CN111249918A - In-situ controllable synthesis method of MOF (Metal-organic framework) membrane - Google Patents
In-situ controllable synthesis method of MOF (Metal-organic framework) membrane Download PDFInfo
- Publication number
- CN111249918A CN111249918A CN201811460270.5A CN201811460270A CN111249918A CN 111249918 A CN111249918 A CN 111249918A CN 201811460270 A CN201811460270 A CN 201811460270A CN 111249918 A CN111249918 A CN 111249918A
- Authority
- CN
- China
- Prior art keywords
- solution
- mof
- carrier
- complex
- zif
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/10—Supported membranes; Membrane supports
- B01D69/105—Support pretreatment
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
Abstract
An in-situ controllable synthesis method of an MOF membrane comprises the step of placing one side of a porous carrier in a solution metal ion solution A for pre-dipping treatment, so that the solution A is adsorbed in the pores of the carrier. Fixing the impregnated carrier in a self-made stainless steel reaction tank, introducing an organic ligand solution B into one side of the pre-impregnated carrier, sealing the reaction tank, and starting a synthesis reaction at a certain temperature for a certain time. And finally obtaining a layer of uniform and compact continuous film which can grow repeatedly after being cleaned by a solvent and dried. The preparation method of the MOF film is simple and feasible, is suitable for industrial amplification, and can be applied to various fields, such as gas separation, liquid separation, sensors, adsorption, functional coatings and the like.
Description
Technical Field
The invention belongs to the fields of membrane separation, inorganic synthesis and the like; in particular to an in-situ controllable synthesis method of an MOF membrane.
Background
The metal-organic framework is a novel porous crystal material, has rich compositions and adjustable pore channel structures, can be widely applied to the field of gas and liquid separation,e.g. for CO2Selective adsorption of (e.g. CO) and related mixtures2/H2、CO2/N2) The separation research of the method, the separation of low-carbon hydrocarbon compounds and ketone compounds and the adsorption separation of some biomass platform compounds.
The continuous thin layer of MOF grains formed on the surface of the support is called a MOF film. Separation by means of MOF membranes is considered to be one of the most promising high-end separation techniques. The preparation method of the MOF film is mainly prepared by an in-situ crystallization method and a secondary growth method. Several MOF films prepared by a secondary growth method are disclosed in the literature (j.gascon, f.kapteijn, microporus mesoporus mater, 2008,113,132; YHu, w.q.jin, chem.commu.2011, 47,737; y.s.li, j.caro, angelw.chem.int, 2010,49,548). The secondary growth method is that the surface of carrier is pre-coated with crystal seed layer and then placed in homogeneous solution containing metal ions and organic ligand to induce nucleation. This method has many steps and poor reproducibility. The in-situ crystallization method is a process of directly forming a film by placing a carrier in a homogeneous solution containing metal ions and organic ligands. Compared with a secondary growth method, the in-situ crystallization method has simple preparation process, is easy to repeat and is suitable for industrial amplification. However, in-situ crystallization relies on homogeneous nucleation in solution to form microparticles, which migrate to the surface of the support layer to form the MOF film. Therefore, the in-situ crystallization method has extremely high nucleation activation energy and has strong dependence on the roughness and chemical properties of the carrier surface, external growth conditions and the like. The preparation of dense, continuous MOF membranes by in situ crystallization methods faces significant challenges. In the literature (a.huang, j.caro, chem.commun.,2012,48, 10981-. Firstly, aminopropyltriethoxysilane is introduced into the surface of a carrier to obtain a modified carrier, and then the modified carrier is placed in a solution for in-situ crystallization to obtain an MOF (metal organic framework) membrane, wherein carrier modification is the key of an in-situ crystallization method. In addition, patent (CN107875863A) discloses a method for in-situ preparation of MOF film by electrodeposition, which comprises introducing various metal precursor modifiers by electrodeposition, and then directly heating to synthesize MOF film in one step without solvent. In the above patents, the applied electric field is critical.
Heretofore, the preparation of MOF films by in situ crystallization methods has remained a difficult point. The fundamental reason is that the in-situ crystallization method is mostly a homogeneous nucleation mechanism, and the nucleation process has randomness and dispersity and is difficult to limit domains and regulate and control. As mentioned above, the current solutions either from the carrier or from the external reaction conditions will definitely make the preparation process tedious and complicated, and involve large consumption of materials and energy. In order to fundamentally solve the problem faced by the in-situ crystallization method, the randomness and the dispersity of the in the nucleation process are changed, the nucleation and growth processes of the film crystal grains are limited to the surface layer of the carrier, and the high controllability of the nucleation and growth processes is realized.
Disclosure of Invention
The invention aims to provide an in-situ controllable synthesis method of an MOF (metal organic framework) membrane, the membrane prepared by the method has certain gas separation and liquid separation performances, and the preparation process has high repeatability, simplicity and wide applicability
The method comprises the following specific steps:
(1) respectively preparing a metal ion solution A and an organic ligand solution B with the concentration range of 1 x 10 < -4 > to 1 mol/L;
(2) porous carrier pre-impregnation treatment: placing the porous carrier in a metal ion solution A for pre-impregnation treatment, so that the solution A is adsorbed on the surface of one side of the porous carrier and in the pores, and obtaining the carrier adsorbed with metal ions;
(3) in-situ reaction: fixing the carrier adsorbed with the metal ions in a self-made stainless steel reaction tank, introducing an organic ligand solution B into one side of the carrier adsorbed with the solution A, sealing the reaction tank, and starting a synthesis reaction at the temperature of 5-200 ℃ for 1 minute-10 days;
(4) and (5) washing the membrane with a solvent and drying. The solvent is one or more of water, methanol, ethanol, acetic acid, isopropanol, N' N-dimethylformamide, toluene and xylene; the drying temperature is 20-180 ℃, and the drying time is 1 hour-2 days.
Based on the above technical scheme, preferably, the metal ion solution a and the organic ligand solution B may further include a deprotonation reagent, a coordination regulator, and a surfactant, wherein the deprotonation reagent is preferably a carboxylate and an organic amine; the coordination regulator is preferably a monodentate ligand containing nitrogen and oxygen; the substances are added into a metal ion solution or an organic ligand solution to adjust the nucleation and crystallization processes of the film, so as to realize the regulation and control of the shape, the size, the arrangement orientation, the film thickness and the film crack (or film defect) of the film crystal grains.
Based on the above technical scheme, preferably, the metal ions in the metal ion solution a are from nitrate, chloride, bromide, sulfate, tetrafluoroborate, acetate of the corresponding metal, or a complex of the corresponding metal. Comprises one of polyacrylic acid complex, polystyrene sulfonic acid complex, polyvinylamine complex, polyacrylonitrile complex, porphyrin complex, pyridine complex, pyrazine complex, piperazine complex, ammonia complex, purine complex, phenanthroline complex, chitosan complex and cyclodextrin complex. The solvent is one or more of water, methanol, ethanol, 1-propanol, 1-butanol, isopropanol, N-hexanol, acetic acid, N 'N-dimethylformamide, N' N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, benzene, toluene, xylene, m-trimethylbenzene, alkane and halogenated alkane.
Based on the technical scheme, preferably, the metal is at least one of Zn, Co, Fe, Cr, Cd, Cu, Ni, Mn, Al, Mg, K, Ti and Zr; the organic ligand in the organic ligand solution B is at least one of benzimidazole, 2-methylimidazole, 2-nitroimidazole, 4-methylimidazole-5-formaldehyde, imidazole-2-formaldehyde, 4-hydroxymethyl-5-methylimidazole, isophthalic acid, terephthalic acid and 2, 5-dihydroxy terephthalic acid.
Based on the above technical scheme, preferably, the solvent in the metal ion solution a and the organic ligand solution B is independently selected from one or more of water, methanol, ethanol, 1-propanol, isopropanol, N-hexanol, acetic acid, N 'N-dimethylformamide, N' N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, benzene, toluene, xylene, m-trimethylbenzene, alkane, and halogenated alkane.
Based on the technical scheme, the porous carrier is preferably an inorganic carrier or an organic polymer carrier, preferably alumina, silica, zirconia, titania, metal, alloy, glass, polysulfone, polyvinylidene fluoride, polyamide, polyimide and the like, and the pore diameter of the porous carrier is 1-100000 nm; the invention does not limit any pretreatment process of the carrier, and the carrier can be modified and grafted with a certain number of functional groups according to the requirement; the shape of the carrier is not limited in the present invention, but is preferably a sheet, a tube, a hollow fiber; the porous carrier comprises a symmetrical material or an asymmetrical material, namely a uniform pore structure or a multilevel pore structure; the porous carrier is unmodified or modified by acid, alkali or polymer and other modifying substances, and the modifying substances are preferably hydrochloric acid, sulfuric acid, sodium hydroxide, potassium hydroxide, silicone rubber, polyacrylic acid and polyacrylonitrile; the modification of the porous carrier refers to that the porous carrier is put into a modifier solution to be treated by heating, pulling, dipping and the like.
The impregnated carrier in the step (2) can be kept in a wet state or subjected to the next reaction after being dried.
Based on the above technical solution, preferably, the dipping treatment in the step (2) can be realized by one or more methods selected from the group consisting of solution dropping under normal pressure, pressurization or depressurization, solution pulling, solution spraying, solution blade coating, solution soaking and solution filtering.
Based on the above technical solution, preferably, after the solvent cleaning in step (4) is completed, steps (1) - (4) may be repeated again or multiple times as required to prepare a more compact and continuous membrane, and even during the repeating process, the types of the metal ions in the metal ion solution a and the organic ligands in the organic ligand solution B may be completely or partially replaced to prepare a hybrid MOF membrane with multiple crystal phases, meanwhile, the present invention does not limit the types of the pre-impregnation solution in step (2) and the reaction solution in step (3), and the hybrid MOF membrane can be successfully prepared if the metal ion solution a is introduced into the pre-impregnation organic ligand solution B for in-situ reaction.
In another aspect, the invention provides a MOF membrane prepared by the preparation method, and the composition, crystal type and topological structure of the MOF membrane are variousIncluding ZIF series, HKUST series, CAU series, MOF-74 series, UiO series, preferably Zn2(bim)4ZIF-7, ZIF-8, ZIF-11, ZIF-22, ZIF-65, ZIF-90, ZIF-93, ZIF-97, ZIF-108, ZIF-78, HKUST-1, CAU-10, Mg-MOF-74, Ni-MOF-74, Co-MOF-74, UiO-66, or a derivative thereof having a similar crystal type or topology to the above materials and bonding multiple functional groups; the MOF film is an ultrathin film with the thickness of 0.1 nm-50 mu m.
In the invention, one precursor solution is pre-impregnated into a porous carrier, and another precursor solution is added, and meets and reacts with the precursor reserved on the surface of the carrier and in the pores to generate the MOF along with the diffusion and permeation of the solution into the pores of the carrier. At a certain temperature, after a certain time and one or more reactions, a continuous separation membrane is finally formed.
Advantageous effects
In the invention, compared with the traditional in-situ crystallization synthesis method, the metal ion and organic ligand precursor solutions are not directly mixed, but gradually meet on the surface and inside of the carrier through successive impregnation and reaction, so that the randomness and the dispersity of the homogeneous nucleation process are changed, the nucleation and growth processes of film crystal grains are limited to the surface layer of the carrier, and the high controllability of the nucleation and growth processes is realized. In addition, according to the method provided by the invention, due to the pre-impregnation treatment, the carrier pore channel has a limited effect on the precursor solution, so that the film crystal grains grow to extend into the carrier pores, and thus, the film crystal grains are well matched with the carrier pore channel, and the falling of the film is effectively avoided.
The preparation method is simple and feasible, is suitable for industrial amplification, and can be applied to various fields, such as gas separation, liquid separation, sensors, adsorption, functional coatings and the like.
Drawings
FIG. 1 is a schematic diagram of the apparatus synthesized in example 1.
FIG. 2 shows Zn synthesized in example 12bim4Film X-ray diffraction pattern.
FIG. 3 shows Zn synthesized in example 12bim4Film scanning electron microscopy。
FIG. 4 shows Zn synthesized in example 22bim4Scanning electron microscopy of the film.
FIG. 5 shows Zn synthesized in example 22bim4Scanning electron microscopy of the film.
FIG. 6 shows Zn synthesized in example 42bim4Scanning electron microscopy of the film.
FIG. 7 is a scanning electron microscope image of the Mg-MOF-74 film synthesized in example 8.
Detailed Description
The following examples further illustrate the invention but are not intended to limit the invention thereto.
Example 1
Zn2(bim)4Preparation of molecular sieve membranes
Preparing a metal ion solution: 0.01116g of zinc nitrate hexahydrate is taken and dissolved in 20ml of methanol for standby.
Preparing an organic ligand solution: 0.02890g of benzimidazole was dissolved in 20ml of methanol and used.
The carrier is a porous α -alumina wafer with the diameter of 18mm and the thickness of 1mm, the carrier is of an asymmetric structure, the surface pore size is about 70nm, the front side is the front side, the bottom pore size is about 2 mu m, the back side is the back side, the carrier is washed by deionized water and acetone before use, and then the carrier is used after being dried.
The carrier impregnation method is negative pressure solution filtration, namely, the carrier is fixed on a device (such as the device shown in figure 1) with the right side facing upwards, the metal ion solution is added above the carrier, and then suction filtration is carried out to ensure that the solution is permeated out of the carrier.
Reaction: directly adding an organic ligand solution on the impregnated carrier, sealing the device, and reacting for 0.1h at room temperature.
Cleaning: the obtained membrane is soaked and cleaned for three times by methanol to replace the solvent.
Drying the membrane at room temperature, and then drying in an oven at 50 ℃ for more than 12h to obtain ultrathin Zn2(bim)4A molecular sieve membrane.
X-ray diffraction confirmed Zn2(bim)4Generated on the surface of the carrier (as shown in figure 2), and a ZIF-7 characteristic peak package appears at 6-7 ℃. Scanning electron microscope display of Zn2(bim)4The film was uniform and dense (see FIG. 3), and had a thickness of less than 100 nm.
The obtained ultrathin Zn2(bim)4The molecular sieve membrane was subjected to a mixed gas separation test. At room temperature, the volume ratio of hydrogen to carbon dioxide on the raw material side is 50: 50, the sweep gas is argon, the separation coefficient of the hydrogen/carbon dioxide under the normal pressure test can reach 67, and the maximum permeation quantity of the hydrogen can reach 1.75 multiplied by 10-6mol/m2The hydrogen/methane separation coefficient can reach 42 per second/Pa.
Example 2
Zn2(bim)4Preparation of molecular sieve membranes
Preparing a metal ion solution: 0.01116g of zinc nitrate hexahydrate is taken and dissolved in 20ml of methanol for standby.
Preparing an organic ligand solution: 0.02890g of benzimidazole was dissolved in 20ml of methanol and used.
The carrier is a porous α -alumina wafer with the diameter of 18mm and the thickness of 1mm, the carrier is of an asymmetric structure, the surface pore size is about 70nm, the front side is the front side, the bottom pore size is about 2 mu m, the back side is the back side, the carrier is washed by deionized water and acetone before use, and then the carrier is used after being dried.
Changing the reaction times according to the same operation of the embodiment 1, namely fixing the membrane after dipping, reacting and cleaning again, repeating the processes of dipping, reacting and cleaning once and twice, and finally drying the membrane to obtain Zn2(bim)4A molecular sieve membrane.
FIG. 4 is a scanning electron microscope image of a membrane prepared by two reactions, from which it can be seen that the membrane has a dense surface, a thickness of about 500nm, and is tightly bound to a carrier; FIG. 5 is a scanning electron microscope image of the membrane prepared by three reactions, from which it can be seen that the upper layer of the membrane surface is obviously cracked, but the carrier, i.e. the carrier has a dense membrane layer, and the membrane thickness is observed to be about 2 μm in the cross section.
Example 3
Zn2(bim)4Preparation of molecular sieve membranes
Preparing a metal ion complex solution: zinc porphyrin/DMF with the concentration of 0.02mol/L is evenly stirred for standby.
Preparing an organic ligand solution: benzimidazole/methanol, 0.026mol/L, stir for subsequent use.
The carrier is a porous α -alumina wafer with the diameter of 18mm and the thickness of 1mm, the carrier is of an asymmetric structure, the surface pore size is about 70nm, the front side is the front side, the bottom pore size is about 2 mu m, the back side is the back side, the carrier is washed by deionized water and acetone before use, and then the carrier is used after being dried.
The carrier dipping mode is solution lifting dipping, namely the carrier is fixed on a lifting machine and is dipped in Zn2+-pulling the porphyrin solution, wherein the pulling can be repeated for a plurality of times, and drying is carried out after the pulling is finished.
Reaction: directly adding an organic ligand solution on the impregnated carrier, sealing the device, and reacting for 24h at room temperature.
Cleaning: the obtained membrane is soaked and cleaned for three times by methanol to replace the solvent.
Drying the membrane for more than 5h at room temperature, and then drying the membrane for more than 12h in a 50 ℃ oven to obtain Zn2(bim)4A molecular sieve membrane.
Example 4
Zn2(bim)4Preparation of molecular sieve membranes
Preparing a metal ion complex solution: zinc porphyrin/DMF with the concentration of 0.02mol/L is dissolved for standby.
Preparing an organic ligand solution: and (3) dissolving benzimidazole/methanol at 0.026mol/L for later use.
The carrier is a porous α -alumina wafer with the diameter of 18mm and the thickness of 1mm, the carrier is of an asymmetric structure, the surface pore size is about 70nm, the front side is the front side, the bottom pore size is about 2 mu m, the back side is the back side, the carrier is washed by deionized water and acetone before use, and then the carrier is used after being dried.
The procedure was followed in the same manner as in example 3 except for changing the manner of impregnation.
The carrier impregnation mode is solution impregnation, namely the carrier is put into the stirred zinc porphyrin solution and is impregnated for 0.1 to 24 hours.
Finally, soaking and cleaning the obtained membrane with methanol for three times to replace the solvent. Drying the membrane to obtain Zn2(bim)4A molecular sieve membrane. Scanning electron microscope display of Zn2(bim)4The film was uniformly dense (see fig. 6).
Example 5
Zn2(bim)4Preparation of molecular sieve membranes
Preparing a metal ion complex solution: 1g of chitosan was taken, 1.689g of acetic acid and 100ml of water were added at 80 ℃ under reflux and stirred, and 50ml of Zn (NO) was added dropwise3)2Aqueous solution (0.045 g/ml).
Preparing an organic ligand solution: 0.0614g of benzimidazole was dissolved in 20ml of methanol and used.
The carrier is a porous α -alumina wafer with the diameter of 18mm and the thickness of 1mm, the carrier is of an asymmetric structure, the surface pore size is about 70nm, the front side is the front side, the bottom pore size is about 2 mu m, the back side is the back side, the carrier is washed by deionized water and acetone before use, and then the carrier is used after being dried.
The carrier impregnation mode is soaking impregnation, namely the carrier is put into the metal ion complex solution which is stirred and impregnated for 0.1 to 24 hours.
Reaction: directly adding an organic ligand solution on the impregnated carrier, sealing the device, and reacting for 24h at room temperature.
Cleaning: the obtained membrane is soaked and cleaned for three times by methanol to replace the solvent.
Drying the membrane for more than 5h at room temperature, and then drying the membrane for more than 12h in a 50 ℃ oven to obtain Zn2(bim)4A molecular sieve membrane.
Example 6
Preparation of ZIF-8 molecular sieve membrane
Preparing a metal ion solution: 0.210g of zinc nitrate hexahydrate is taken and dissolved in 20ml of methanol for standby. Preparing an organic ligand solution: 1.800g of 2-methylimidazole and 0.2g of sodium formate (deprotonating solvent) are dissolved in 20ml of methanol and are used.
The carrier is a porous silicon oxide wafer, the diameter of the carrier is 18mm, the thickness of the carrier is 1mm, the carrier is of a symmetrical structure, the size of pores is about 2 mu m, the carrier is uniformly polished by 2000-mesh abrasive paper before use, and then the carrier is ultrasonically cleaned by deionized water and acetone and dried.
And (3) modifying a carrier: the porous silicon oxide is used after being lifted and modified in polyacrylonitrile aqueous solution with certain concentration and dried.
The carrier impregnation method is solution dropwise permeation impregnation under normal pressure, namely, the carrier is fixed (as shown in figure 1), 2-methylimidazole solution is added on the surface of the carrier, then, after about 60min, the solution is observed to seep out from the front surface of the carrier, and after 60min, the residual solution on the surface is poured out.
Reaction: adding a zinc nitrate hexahydrate solution into the front surface of the carrier, sealing the device, and reacting at room temperature for 12 hours.
And soaking and cleaning the obtained membrane with methanol for three times, replacing the solvent, drying at room temperature for more than 5 hours, and drying in a 50 ℃ oven for more than 12 hours to obtain the ZIF-8 molecular sieve membrane. X-ray diffraction confirms that ZIF-8 is generated on the surface of the carrier, and scanning electron microscopy shows that a uniform ZIF-8 film is formed on the surface of the carrier.
Example 7
Preparation of ZIF-108 molecular sieve membrane
Preparing metal ion solution, namely taking 0.424g of zinc acetate dihydrate, adding 20ml of DMF for dissolving for later use, preparing organic ligand solution, namely taking 0.437g of 2-nitroimidazole, adding 20ml of DMF for dissolving for later use, preparing a carrier, namely a porous α -alumina wafer, wherein the diameter is 18mm, the thickness is 1mm, the carrier is of an asymmetric structure, the size of a surface pore is about 70nm, the front surface is a front surface, a bottom hole is about 2 mu m, the back surface is a back surface, and the carrier is washed by deionized water and acetone before use, and then is used after being heated and dried.
The carrier impregnation method is negative pressure solution filtration, namely, the carrier is fixed on a device (such as the device shown in figure 1) with the right side facing upwards, the metal ion solution is added above the carrier, and then suction filtration is carried out to ensure that the solution is permeated out of the carrier.
Reaction: directly adding organic ligand solution on the impregnated carrier, sealing the device, and reacting at room temperature for 0.1h, 3h and 6 h.
Cleaning: the obtained membrane is soaked and cleaned for three times by methanol to replace the solvent.
Drying the membrane for more than 5h at room temperature, and then drying in an oven at 50 ℃ for more than 12 h. X-ray diffraction proves that ZIF-108 is generated on the surface of the carrier under different reaction durations, and scanning electron microscopes show that the ZIF-108 films obtained under different reaction durations have different compactness degrees.
Example 8
Preparation of Mg-MOF-74 molecular sieve membrane:
preparing a metal ion solution: 0.712g of magnesium nitrate hexahydrate is taken and dissolved in 18ml of DMF, 1.5ml of ethanol and 1.5ml of deionized water for standby. Preparing an organic ligand solution: 0.167g of 2, 5-dihydroxy terephthalic acid is taken and dissolved in 18ml of DMF, 1.5ml of ethanol and 1.5ml of deionized water for standby.
The carrier is a porous gamma-alumina wafer, the diameter of the carrier is 18mm, the thickness of the carrier is 1mm, the carrier is of an asymmetric structure, the surface pore size is about 5nm, the front surface is the front surface, the bottom hole is about 2 microns, the back surface is the back surface, the carrier is washed by deionized water and acetone before use, and the carrier is used after being heated and dried.
The carrier impregnation method comprises the combination of negative pressure solution filtration and solution dripping and permeation impregnation under normal pressure, namely fixing the carrier on a device (shown in figure 1), allowing the front side to face upwards, adding a metal ion solution above the carrier, performing suction filtration for 1min to allow the solution to permeate out of the carrier, stopping suction filtration after 1min, standing for permeation for 1h, and pouring out the residual solution on the surface after 1 h. .
Reaction: adding organic ligand solution on the impregnated carrier, and reacting at 100 deg.C for 72 h. And soaking and cleaning the obtained membrane sheet with methanol for three times, replacing the solvent, then drying at room temperature for more than 5h, and then drying in a 50 ℃ oven for more than 12h to obtain the Mg-MOF-74 molecular sieve membrane.
X-ray diffraction confirmed that Mg-MOF-74 was produced on the support surface, and scanning electron microscopy showed that a uniform Mg-MOF-74 film was formed on the support surface (FIG. 7).
Claims (10)
1. A method for the in situ controlled synthesis of a MOF film, comprising the steps of:
(1) respectively arranged at a concentration of 1 × 10-4About 1mol/L of metal ion solution A and the concentration of 1 multiplied by 10-41mol/L organic ligand solution B;
(2) impregnation treatment of the porous carrier: placing the porous carrier in a metal ion solution A for dipping treatment, so that metal ions are adsorbed on the surface and in the pores of one side of the porous carrier, and obtaining the carrier adsorbed with the metal ions;
(3) in-situ reaction: fixing the carrier adsorbed with the metal ions in a reaction tank, introducing an organic ligand solution B into one side of the carrier adsorbed with the metal ions, sealing the reaction tank, and starting a synthesis reaction; the temperature of the synthesis reaction is 5-200 ℃, and the reaction time is 1 minute-10 days;
(4) cleaning the membrane sheet obtained in the step (3) with a solvent, and drying to obtain the MOF membrane, wherein the solvent is at least one of water, methanol, ethanol, acetic acid, isopropanol, N' N-dimethylformamide, toluene and xylene; the drying temperature is 20-180 ℃, and the drying time is 1 hour-2 days.
2. The method for the in-situ controlled synthesis of MOF membranes according to claim 1, wherein the metal ion solution A and the organic ligand solution B further comprise a deprotonating agent, a coordination regulator or a surfactant; carboxylate, organic amine and monodentate ligand containing nitrogen and oxygen are preferred.
3. The method for the in situ controlled synthesis of MOF film according to claim 1, wherein in step (1) the metal ions in the metal ion solution a are derived from metal ion salts or metal ion complexes.
4. The in-situ controllable synthesis method of the MOF film according to claim 1, wherein the metal in the metal ion solution A is at least one of Zn, Co, Fe, Cr, Cd, Cu, Ni, Mn, Al, Mg, K, Ti and Zr; the organic ligand is one or more of benzimidazole, 2-methylimidazole, 2-nitroimidazole, 4-methylimidazole-5-formaldehyde, imidazole-2-formaldehyde, 4-hydroxymethyl-5-methylimidazole, isophthalic acid or 2, 5-dihydroxyterephthalic acid.
5. The method for the in situ controlled synthesis of MOF membrane according to claim 1, wherein the solvent of solution a and solution B is independently selected from one or more of water, methanol, ethanol, 1-propanol, 1-butanol, isopropanol, N-hexanol, acetic acid, N 'N-dimethylformamide, N' N-dimethylacetamide, N-methylpyrrolidone, tetrahydrofuran, benzene, toluene, xylene, m-trimethylbenzene, alkane, halogenated alkane.
6. A process for the in situ controlled synthesis of MOF membranes according to claim 1, wherein the porous support is an inorganic support or an organic polymer support, preferably alumina, silica, zirconia, titania, metals, alloys, glass, polysulfone, polyvinylidene fluoride, polyamide, polyimide; the pore diameter of the porous carrier is 1-100000 nm; the porous carrier is tubular, flaky or hollow fiber; the porous carrier is in a uniform pore structure or a multilevel pore structure; the porous carrier is unmodified or modified by acid, alkali or polymer.
7. The method for the in-situ controlled synthesis of the MOF membrane according to claim 1, wherein the dipping treatment mode in the step (2) is one or more of the combination of normal pressure, solution dropping under pressure or reduced pressure, solution pulling, solution spraying, solution blade coating, solution soaking and solution filtering.
8. A method for the in situ controlled synthesis of MOF membrane according to claim 1 wherein after completion of the solvent wash of step (4), steps (1) - (4) are repeated one or more times, with or without changing the type of metal ion solution a and organic ligand solution B during the repetition.
9. The method for the in situ controlled synthesis of a MOF film according to claim 3, wherein the metal ion complex is one of polyacrylic complex, polystyrene sulfonic acid complex, polyvinylamine complex, polyacrylonitrile complex, porphyrin complex, pyridine complex, pyrazine complex, piperazine complex, ammonia complex, purine complex, phenanthroline complex, chitosan complex, cyclodextrin complex.
10. An MOF membrane synthesized by the in-situ controllable synthesis method of the MOF membrane according to claim 1, wherein the thickness of the MOF membrane is 0.1 nm-50 μm; the MOFs are ZIF series, HKUST series, CAU series, MOF-74 series and UiO series; preferably Zn2(bim)4ZIF-7, ZIF-8, ZIF-11, ZIF-22, ZIF-65, ZIF-90, ZIF-93, ZIF-97, ZIF-108, ZIF-78, HKUST-1, CAU-10, Mg-MOF-74, Ni-MOF-74, Co-MOF-74, UiO-66, or derivatives thereof having a plurality of functional groups bonded thereto.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811460270.5A CN111249918B (en) | 2018-11-30 | 2018-11-30 | In-situ controllable synthesis method of MOF (Metal-organic framework) membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811460270.5A CN111249918B (en) | 2018-11-30 | 2018-11-30 | In-situ controllable synthesis method of MOF (Metal-organic framework) membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111249918A true CN111249918A (en) | 2020-06-09 |
| CN111249918B CN111249918B (en) | 2022-01-28 |
Family
ID=70946563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811460270.5A Active CN111249918B (en) | 2018-11-30 | 2018-11-30 | In-situ controllable synthesis method of MOF (Metal-organic framework) membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111249918B (en) |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111672330A (en) * | 2020-06-16 | 2020-09-18 | 北京工业大学 | Method for preparing MOF nanofiltration membrane by adopting synthesis technology after thermal annealing |
| CN111744375A (en) * | 2020-07-21 | 2020-10-09 | 天津工业大学 | Mixed matrix membrane with high-selectivity gas channel and preparation method thereof |
| CN111888944A (en) * | 2020-09-02 | 2020-11-06 | 吉林建筑大学 | Metal-organic framework material/film composite material and preparation method and application thereof |
| CN112246111A (en) * | 2020-10-11 | 2021-01-22 | 天津工业大学 | Preparation method of metal organic framework film |
| CN112574429A (en) * | 2020-12-23 | 2021-03-30 | 常州大学 | Organically modified MIL-101(Cr, Cu) material and preparation method and application thereof |
| CN112592486A (en) * | 2020-12-10 | 2021-04-02 | 南京科技职业学院 | Cd (II) coordination polymer with two-dimensional supramolecular structure and preparation method thereof |
| CN113024829A (en) * | 2021-03-09 | 2021-06-25 | 东北大学 | In-situ rapid preparation method of metal organic coordination polymer film suitable for various void-rich substrates |
| CN113041863A (en) * | 2021-03-24 | 2021-06-29 | 大连理工大学 | Preparation method and application of defect-free and pollution-resistant zirconium-based metal organic framework film |
| CN113522292A (en) * | 2021-06-17 | 2021-10-22 | 三峡大学 | Preparation method and application of porous carbon-loaded nickel material |
| CN114292413A (en) * | 2021-12-31 | 2022-04-08 | 贵州乌江水电开发有限责任公司思林发电厂 | Preparation method and application of self-repairing material based on aromatic carboxylic acids MOFs |
| CN114471174A (en) * | 2021-02-25 | 2022-05-13 | 大连理工大学 | Preparation method of in-pore synthesized ZIF-8 membrane |
| CN114602331A (en) * | 2020-12-07 | 2022-06-10 | 宁波市电力设计院有限公司 | Preparation method and application of polymer-based composite membrane |
| CN114733368A (en) * | 2022-04-25 | 2022-07-12 | 江西师范大学 | ZIF-8 film and spraying preparation method and application thereof |
| CN115028846A (en) * | 2022-05-13 | 2022-09-09 | 山东理工大学 | Two-dimensional Zn 2 (bim) 4 Method for synthesizing metal organic framework material |
| CN115870006A (en) * | 2022-11-29 | 2023-03-31 | 北京工业大学 | Ceramic matrix composite for degrading low-concentration formaldehyde and preparation method thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890305A (en) * | 2010-04-01 | 2010-11-24 | 大连理工大学 | Method for preparing metallic organic frame films |
| CN103272491A (en) * | 2013-06-19 | 2013-09-04 | 北京工业大学 | Preparation method for in situ self-assembled organic/inorganic hybrid membrane based on coordination |
| CN104001426A (en) * | 2014-05-29 | 2014-08-27 | 北京工业大学 | Preparation method of high dispersion metal-organic framework (MOF)/organic hybrid priority alcohol through composite membrane |
| CN104624160A (en) * | 2015-01-21 | 2015-05-20 | 北京科技大学 | Preparation method of thermal conduction enhanced metal organic framework gas storage material |
| CN104959044A (en) * | 2015-06-30 | 2015-10-07 | 浙江工业大学 | Synthetic method of metal organic skeleton membrane |
| US20160151762A1 (en) * | 2014-12-02 | 2016-06-02 | Numat Technologies, Inc. | Formation of high surface area metal-organic frameworks |
| CN106178982A (en) * | 2016-07-21 | 2016-12-07 | 北京工业大学 | A kind of preparation method of the metal organic framework film inverting based on subcarbonate |
| CN107159130A (en) * | 2017-05-22 | 2017-09-15 | 山东大学 | A kind of preparation method of metal organic framework tunica fibrosa |
-
2018
- 2018-11-30 CN CN201811460270.5A patent/CN111249918B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101890305A (en) * | 2010-04-01 | 2010-11-24 | 大连理工大学 | Method for preparing metallic organic frame films |
| CN103272491A (en) * | 2013-06-19 | 2013-09-04 | 北京工业大学 | Preparation method for in situ self-assembled organic/inorganic hybrid membrane based on coordination |
| CN104001426A (en) * | 2014-05-29 | 2014-08-27 | 北京工业大学 | Preparation method of high dispersion metal-organic framework (MOF)/organic hybrid priority alcohol through composite membrane |
| US20160151762A1 (en) * | 2014-12-02 | 2016-06-02 | Numat Technologies, Inc. | Formation of high surface area metal-organic frameworks |
| CN104624160A (en) * | 2015-01-21 | 2015-05-20 | 北京科技大学 | Preparation method of thermal conduction enhanced metal organic framework gas storage material |
| CN104959044A (en) * | 2015-06-30 | 2015-10-07 | 浙江工业大学 | Synthetic method of metal organic skeleton membrane |
| CN106178982A (en) * | 2016-07-21 | 2016-12-07 | 北京工业大学 | A kind of preparation method of the metal organic framework film inverting based on subcarbonate |
| CN107159130A (en) * | 2017-05-22 | 2017-09-15 | 山东大学 | A kind of preparation method of metal organic framework tunica fibrosa |
Cited By (23)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111672330A (en) * | 2020-06-16 | 2020-09-18 | 北京工业大学 | Method for preparing MOF nanofiltration membrane by adopting synthesis technology after thermal annealing |
| CN111744375B (en) * | 2020-07-21 | 2021-08-06 | 天津工业大学 | Mixed matrix membrane with high-selectivity gas channel and preparation method thereof |
| CN111744375A (en) * | 2020-07-21 | 2020-10-09 | 天津工业大学 | Mixed matrix membrane with high-selectivity gas channel and preparation method thereof |
| CN111888944A (en) * | 2020-09-02 | 2020-11-06 | 吉林建筑大学 | Metal-organic framework material/film composite material and preparation method and application thereof |
| CN111888944B (en) * | 2020-09-02 | 2022-06-03 | 吉林建筑大学 | Metal-organic framework material/film composite material and preparation method and application thereof |
| CN112246111A (en) * | 2020-10-11 | 2021-01-22 | 天津工业大学 | Preparation method of metal organic framework film |
| CN112246111B (en) * | 2020-10-11 | 2021-08-06 | 天津工业大学 | Preparation method of metal organic framework film |
| CN114602331B (en) * | 2020-12-07 | 2023-11-17 | 宁波市电力设计院有限公司 | Preparation method and application of polymer-based composite film |
| CN114602331A (en) * | 2020-12-07 | 2022-06-10 | 宁波市电力设计院有限公司 | Preparation method and application of polymer-based composite membrane |
| CN112592486A (en) * | 2020-12-10 | 2021-04-02 | 南京科技职业学院 | Cd (II) coordination polymer with two-dimensional supramolecular structure and preparation method thereof |
| CN112592486B (en) * | 2020-12-10 | 2022-07-05 | 南京科技职业学院 | Cd (II) coordination polymer with two-dimensional supramolecular structure and preparation method thereof |
| CN112574429A (en) * | 2020-12-23 | 2021-03-30 | 常州大学 | Organically modified MIL-101(Cr, Cu) material and preparation method and application thereof |
| CN114471174A (en) * | 2021-02-25 | 2022-05-13 | 大连理工大学 | Preparation method of in-pore synthesized ZIF-8 membrane |
| CN113024829B (en) * | 2021-03-09 | 2022-05-17 | 东北大学 | In-situ rapid preparation method of metal organic coordination polymer film suitable for various void-rich substrates |
| CN113024829A (en) * | 2021-03-09 | 2021-06-25 | 东北大学 | In-situ rapid preparation method of metal organic coordination polymer film suitable for various void-rich substrates |
| CN113041863A (en) * | 2021-03-24 | 2021-06-29 | 大连理工大学 | Preparation method and application of defect-free and pollution-resistant zirconium-based metal organic framework film |
| CN113522292A (en) * | 2021-06-17 | 2021-10-22 | 三峡大学 | Preparation method and application of porous carbon-loaded nickel material |
| CN114292413B (en) * | 2021-12-31 | 2023-10-27 | 贵州乌江水电开发有限责任公司思林发电厂 | Preparation method and application of self-repairing material based on aromatic carboxylic acid MOFs |
| CN114292413A (en) * | 2021-12-31 | 2022-04-08 | 贵州乌江水电开发有限责任公司思林发电厂 | Preparation method and application of self-repairing material based on aromatic carboxylic acids MOFs |
| CN114733368A (en) * | 2022-04-25 | 2022-07-12 | 江西师范大学 | ZIF-8 film and spraying preparation method and application thereof |
| CN115028846A (en) * | 2022-05-13 | 2022-09-09 | 山东理工大学 | Two-dimensional Zn 2 (bim) 4 Method for synthesizing metal organic framework material |
| CN115028846B (en) * | 2022-05-13 | 2023-09-26 | 山东理工大学 | Two-dimensional Zn 2 (bim) 4 Synthesis method of metal organic framework material |
| CN115870006A (en) * | 2022-11-29 | 2023-03-31 | 北京工业大学 | Ceramic matrix composite for degrading low-concentration formaldehyde and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111249918B (en) | 2022-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN111249918B (en) | In-situ controllable synthesis method of MOF (Metal-organic framework) membrane | |
| Xiao et al. | Metal-phenolic network as precursor for fabrication of metal-organic framework (MOF) nanofiltration membrane for efficient desalination | |
| Xu et al. | MOF-based membranes for pervaporation | |
| Wang et al. | Secondary growth of covalent organic frameworks (COFs) on porous substrates for fast desalination | |
| Yeo et al. | An overview: synthesis of thin films/membranes of metal organic frameworks and its gas separation performances | |
| Li et al. | In-situ growth of UiO-66-NH2 in porous polymeric substrates at room temperature for fabrication of mixed matrix membranes with fast molecular separation performance | |
| Kong et al. | Synthesis of a highly stable ZIF-8 membrane on a macroporous ceramic tube by manual-rubbing ZnO deposition as a multifunctional layer | |
| Li et al. | Sol–gel asynchronous crystallization of ultra-selective metal–organic framework membranes for gas separation | |
| Tao et al. | A hollow ceramic fiber supported ZIF-8 membrane with enhanced gas separation performance prepared by hot dip-coating seeding | |
| US20150367294A1 (en) | Process for the preparation of mofs-porous polymeric membrane composites | |
| US20150246318A1 (en) | Methods to Rapidly Deposit Thin Films (or Coatings) of Microporous Material on Supports Using Thermally Induced Self-Assembly | |
| CN111298665A (en) | UIO-66-NH2Doped organic silicon high-salt wastewater treatment membrane and preparation method thereof | |
| CN113041864A (en) | Method for modifying ceramic-based TFN forward osmosis membrane by titanium dioxide intermediate layer and application of method | |
| Yao et al. | Formation of ZIF-8 membranes and crystals in a diluted aqueous solution | |
| CN108704491B (en) | Method for preparing layered metal organic framework film by vapor gel method | |
| CN105879708B (en) | A kind of method for preparing the metal organic framework films of Co ZIF 67 using not homologous zinc oxide film induction | |
| Nian et al. | Preparation of a pure ZIF-67 membrane by self-conversion of cobalt carbonate hydroxide nanowires for H 2 separation | |
| CN114585432A (en) | Polycrystalline metal-organic framework membranes for separating mixtures | |
| Wu et al. | ZIF-8/GO sandwich composite membranes through a precursor conversion strategy for H2/CO2 separation | |
| CN113041863A (en) | Preparation method and application of defect-free and pollution-resistant zirconium-based metal organic framework film | |
| CN110665378A (en) | Transition metal ion modified covalent organic framework/polymer hybrid membrane, preparation and application | |
| KR101261994B1 (en) | Filmy self-supporting thin metal film for hydrogen separation and process for producing the same | |
| CN114797799A (en) | Preparation method of MOFs-based lithium ion imprinting composite nanofiber membrane | |
| CN112029104B (en) | Metal organic framework film prepared by vapor-assisted epitaxial growth method and application thereof | |
| He et al. | High hydrogen permeable ZIF-8 membranes on double modified substrates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |