CN114367199A - Method for preparing MOF film by in-situ phase inversion method and application - Google Patents
Method for preparing MOF film by in-situ phase inversion method and application Download PDFInfo
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Abstract
The invention discloses a method for preparing an MOF film by an in-situ phase inversion method and application thereof, wherein the influences of factors related to seed loading capacity, formic acid amount, synthesis time and synthesis temperature on the compactness, thickness, surface roughness and film hydrophilicity of the MOF film are researched in the process, and the method is applied to ethanol/water and butanol/water separation. The invention successfully prepares the ultrathin MOF membrane, has excellent separation performance and good long-term stability, and is a separation technology with great potential.
Description
Technical Field
The invention belongs to the field of new materials, and particularly relates to a method for preparing an MOF film by an in-situ phase inversion method and application thereof.
Background
As an alternative technology of rectification separation, pervaporation technology has been developed as an industrially acceptable practical technology, and has been in the history for decades, and plays an important role in energy conservation and consumption reduction in related industries such as organic solvent dehydration, azeotropic component separation and the like, thus proving the reliability and competitiveness of the new membrane technology.
Conventional pervaporation membrane materials include polymeric membranes, ceramic membranes, zeolite membranes, and the like. The polymer membrane is easy to prepare and has strong mechanical strength, is widely applied to the processes of industrial gas separation, reverse osmosis and the like, and has the problem of poor chemical stability and thermal stability in pervaporation application. Inorganic membranes, particularly zeolite membranes, have been widely used for dehydration of organic materials, but the structure is more fragile, limiting the application of the membranes. The Metal Organic Framework (MOF) membrane has a universal topological structure, a precisely adjustable nano-pore structure and a strong framework structure, so that the MOF membrane is a separation material with great potential. Metal-organic frameworks (MOFs) are a class of materials with periodic network structure formed by coordination interaction of organic ligands and metal centers. Compared with the traditional inorganic porous material, the MOFs material has the advantages of larger specific surface area, higher porosity, adjustable structure and pore channel height and the like.
The common preparation methods of the metal organic framework film comprise in-situ hydrothermal synthesis, a secondary growth method and the like. These methods are all limited to varying degrees by factors such as: large amount of raw material liquid, influence of membrane assembly mode, etc. Under the steam-assisted action, the preparation of the ultrathin MOF film material is realized by the original taste phase conversion of the metal organic framework material, and the prepared MOF film has excellent pervaporation performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, and provides an MOF film with ultrathin thickness prepared by an in-situ phase inversion technology and application thereof.
The technical scheme of the invention is a method for preparing an MOF film by an in-situ phase inversion method, which mainly comprises the following steps:
(1) preparing NU-906 particles;
(2) polishing the surface of a self-made silicon dioxide carrier by using sand paper, coating 50nm silicon dioxide particles, and calcining for 5 hours at 550 ℃ to obtain the silicon dioxide carrier with a smooth and flat surface;
(3) dispersing the prepared NU-906 seed crystals in a solvent, and assembling the seed crystals on a modified silicon dioxide carrier by a wet coating mode to form a compact NU-906 layer for later use;
(4) placing the carrier loaded with the NU-906 particles in a polytetrafluoroethylene liner with a support, adding formic acid, controlling time and temperature to enable the NU-906 particles to generate a compact MOF film through in-situ phase transformation, and soaking the obtained MOF film in acetone for storage after the reaction is finished;
(5) evaluating the permeability of the MOF film by using a self-assembled device, and evaluating the long-term stability of the film;
(6) the surface appearance and the thickness of the MOF film are represented by SEM, the XRD reflects the orientation of the MOF film, the surface roughness of the MOF film is observed by AFM, the water contact angle is tested to test the hydrophilicity of the MOF film at different time, and the structural characteristics and the separation performance of the oriented MOF film are further explained;
the load of the NU-906 in the step (3) is 5-500mg/cm2；
The reaction temperature of the MOF film in the step (4) is 25-150 ℃;
the reaction time of the MOF film in the step (4) is 2-48 h;
the amount of formic acid in the step (4) is 0.08-2000 mu L/mg NU-906.
The solvent in the step (3) comprises N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, water, lower alkane alcohol (C1-C6), acetonitrile, acetone or ethyl acetate.
The preparation method of the MOF film in the step (4) is in-situ phase inversion.
The penetration evaluation system in the step (5) is 20-95 wt% of ethanol/water respectively, and the operation temperature is 20-120 ℃; 20 wt% -95 wt% butanol/water, and the operation temperature is 20-120 ℃.
The invention prepares NU-906 particles, which comprises the following steps: solution A: dissolving 58.5mg of zirconium chloride and 24mg of benzoic acid in 1.8mL of N, N-dimethylformamide, heating at 80 ℃ for 1h, and cooling to room temperature; and B, liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxyphenyl substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; mixing the prepared solution A, solution B and 288mg benzoic acid, and heating at 100 deg.C for 2-72 hr to obtain white powdered NU-906 granules.
The second technical scheme of the invention is that the MOF film prepared by the in-situ phase inversion method prepared by the method is applied to ethanol/water and butanol/water separation.
The invention has the advantages that:
the MOF film is successfully prepared by using an in-situ phase inversion method, the preparation method is simple, convenient and quick, and no additional chemical reagent is needed. In separation application, the separation factor of the MOF film to ethanol/water is up to 600, and the flux is 2.5 kg/(m)2H) a butanol/water separation factor of up to 6000 and a flux of 3.8 kg/(m)2H). The MOF film prepared by the invention has ultrathin thickness, excellent separation performance and good long-term stability, and is a separation technology with great potential.
Drawings
FIG. 1: the loading capacity is 250mg/cm2And when the amount of formic acid is 2 mu L/mg NU-906, the XRD pattern of the MOF membrane prepared after 24 hours of reaction at 100 ℃.
FIG. 2: the loading capacity is 250mg/cm2And the amount of formic acid is 2 muL/mg NU-906, surface map of MOF membrane prepared after 24h reaction at 100 ℃.
FIG. 3: the loading capacity is 250mg/cm2And the cross-sectional view of the MOF membrane prepared after 24h of reaction at 100 ℃ when the amount of formic acid is 2 mu L/mg NU-906.
FIG. 4: the loading capacity is 250mg/cm2And the amount of formic acid was 2. mu.L/mg NU-906, AFM profile of MOF film prepared after 24h reaction at 100 ℃.
FIG. 5: the loading capacity is 250mg/cm2And the water contact angle of the MOF membrane prepared after 24h of reaction at 100 ℃ when the amount of formic acid is 2 mu L/mg NU-906.
Detailed Description
The present invention will be further described with reference to the following examples.
Preparation of NU-906 seeds of the invention, reference is made to: phase Transitions In Metal-Organic framework direct Monitored through In silicon Variable Transmission Electron Microscopy and In silicon Xray Diffraction [ J ] Journal of the American Chemical Society,2020, 142(10): 4609-.
Example 1:
(1) solution A: dissolving 58.5mg of zirconium chloride and 24mg of benzoic acid in 1.8mL of N, N-dimethylformamide, heating at 80 ℃ for 1h, and cooling to room temperature; and B, liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxyphenyl substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; mixing the prepared solution A, solution B and 288mg benzoic acid, heating at 100 deg.C for 2-72 hr to obtain white powdered NU-906 granule;
(2) polishing the surface of a self-made silicon dioxide carrier by using sand paper, coating 50nm silicon dioxide particles, and calcining for 5 hours at 550 ℃ to obtain the silicon dioxide carrier with a smooth surface;
(3) 2.5mg of NU-906 seed crystals were dispersed in 2.6mL of N, N-dimethylformamide to a monolithic loading of 5mg/cm2Assembling the modified silicon dioxide carrier by a wet coating mode to form a compact NU-906 layer for later use;
(4) placing the carrier precoated with NU-906 in a polytetrafluoroethylene lining with a support, controlling the synthesis time, the synthesis temperature and the amount of formic acid, assisting the NU-906 particles with formic acid vapor to generate a compact MOF film through in-situ phase transformation, and soaking the obtained MOF film in acetone for storage after the reaction is finished;
(5) evaluating the permeability of the MOF film by using a self-assembled device, and evaluating the long-term stability of the film;
(6) the preparation method of the MOF membrane is in-situ phase inversion;
(7) the synthesis temperature of the MOF film is 25-150 DEG C℃；
(8) The synthesis time of the MOF membrane is 2-48 h;
(9) the amount of the MOF film formic acid is 0.08-2000 mu L/mg NU-906;
(10) the penetration evaluation system is 20-95 wt% ethanol/water, and the operation temperature is 20-120℃(ii) a 20 wt% -95 wt% butanol/water, operating temperature 20-120℃。
(11) When the amount of formic acid is 2 muWhen the concentration is L/mg NU-906, the MOF membrane prepared after the reaction is carried out for 24 hours at 100 ℃ has a 90 wt% ethanol/water separation factor of 390 and a flux of 3.8 kg/(m)2H); the separation factor of 90 wt% butanol/water is 4020, and the flux is 2.3 kg/(m)2·h)。
(12) When the amount of formic acid is 2 muL/mg NU-906, the film thickness prepared after 24h of reaction at 100 ℃ is 130nm, the roughness of the film is 8.9nm, and the water contact angle is 65 degrees.
Example 2:
(1) solution A: dissolving 58.5mg of zirconium chloride and 24mg of benzoic acid in 1.8mL of N, N-dimethylformamide, heating at 80 ℃ for 1h, and cooling to room temperature; and B, liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxyphenyl substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; mixing the prepared solution A, solution B and 288mg benzoic acid, heating at 100 deg.C for 2-72 hr to obtain white powdered NU-906 granule;
(2) polishing the surface of a self-made silicon dioxide carrier by using sand paper, coating 50nm silicon dioxide particles, and calcining for 5 hours at 550 ℃ to obtain the silicon dioxide carrier with a smooth surface;
(3) 10mg of NU-906 seed crystals were dispersed in 2.6mL of N, N-dimethylformamide to a monolithic loading of 20mg/cm2Assembling the modified silicon dioxide carrier by a wet coating mode to form a compact NU-906 layer for later use;
(4) placing the carrier precoated with NU-906 in a polytetrafluoroethylene lining with a support, controlling the synthesis time, the synthesis temperature and the amount of formic acid, assisting the NU-906 particles with formic acid vapor to generate a compact MOF film through in-situ phase transformation, and soaking the obtained MOF film in acetone for storage after the reaction is finished;
(5) evaluating the permeability of the MOF film by using a self-assembled device, and evaluating the long-term stability of the film;
(6) the preparation method of the MOF membrane is in-situ phase inversion;
(7) the synthesis temperature of the MOF film is 25-150 DEG C℃；
(8) The synthesis time of the MOF membrane is 2-48 h;
(9) the amount of the MOF film formic acid is 0.08-2000 mu L/mg NU-906;
(10) the penetration evaluation system is 20-95 wt% ethanol/water, and the operation temperature is 20-120℃(ii) a 20 wt% -95 wt% butanol/water, operating temperature 20-120℃。
(10) When the amount of formic acid is 2 mu L/mg NU-906, the MOF membrane prepared after 24 hours of reaction at 100 ℃ has a 90 wt% ethanol/water separation factor of 437, and the flux is 3.1 kg/(m)2H); the separation factor of the 90 wt% butanol/water is 4250, and the flux is 2.1 kg/(m)2·h)。
(11) When the amount of formic acid is 2 muL/mg NU-906, the thickness of the MOF film prepared after 24h reaction at 100 ℃ is 130nm, the roughness of the film is 6.7nm, and the water contact angle is 57 degrees.
Example 3:
(1) solution A: dissolving 58.5mg of zirconium chloride and 24mg of benzoic acid in 1.8mL of N, N-dimethylformamide, heating at 80 ℃ for 1h, and cooling to room temperature; and B, liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxyphenyl substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; mixing the prepared solution A, solution B and 288mg benzoic acid, heating at 100 deg.C for 2-72 hr to obtain white powdered NU-906 granule;
(2) polishing the surface of a self-made silicon dioxide carrier by using sand paper, coating 50nm silicon dioxide particles, and calcining for 5 hours at 550 ℃ to obtain the silicon dioxide carrier with a smooth surface;
(3) 40mg of NU-906 seed crystals were dispersed in 2.6mL of N, N-dimethylformamide to give a monolithic loading of 80mg/cm2Assembling the modified silicon dioxide carrier by a wet coating mode to form a compact NU-906 layer for later use;
(4) placing the carrier precoated with NU-906 in a polytetrafluoroethylene lining with a support, controlling the synthesis time, the synthesis temperature and the amount of formic acid, assisting the NU-906 particles with formic acid vapor to generate a compact MOF film through in-situ phase transformation, and soaking the obtained MOF film in acetone for storage after the reaction is finished;
(5) evaluating the permeability of the MOF film by using a self-assembled device, and evaluating the long-term stability of the film;
(6) the preparation method of the MOF membrane is in-situ phase inversion;
(7) synthesis temperature of the MOF membraneIs 25-150℃；
(8) The synthesis time of the MOF membrane is 2-48 h;
(9) the amount of the MOF film formic acid is 0.08-2000 mu L/mg NU-906;
(10) the penetration evaluation system is 20-95 wt% ethanol/water, and the operation temperature is 20-120℃(ii) a 20 wt% -95 wt% butanol/water, operating temperature 20-120℃。
(11) When the amount of formic acid is 2 muL/mg NU-906, the MOF membrane prepared after 24h of reaction at 100 ℃ has 473 of 90 wt% ethanol/water separation factor and 2.8 kg/(m) of flux2H); 4532 for 90 wt% butanol/water separation factor and 2.2 kg/(m)2·h)。
(12) When the amount of formic acid is 2 muL/mg NU-906, the thickness of the MOF film prepared after 24h reaction at 100 ℃ is 140nm, the roughness of the film is 4.5nm, and the water contact angle is 45 degrees.
Example 4:
(1) solution A: dissolving 58.5mg of zirconium chloride and 24mg of benzoic acid in 1.8mL of N, N-dimethylformamide, heating at 80 ℃ for 1h, and cooling to room temperature; and B, liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxyphenyl substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; mixing the prepared solution A, solution B and 288mg benzoic acid, heating at 100 deg.C for 2-72 hr to obtain white powdered NU-906 granule;
(2) polishing the surface of a self-made silicon dioxide carrier by using sand paper, coating 50nm silicon dioxide particles, and calcining for 5 hours at 550 ℃ to obtain the silicon dioxide carrier with a smooth surface;
(3) 90mg of NU-906 seed crystals were dispersed in 2.6mL of N, N-dimethylformamide to give a monolithic loading of 180mg/cm2Assembling the modified silicon dioxide carrier by a wet coating mode to form a compact NU-906 layer for later use;
(4) placing the carrier precoated with NU-906 in a polytetrafluoroethylene lining with a support, controlling the synthesis time, the synthesis temperature and the amount of formic acid, assisting the NU-906 particles with formic acid vapor to generate a compact MOF film through in-situ phase transformation, and soaking the obtained MOF film in acetone for storage after the reaction is finished;
(5) evaluating the permeability of the MOF film by using a self-assembled device, and evaluating the long-term stability of the film;
(6) the preparation method of the MOF membrane is in-situ phase inversion;
(7) the synthesis temperature of the MOF film is 25-150 DEG C℃；
(8) The synthesis time of the MOF membrane is 2-48 h;
(9) the amount of the MOF film formic acid is 0.08-2000 mu L/mg NU-906;
(10) the penetration evaluation system is 20-95 wt% ethanol/water, and the operation temperature is 20-120℃(ii) a 20 wt% -95 wt% butanol/water, operating temperature 20-120℃。
(11) When the amount of formic acid is 2 mu L/mg NU-906, the MOF membrane prepared after 24 hours of reaction at 100 ℃ has a factor of 455 to 90 wt% ethanol/water separation and a flux of 3.3 kg/(m)2H); the separation factor of 90 wt% butanol/water is 4672, and the flux is 2.5 kg/(m)2·h)。
(12) When the amount of formic acid is 2 muL/mg NU-906, the thickness of the MOF film prepared after 24h reaction at 100 ℃ is 150nm, the roughness of the film is 3.9nm, and the water contact angle is 34 degrees.
Example 5:
(1) solution A: dissolving 58.5mg of zirconium chloride and 24mg of benzoic acid in 1.8mL of N, N-dimethylformamide, heating at 80 ℃ for 1h, and cooling to room temperature; and B, liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxyphenyl substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; mixing the prepared solution A, solution B and 288mg benzoic acid, heating at 100 deg.C for 2-72 hr to obtain white powdered NU-906 granule;
(2) polishing the surface of a self-made silicon dioxide carrier by using sand paper, coating 50nm silicon dioxide particles, and calcining for 5 hours at 550 ℃ to obtain the silicon dioxide carrier with a smooth surface;
(3) 125mg of NU-906 seed crystals were dispersed in 2.6mL of N, N-dimethylformamide to a single loading of 250mg/cm2Assembling the modified silica carrier by a wet coating mode to form compact NU-906 for later use;
(4) placing the carrier precoated with NU-906 in a polytetrafluoroethylene lining with a support, controlling the synthesis time, the synthesis temperature and the amount of formic acid, assisting the NU-906 particles with formic acid vapor to generate a compact MOF film through in-situ phase transformation, and soaking the obtained MOF film in acetone for storage after the reaction is finished;
(5) evaluating the permeability of the MOF film by using a self-assembled device, and evaluating the long-term stability of the film;
(6) the preparation method of the MOF membrane is in-situ phase inversion;
(7) the synthesis temperature of the MOF film is 25-150 DEG C℃；
(8) The synthesis time of the MOF membrane is 2-48 h;
(9) the amount of the MOF film formic acid is 0.08-2000 mu L/mg NU-906;
(10) the penetration evaluation system is 20-95 wt% ethanol/water, and the operation temperature is 20-120℃(ii) a 20 wt% -95 wt% butanol/water, operating temperature 20-120℃。
(11) When the amount of formic acid is 2 mu L/mg NU-906, the MOF membrane prepared after the reaction at 100 ℃ for 24 hours has a factor of 600 for separating 90 wt% ethanol from water and a flux of 3.5 kg/(m)2H); the separation factor of 90 wt% butanol/water is 8000, and the flux is 2.5 kg/(m)2·h)。
(12) When the amount of formic acid is 2 muL/mg NU-906, the thickness of the MOF film prepared after the reaction is carried out for 24h at 100 ℃ is 110nm, the roughness of the film is 1.6nm, and the water contact angle is 15 degrees.
Example 6:
(1) solution A: dissolving 58.5mg of zirconium chloride and 24mg of benzoic acid in 1.8mL of N, N-dimethylformamide, heating at 80 ℃ for 1h, and cooling to room temperature; and B, liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxyphenyl substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; mixing the prepared solution A, solution B and 288mg benzoic acid, heating at 100 deg.C for 2-72 hr to obtain white powdered NU-906 granule;
(2) polishing the surface of a self-made silicon dioxide carrier by using sand paper, coating 50nm silicon dioxide particles, and calcining for 5 hours at 550 ℃ to obtain the silicon dioxide carrier with a smooth surface;
(3) 188mg of NU-906 seed crystals were dispersed in 2.6mL of N, N-dimethylformamide to give a single loading of 376mg/cm2By wet coatingThe method is assembled on a modified silicon dioxide carrier to form a compact NU-906 layer for standby;
(4) placing the carrier precoated with NU-906 in a polytetrafluoroethylene lining with a support, controlling the synthesis time, the synthesis temperature and the amount of formic acid, assisting the NU-906 particles with formic acid vapor to generate a compact MOF film through in-situ phase transformation, and soaking the obtained MOF film in acetone for storage after the reaction is finished;
(5) evaluating the permeability of the MOF film by using a self-assembled device, and evaluating the long-term stability of the film;
(6) the preparation method of the MOF membrane is in-situ phase inversion;
(7) the synthesis temperature of the MOF film is 25-150 DEG C℃；
(8) The synthesis time of the MOF membrane is 2-48 h;
(9) the amount of the MOF film formic acid is 0.08-2000 mu L/mg NU-906;
(10) the penetration evaluation system is 20-95 wt% ethanol/water, and the operation temperature is 20-120℃(ii) a 20 wt% -95 wt% butanol/water, operating temperature 20-120℃。
(11) When the amount of formic acid is 2 muL/mg NU-906, the MOF membrane prepared after 24h reaction at 100 ℃ has a 90 wt% ethanol/water separation factor of 564 and a flux of 3.8 kg/(m)2H); the separation factor of butanol/water of 90 wt% is 6030, and the flux is 2.9 kg/(m)2·h)。
(12) When the amount of formic acid is 2 muL/mg NU-906, the thickness of the MOF film prepared after 24h reaction at 100 ℃ is 160nm, the roughness of the film is 2.3nm, and the water contact angle is 23 degrees.
Example 7:
(1) solution A: dissolving 58.5mg of zirconium chloride and 24mg of benzoic acid in 1.8mL of N, N-dimethylformamide, heating at 80 ℃ for 1h, and cooling to room temperature; and B, liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxyphenyl substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; mixing the prepared solution A, solution B and 288mg benzoic acid, heating at 100 deg.C for 2-72 hr to obtain white powdered NU-906 granule;
(2) polishing the surface of a self-made silicon dioxide carrier by using sand paper, coating 50nm silicon dioxide particles, and calcining for 5 hours at 550 ℃ to obtain the silicon dioxide carrier with a smooth surface;
(3) 250mg of NU-906 seed crystals were dispersed in 2.6mL of N, N-dimethylformamide to a monolithic loading of 500mg/cm2Assembling the modified silicon dioxide carrier by a wet coating mode to form a compact NU-906 layer for later use;
(4) placing the carrier precoated with NU-906 in a polytetrafluoroethylene lining with a support, controlling the synthesis time, the synthesis temperature and the amount of formic acid, assisting the NU-906 particles with formic acid vapor to generate a compact MOF film through in-situ phase transformation, and soaking the obtained MOF film in acetone for storage after the reaction is finished;
(5) evaluating the permeability of the MOF film by using a self-assembled device, and evaluating the long-term stability of the film;
(6) the preparation method of the MOF membrane is in-situ phase inversion;
(7) the synthesis temperature of the MOF film is 25-150 DEG C℃；
(8) The synthesis time of the MOF membrane is 2-48 h;
(9) the amount of the MOF film formic acid is 0.08-2000 mu L/mg NU-906;
(10) the penetration evaluation system is 20-95 wt% ethanol/water, and the operation temperature is 20-120℃(ii) a 20 wt% -95 wt% butanol/water, operating temperature 20-120℃。
(11) When the amount of formic acid is 2 mu L/mg NU-906, the MOF membrane prepared after the reaction at 100 ℃ for 24 hours has a 597 factor of 90 wt% ethanol/water separation and a flux of 3.7 kg/(m)2H); the separation factor of the 90 wt% butanol/water is 7869, and the flux is 3.2 kg/(m)2·h)。
(12) When the amount of formic acid is 2 muL/mg NU-906, the thickness of the MOF film prepared after 24h reaction at 100 ℃ is 170nm, the roughness of the film is 2.1nm, and the water contact angle is 25 degrees.
The process conditions of examples 8 to 16 are specified in Table 1 (otherwise, the same conditions as in example 1)
TABLE 1
In summary, as shown in FIGS. 1 to 5, the study was conducted at a formic acid content of 2. mu.L/mg NU-906 and a seed loading of 250mg/cm2In the process, after the reaction is carried out for 24 hours at 100 ℃, the thickness of the MOF film prepared by the in-situ phase inversion method is 110nm, the roughness of the film is 1.6nm, and the water contact angle is 15 degrees. The MOF membranes prepared under different synthesis conditions were all relatively dense and had a thickness of hundred nanometers, with a seed loading of 250mg/cm2In time, the membranes prepared by the in-situ phase inversion method are the thinnest, so the research can provide rich theoretical guidance for the preparation of ultrathin MOF. Meanwhile, in the separation process, the MOF films prepared under different conditions show better separation effect, and a solid foundation is laid for the industrial application of the films. The present invention is not limited to the above-mentioned embodiments, which are only illustrative and not restrictive, and those skilled in the art can make many modifications without departing from the spirit of the present invention, and these modifications are within the scope of the present invention.
Claims (6)
1. The method for preparing the MOF film by the in-situ phase inversion method is characterized by mainly comprising the following steps:
(1) preparing NU-906 particles;
(2) polishing the surface of a self-made silicon dioxide carrier by using sand paper, coating 50nm silicon dioxide particles, and calcining for 5 hours at 550 ℃ to obtain the silicon dioxide carrier with a smooth and flat surface;
(3) dispersing the prepared NU-906 seed crystals in a solvent, and assembling the seed crystals on a modified silicon dioxide carrier by a wet coating mode to form a compact NU-906 layer for later use;
(4) placing the carrier loaded with the NU-906 particles in a polytetrafluoroethylene liner with a support, adding formic acid, controlling time and temperature to enable the NU-906 particles to generate a compact MOF film through in-situ phase transformation, and soaking the obtained MOF film in acetone for storage after the reaction is finished;
(5) evaluating the permeability of the MOF film by using a self-assembled device, and evaluating the long-term stability of the film;
(6) the surface appearance and the thickness of the MOF film are represented by SEM, the XRD reflects the orientation of the MOF film, the surface roughness of the MOF film is observed by AFM, the water contact angle is tested to test the hydrophilicity of the MOF film at different time, and the structural characteristics and the separation performance of the oriented MOF film are further explained;
the load of the NU-906 in the step (3) is 5-500mg/cm2；
The reaction temperature of the MOF film in the step (4) is 25-150 ℃;
the reaction time of the MOF film in the step (4) is 2-48 h;
the amount of formic acid in the step (4) is 0.08-2000 mu L/mg NU-906.
2. The method according to claim 1, wherein the solvent of step (3) comprises N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, water, lower alkanols (C1-C6), acetonitrile, acetone or ethyl acetate.
3. The method of claim 1, wherein the step (4) MOF film is prepared by in-situ phase inversion.
4. The method according to claim 1, wherein the penetration evaluation systems of the step (5) are 20 wt% -95 wt% ethanol/water respectively, and the operating temperature is 20-120 ℃; 20 wt% -95 wt% butanol/water, and the operation temperature is 20-120 ℃.
5. The method according to claim 1, characterized in that step (1) is in particular:
solution A: dissolving 58.5mg of zirconium chloride and 24mg of benzoic acid in 1.8mL of N, N-dimethylformamide, heating at 80 ℃ for 1h, and cooling to room temperature; and B, liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxyphenyl substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; mixing the prepared solution A, solution B and 288mg benzoic acid, and heating at 100 deg.C for 2-72 hr to obtain white powdered NU-906 granule.
6. Use of MOF films prepared by in situ phase inversion prepared by the method of any of claims 1 to 5 for ethanol/water, butanol/water separations.
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