2(bim)4Preparation of nanosheets
Zn prepared in example 12(bim)4The particles were dispersed in 100 ml of methanol solution, sealed in a ball mill jar of 150 ml volume and ball milled at 60 rpm for 1 hour. The solution was then diluted 1.5 times with the same solvent and sonicated in a water bath at 600 watts power for 30 minutes. Zn2(bim)4The dispersion of nanoplatelets was allowed to stand for two weeks to remove the large unpeeled particles. Ultra-thin two-dimensional layered Zn2(bim)4The number of the nano-sheets is nano-sheet a.
Examples 6-8 ultrathin two-dimensional layered 5-NH2-Zn2(bim)4Preparation of nanosheets
5-NH of different amino contents prepared in examples 2, 3 and 4 was reacted in the same manner as described above2-Zn2(bim)4The particles were ball milled and then the solution was diluted 1.5 times with the same solvent and allowed to stand for more than two weeks to remove large particles that did not delaminate. Wherein, the ultrathin two-dimensional layered 5% -NH2-Zn2(bim)4The number of the nano-sheets is nano-sheet b, and the ultra-thin two-dimensional layered is 10% -NH2-Zn2(bim)4The number of the nano-sheets is nano-sheet c, and the ultrathin two-dimensional layered 15% -NH2-Zn2(bim)4The number of the nano-sheets is nano-sheet d.
Example 9 ultra-thin Zn2(bim)4Nanosheet-supporting film and NH2-Zn2(bim)4Preparation of nanosheet supported film
alpha-Al is added2O3Preheating a porous carrier to 120 ℃ on a horizontal heating platform, respectively taking 15mL of the four nanosheet dispersions obtained in the examples 5, 6, 7 and 8, dropwise adding 15mL of the dispersion on the surface of an alpha-alumina carrier (circular with the radius of 0.9 cm) with the aperture of 70nm by using a syringe until the solvent is completely volatilized, namely, a 'hot dropwise adding coating' method. The prepared supported membrane was dried at 120 ℃ for 1 hour and stored in a petri dish at room temperature. Wherein, the ultra-thin Zn2(bim)4The number of the nano-sheet supported film is a nano-sheet supported film a, ultrathin 5% -NH2-Zn2(bim)4The number of the nano-sheet supported film is a nano-sheet supported film b, which is ultrathin 10% -NH2-Zn2(bim)4The number of the nano-sheet supported film is a nano-sheet supported film c, which is ultrathin 15% -NH2-Zn2(bim)4The number of the nano-sheet supporting film is a nano-sheet supporting film d. Scanning electron microscope pictures of the nanosheet supported membrane (see fig. 9-11, in which fig. 9 is ultra-thin 5% -NH)2-Zn2(bim)4A nanosheet-supporting film (nanosheet-supporting film b); FIG. 10 is an ultra-thin 10% -NH2-Zn2(bim)4A nanosheet-supporting film (nanosheet-supporting film c); FIG. 11 is an ultra-thin 15% -NH2-Zn2(bim)4Nanosheet-supporting film (nanosheet-supporting film d)).
Example 7 ultra-thin NH2-Zn2(bim)4Hydrogen/carbon dioxide gas separation test of nanosheet supported membrane
The four supported membranes prepared in examples 5 to 8 were packed in a vecco-karenbach (Wicke-Kallenbach) membrane module, and a hydrogen/carbon dioxide mixed gas separation test was performed under conditions of normal temperature and Δ P ═ 0 bar, with argon as a purge gas. (standard case 1GPU ═ 1 × 10-6cm3/cm2S · cmHg). It can be seen from the data in the table that the gas separation performance of the membrane material is improved after the amino group is introduced compared with the unmodified membrane material.
Claims (5)
1. The application of the two-dimensional metal organic framework nanosheet membrane in hydrogen/carbon dioxide separation is characterized in that the preparation method of the two-dimensional metal organic framework nanosheet membrane comprises the following steps:
(1) mixing divalent zinc salt, an organic ligand, sodium formate and an organic solvent, and reacting at 0-200 ℃ for 24-168 hours to obtain a precursor of a two-dimensional layered metal organic framework;
wherein the organic ligand is benzimidazole and 5-aminobenzimidazole, and the molar ratio of the raw materials is Zn2+: benzimidazole: 5-aminobenzimidazole: sodium formate: organic solvent ═ 1: 0-0.5: 0-0.5: 0-1.0: 150, and both benzimidazole and aminobenzimidazole cannot be 0 at the same time, and sodium formate cannot be 0;
(2) mixing the precursor of the two-dimensional layered metal organic framework obtained in the step (1) with an organic solvent, performing ball milling to obtain a two-dimensional layered nanosheet, dispersing the two-dimensional layered nanosheet in the organic solvent to obtain a nanosheet dispersion liquid, and standing and settling for 1-730 d;
wherein the mass concentration of the two-dimensional layered nanosheets in the nanosheet dispersion is 0.001-1%;
(3) dripping the nanosheet dispersed liquid obtained in the step (2) on the surface of a porous carrier at room temperature to 200 ℃ to form a film, and drying to obtain a two-dimensional metal organic framework nanosheet film;
when the two-dimensional metal organic framework nanosheet film is prepared, the dropping amount of the two-dimensional layered nanosheet dispersion liquid is 1-50 mL/cm based on the carrier in unit area2A carrier;
in the step (1) and the step (2), the organic solvent is absolute methanol, absolute ethanol or N, N-dimethylformamide.
2. Use according to claim 1, characterized in that in step (1) the divalent zinc salt is Zn (NO)3)2Or ZnCl2。
3. The use according to claim 1, wherein in step (3), the film is formed by a dropping method, a vacuum filtration method, an interfacial self-assembly method or a Langmuir-Shaefer method.
4. The use according to claim 1, wherein in step (3), the porous support is a silica support, α -Al2O3Support, gamma-Al2O3Support, TiO2One of a carrier, an anodic alumina carrier and a stainless steel carrier; the pore diameter of the porous carrier is 5 nm-1 μm; the porous carrier is in a sheet structure, a fiber structure or a tubular structure.
5. The use according to claim 1, wherein in step (3), the drying conditions are: the temperature is 0-200 ℃, and the time is 1-24 h.
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| CN104307482A (en) * | 2014-10-14 | 2015-01-28 | 中国科学院宁波材料技术与工程研究所 | Functionalized ZIF type metal organic framework (MOF) porous material as well as preparation method and application of material |
| CN105709614A (en) * | 2014-11-30 | 2016-06-29 | 中国科学院大连化学物理研究所 | Ultrathin layered material, and preparation method thereof |
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| CN104307482A (en) * | 2014-10-14 | 2015-01-28 | 中国科学院宁波材料技术与工程研究所 | Functionalized ZIF type metal organic framework (MOF) porous material as well as preparation method and application of material |
| CN105709614A (en) * | 2014-11-30 | 2016-06-29 | 中国科学院大连化学物理研究所 | Ultrathin layered material, and preparation method thereof |
| CN110270232A (en) * | 2019-05-31 | 2019-09-24 | 浙江工业大学 | A kind of metal organic framework nanometer sheet composite membrane and its preparation method and application |
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