CN114367199B - 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 a MOF film by an in-situ phase inversion method and application thereof, wherein the influences of factors related to seed load, formic acid amount, synthesis time and synthesis temperature on the surface compactness, thickness, surface roughness and film hydrophilicity of the MOF film are explored in the process, and the method is simultaneously 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 a MOF film by an in-situ phase inversion method and application thereof.
Background
As an alternative technology for rectification separation, the pervaporation technology has been developed into a practical technology which can be accepted by industry, so far, the technology has a history of more than several decades, plays an important role in energy conservation and consumption reduction in related industries such as organic solvent dehydration, azeotropic component separation and the like, and proves 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, and is widely applied to industrial gas separation, reverse osmosis and other processes, and partial polymer membrane materials have the problem of poor chemical stability and thermal stability in pervaporation application. Inorganic membranes, particularly zeolite membranes, have been widely used for dewatering organic matter, but the structural brittleness is high, limiting the application of the membranes. Metal Organic Framework (MOF) membranes have a general topology and precisely adjustable nanopore structure, while having a robust framework structure, and therefore, MOF membranes are a very potential separation material. Metal-organic frameworks (MOFs) materials are a class of materials with periodic network structures formed by coordination interactions of organic ligands with 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 preparation method of the metal organic framework film commonly used at present comprises an in-situ hydrothermal synthesis method, a secondary growth method and the like. These methods are all limited to varying degrees by factors such as: a large amount of raw material liquid, influence of a film assembly method, and the like. Under the auxiliary action of steam, the preparation of the ultrathin MOF film material is realized through the original-flavor phase transformation 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 prepares the MOF film with ultrathin thickness 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 sand paper to be smooth, coating 50nm silicon dioxide particles, and calcining at 550 ℃ for 5 hours to obtain a silicon dioxide carrier with a smooth and flat surface;
(3) Dispersing the prepared NU-906 seed crystal in a solvent, and assembling the seed crystal on a modified silicon dioxide carrier in a wet coating mode to form a compact NU-906 layer for later use;
(4) Placing a carrier loaded with NU-906 particles into a polytetrafluoroethylene lining with a bracket, 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) SEM characterizes the surface morphology and thickness of the MOF film, XRD reflects the orientation of the MOF film, AFM observes the surface roughness of the MOF film, water contact angle tests the hydrophilicity of the MOF film at different times, further illustrates the structural characteristics and separation performance of the oriented MOF film;
the NU-906 load amount in the step (3) is 5-500mg/cm 2 ；
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 2-48h;
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 respectively 20-95 wt% of ethanol/water, and the operation temperature is 20-120 ℃; 20-95 wt% butanol/water, and the operation temperature is 20-120 ℃.
The invention prepares NU-906 particles, which comprises the following steps: and (3) solution A: 58.5mg of zirconium chloride and 24mg of benzoic acid are dissolved in 1.8mL of N, N-dimethylformamide, heated at 80 ℃ for 1h and cooled to room temperature; and (2) liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxylic acid phenyl-substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; uniformly mixing the prepared solution A, solution B and 288mg of benzoic acid, and heating at 100 ℃ for 2-72h to obtain white powdery NU-906 particles for later use.
The second technical scheme of the invention is that the MOF film prepared by the in-situ phase inversion method is applied to ethanol/water and butanol/water separation.
The invention has the advantages that:
the MOF film is successfully prepared by an in-situ phase inversion method, and the preparation method is simple, convenient and quick and does not need to add additional chemical reagents. In separation applications, MOF membranes have a separation factor of up to 600 for ethanol/water with a flux of 2.5 kg/(m) 2 H) butanol/water separation factor up to 6000, flux 3.8 kg/(m) 2 H). The MOF film prepared by the invention has ultra-thin thickness,has excellent separation performance and good long-term stability, and is a potential separation technology.
Drawings
Fig. 1: the loading was 250mg/cm 2 And the XRD pattern of the MOF film prepared after 24 hours of reaction at 100℃when the amount of formic acid was 2. Mu.L/mg NU-906.
Fig. 2: the loading was 250mg/cm 2 And the amount of formic acid was 2. Mu.L/mg NU-906, at 100℃for 24 hours.
Fig. 3: the loading was 250mg/cm 2 And the amount of formic acid was 2. Mu.L/mg NU-906, a cross-sectional view of the MOF film prepared after 24 hours of reaction at 100 ℃.
Fig. 4: the loading was 250mg/cm 2 And the amount of formic acid was 2. Mu.L/mg NU-906, at 100℃for 24 hours.
Fig. 5: the loading was 250mg/cm 2 And the water contact angle graph of MOF films prepared after 24h reaction at 100℃when the amount of formic acid was 2. Mu.L/mg NU-906.
Detailed Description
The invention is further illustrated below in conjunction with specific embodiments.
Preparation of NU-906 seed of the invention, reference: phase Transitions in Metal-Organic Frameworks Directly Monitored through In Situ Variable Temperature Liquid-Cell Transmission Electron Microscopy and In Situ Xray Diffraction [ J ]. Journal of the American Chemical Society,2020,142 (10): 4609-4615.
Example 1:
(1) And (3) solution A: 58.5mg of zirconium chloride and 24mg of benzoic acid are dissolved in 1.8mL of N, N-dimethylformamide, heated at 80 ℃ for 1h and cooled to room temperature; and (2) liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxylic acid phenyl-substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; uniformly mixing the prepared solution A, solution B and 288mg of benzoic acid, and heating at 100 ℃ for 2-72h to obtain white powdery NU-906 particles for later use;
(2) Polishing the surface of a self-made silicon dioxide carrier by sand paper to be smooth, coating 50nm silicon dioxide particles, and calcining at 550 ℃ for 5 hours to obtain the silicon dioxide carrier with smooth surface;
(3) 2.5mg NU-906 seed was dispersed in 2.6mL N, N-dimethylformamide to give a monolithic loading of 5mg/cm 2 Forming a compact NU-906 layer on the modified silicon dioxide carrier by wet coating for later use;
(4) Placing a pre-coated NU-906 carrier into a polytetrafluoroethylene lining with a bracket, controlling synthesis time, synthesis temperature and formic acid amount, generating a compact MOF film by in-situ phase conversion of formic acid steam-assisted NU-906 particles, and soaking the obtained MOF film in acetone for later use 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 film is in-situ phase inversion;
(7) The synthesis temperature of the MOF film is 25-150 ℃ ；
(8) The synthesis time of the MOF film is 2-48h;
(9) The amount of 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 ℃ The method comprises the steps of carrying out a first treatment on the surface of the 20-95 wt% butanol/water at an operating temperature of 20-120 ℃ 。
(11) When the amount of formic acid was 2. Mu.L/mg NU-906, the MOF membrane prepared after 24 hours of reaction at 100℃had a flux of 3.8 kg/(m) for a 90wt% ethanol/water separation factor of 390 2 H); for 90wt% butanol/water separation factor 4020, flux was 2.3 kg/(m) 2 ·h)。
(12) When the amount of formic acid was 2. Mu.L/mg NU-906, the film thickness prepared after 24 hours of reaction at 100℃was 130nm, the roughness of the film was 8.9nm, and the water contact angle was 65 ℃.
Example 2:
(1) And (3) solution A: 58.5mg of zirconium chloride and 24mg of benzoic acid are dissolved in 1.8mL of N, N-dimethylformamide, heated at 80 ℃ for 1h and cooled to room temperature; and (2) liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxylic acid phenyl-substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; uniformly mixing the prepared solution A, solution B and 288mg of benzoic acid, and heating at 100 ℃ for 2-72h to obtain white powdery NU-906 particles for later use;
(2) Polishing the surface of a self-made silicon dioxide carrier by sand paper to be smooth, coating 50nm silicon dioxide particles, and calcining at 550 ℃ for 5 hours to obtain the silicon dioxide carrier with smooth surface;
(3) 10mg NU-906 seed was dispersed in 2.6mL N, N-dimethylformamide to give a monolithic loading of 20mg/cm 2 Forming a compact NU-906 layer on the modified silicon dioxide carrier by wet coating for later use;
(4) Placing a pre-coated NU-906 carrier into a polytetrafluoroethylene lining with a bracket, controlling synthesis time, synthesis temperature and formic acid amount, generating a compact MOF film by in-situ phase conversion of formic acid steam-assisted NU-906 particles, and soaking the obtained MOF film in acetone for later use 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 film is in-situ phase inversion;
(7) The synthesis temperature of the MOF film is 25-150 ℃ ；
(8) The synthesis time of the MOF film is 2-48h;
(9) The amount of 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 ℃ The method comprises the steps of carrying out a first treatment on the surface of the 20-95 wt% butanol/water at an operating temperature of 20-120 ℃ 。
(10) When the amount of formic acid was 2. Mu.L/mg NU-906, the MOF membrane prepared after 24 hours of reaction at 100℃had a flux of 3.1 kg/(m) for a 90wt% ethanol/water separation factor of 437 2 H); for 90wt% butanol/water separation factor of 4250, flux was 2.1 kg/(m) 2 ·h)。
(11) When the amount of formic acid was 2. Mu.L/mg NU-906, the MOF film prepared after 24 hours of reaction at 100℃had a thickness of 130nm, a roughness of 6.7nm and a water contact angle of 57 ℃.
Example 3:
(1) And (3) solution A: 58.5mg of zirconium chloride and 24mg of benzoic acid are dissolved in 1.8mL of N, N-dimethylformamide, heated at 80 ℃ for 1h and cooled to room temperature; and (2) liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxylic acid phenyl-substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; uniformly mixing the prepared solution A, solution B and 288mg of benzoic acid, and heating at 100 ℃ for 2-72h to obtain white powdery NU-906 particles for later use;
(2) Polishing the surface of a self-made silicon dioxide carrier by sand paper to be smooth, coating 50nm silicon dioxide particles, and calcining at 550 ℃ for 5 hours to obtain the silicon dioxide carrier with smooth surface;
(3) 40mg NU-906 seed was dispersed in 2.6mL N, N-dimethylformamide to give a monolithic loading of 80mg/cm 2 Forming a compact NU-906 layer on the modified silicon dioxide carrier by wet coating for later use;
(4) Placing a pre-coated NU-906 carrier into a polytetrafluoroethylene lining with a bracket, controlling synthesis time, synthesis temperature and formic acid amount, generating a compact MOF film by in-situ phase conversion of formic acid steam-assisted NU-906 particles, and soaking the obtained MOF film in acetone for later use 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 film is in-situ phase inversion;
(7) The synthesis temperature of the MOF film is 25-150 ℃ ；
(8) The synthesis time of the MOF film is 2-48h;
(9) The amount of 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 ℃ The method comprises the steps of carrying out a first treatment on the surface of the 20-95 wt% butanol/water at an operating temperature of 20-120 ℃ 。
(11) When the amount of formic acid was 2. Mu.L/mg NU-906, the MOF membrane prepared after 24 hours of reaction at 100℃had a flux of 2.8 kg/(m) for a 473 wt% ethanol/water separation factor of 90wt% 2 H); for 90wt% butanol/water separation factor 4532, flux was 2.2 kg/(m) 2 ·h)。
(12) When the amount of formic acid was 2. Mu.L/mg NU-906, the MOF film prepared after 24 hours of reaction at 100℃had a thickness of 140nm, a roughness of 4.5nm and a water contact angle of 45 ℃.
Example 4:
(1) And (3) solution A: 58.5mg of zirconium chloride and 24mg of benzoic acid are dissolved in 1.8mL of N, N-dimethylformamide, heated at 80 ℃ for 1h and cooled to room temperature; and (2) liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxylic acid phenyl-substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; uniformly mixing the prepared solution A, solution B and 288mg of benzoic acid, and heating at 100 ℃ for 2-72h to obtain white powdery NU-906 particles for later use;
(2) Polishing the surface of a self-made silicon dioxide carrier by sand paper to be smooth, coating 50nm silicon dioxide particles, and calcining at 550 ℃ for 5 hours to obtain the silicon dioxide carrier with smooth surface;
(3) 90mg NU-906 seed was dispersed in 2.6mL N, N-dimethylformamide to give a monolithic loading of 180mg/cm 2 Forming a compact NU-906 layer on the modified silicon dioxide carrier by wet coating for later use;
(4) Placing a pre-coated NU-906 carrier into a polytetrafluoroethylene lining with a bracket, controlling synthesis time, synthesis temperature and formic acid amount, generating a compact MOF film by in-situ phase conversion of formic acid steam-assisted NU-906 particles, and soaking the obtained MOF film in acetone for later use 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 film is in-situ phase inversion;
(7) The synthesis temperature of the MOF film is 25-150 ℃ ；
(8) The synthesis time of the MOF film is 2-48h;
(9) The amount of 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 ℃ The method comprises the steps of carrying out a first treatment on the surface of the 20-95 wt% butanol/water at an operating temperature of 20-120 ℃ 。
(11) When the amount of formic acid was 2. Mu.L/mg NU-906, the MOF membrane prepared after 24h reaction at 100℃had a flux of 3.3 kg-(m 2 H); for 90wt% butanol/water separation factor 4672, flux was 2.5 kg/(m) 2 ·h)。
(12) When the amount of formic acid was 2. Mu.L/mg NU-906, the film thickness of the prepared MOF after 24 hours of reaction at 100℃was 150nm, the roughness of the film was 3.9nm, and the water contact angle was 34 ℃.
Example 5:
(1) And (3) solution A: 58.5mg of zirconium chloride and 24mg of benzoic acid are dissolved in 1.8mL of N, N-dimethylformamide, heated at 80 ℃ for 1h and cooled to room temperature; and (2) liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxylic acid phenyl-substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; uniformly mixing the prepared solution A, solution B and 288mg of benzoic acid, and heating at 100 ℃ for 2-72h to obtain white powdery NU-906 particles for later use;
(2) Polishing the surface of a self-made silicon dioxide carrier by sand paper to be smooth, coating 50nm silicon dioxide particles, and calcining at 550 ℃ for 5 hours to obtain the silicon dioxide carrier with smooth surface;
(3) 125mg NU-906 seed was dispersed in 2.6mL N, N-dimethylformamide to give a monolithic loading of 250mg/cm 2 Forming compact NU-906 on the modified silicon dioxide carrier by wet coating;
(4) Placing a pre-coated NU-906 carrier into a polytetrafluoroethylene lining with a bracket, controlling synthesis time, synthesis temperature and formic acid amount, generating a compact MOF film by in-situ phase conversion of formic acid steam-assisted NU-906 particles, and soaking the obtained MOF film in acetone for later use 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 film is in-situ phase inversion;
(7) The synthesis temperature of the MOF film is 25-150 ℃ ；
(8) The synthesis time of the MOF film is 2-48h;
(9) The amount of 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 ℃ ；20wt％-95wt% butanol/water at an operating temperature of 20-120 ℃ 。
(11) When the amount of formic acid was 2. Mu.L/mg NU-906, the MOF membrane prepared after 24 hours of reaction at 100℃had a flux of 3.5 kg/(m) for a factor of 600 against 90wt% ethanol/water separation 2 H); for 90wt% butanol/water separation factor of 8000, flux was 2.5 kg/(m) 2 ·h)。
(12) When the amount of formic acid was 2. Mu.L/mg NU-906, the MOF film prepared after 24 hours of reaction at 100℃had a thickness of 110nm, a roughness of 1.6nm and a water contact angle of 15 ℃.
Example 6:
(1) And (3) solution A: 58.5mg of zirconium chloride and 24mg of benzoic acid are dissolved in 1.8mL of N, N-dimethylformamide, heated at 80 ℃ for 1h and cooled to room temperature; and (2) liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxylic acid phenyl-substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; uniformly mixing the prepared solution A, solution B and 288mg of benzoic acid, and heating at 100 ℃ for 2-72h to obtain white powdery NU-906 particles for later use;
(2) Polishing the surface of a self-made silicon dioxide carrier by sand paper to be smooth, coating 50nm silicon dioxide particles, and calcining at 550 ℃ for 5 hours to obtain the silicon dioxide carrier with smooth surface;
(3) 188mg of NU-906 seed crystals were dispersed in 2.6mL of N, N-dimethylformamide to give a monolithic loading of 376mg/cm 2 Forming a compact NU-906 layer on the modified silicon dioxide carrier by wet coating for later use;
(4) Placing a pre-coated NU-906 carrier into a polytetrafluoroethylene lining with a bracket, controlling synthesis time, synthesis temperature and formic acid amount, generating a compact MOF film by in-situ phase conversion of formic acid steam-assisted NU-906 particles, and soaking the obtained MOF film in acetone for later use 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 film is in-situ phase inversion;
(7) The synthesis temperature of the MOF film is 25-150 ℃ ；
(8) The synthesis time of the MOF film is 2-48h;
(9) The amount of 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 ℃ The method comprises the steps of carrying out a first treatment on the surface of the 20-95 wt% butanol/water at an operating temperature of 20-120 ℃ 。
(11) When the amount of formic acid was 2. Mu.L/mg NU-906, the MOF membrane prepared after 24 hours of reaction at 100℃had a flux of 3.8 kg/(m) for 564% by weight ethanol/water separation factor 2 H); for a 90wt% butanol/water separation factor of 6030, flux is 2.9 kg/(m) 2 ·h)。
(12) When the amount of formic acid was 2. Mu.L/mg NU-906, the MOF film prepared after 24 hours of reaction at 100℃had a thickness of 160nm, a roughness of 2.3nm and a water contact angle of 23 ℃.
Example 7:
(1) And (3) solution A: 58.5mg of zirconium chloride and 24mg of benzoic acid are dissolved in 1.8mL of N, N-dimethylformamide, heated at 80 ℃ for 1h and cooled to room temperature; and (2) liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxylic acid phenyl-substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; uniformly mixing the prepared solution A, solution B and 288mg of benzoic acid, and heating at 100 ℃ for 2-72h to obtain white powdery NU-906 particles for later use;
(2) Polishing the surface of a self-made silicon dioxide carrier by sand paper to be smooth, coating 50nm silicon dioxide particles, and calcining at 550 ℃ for 5 hours to obtain the silicon dioxide carrier with smooth surface;
(3) 250mg NU-906 seed was dispersed in 2.6mL N, N-dimethylformamide to give a monolithic loading of 500mg/cm 2 Forming a compact NU-906 layer on the modified silicon dioxide carrier by wet coating for later use;
(4) Placing a pre-coated NU-906 carrier into a polytetrafluoroethylene lining with a bracket, controlling synthesis time, synthesis temperature and formic acid amount, generating a compact MOF film by in-situ phase conversion of formic acid steam-assisted NU-906 particles, and soaking the obtained MOF film in acetone for later use 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 film is in-situ phase inversion;
(7) The synthesis temperature of the MOF film is 25-150 ℃ ；
(8) The synthesis time of the MOF film is 2-48h;
(9) The amount of 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 ℃ The method comprises the steps of carrying out a first treatment on the surface of the 20-95 wt% butanol/water at an operating temperature of 20-120 ℃ 。
(11) When the amount of formic acid was 2. Mu.L/mg NU-906, the MOF membrane prepared after 24 hours of reaction at 100℃had a flux of 3.7 kg/(m) for a 90wt% ethanol/water separation factor of 597 2 H); for a 90wt% butanol/water separation factor of 7869, the flux was 3.2 kg/(m) 2 ·h)。
(12) When the amount of formic acid was 2. Mu.L/mg NU-906, the MOF film prepared after 24 hours of reaction at 100℃had a thickness of 170nm, the roughness of the film was 2.1nm, and the water contact angle was 25 ℃.
The process conditions of examples 8 to 16 are shown in Table 1 (other conditions are the same as in example 1)
TABLE 1
In summary, as shown in FIGS. 1 to 5, the present study was conducted at a formic acid level of 2. Mu.L/mg NU-906 and a seed loading of 250mg/cm 2 At this time, the MOF film prepared by the in-situ phase inversion method after 24 hours of reaction at 100℃had a thickness of 110nm, a roughness of 1.6nm and a water contact angle of 15 ℃. MOF films prepared under different synthesis conditions were dense and had a thickness of hundred nanometers, where the seed loading was 250mg/cm 2 In the process, the film prepared by the in-situ phase inversion method is thinnest, so that the research can provide rich theoretical guidance for preparing the ultrathin MOF. Meanwhile, in the separation process, the MOF films prepared under different conditions all show better separation effects, and a solid foundation is laid for the industrial application of the films. The present invention is not limited to the above embodiments, which are merelyBy way of illustration and not limitation, one of ordinary skill in the art, in light of the present disclosure, could make many variations without departing from the spirit of the present disclosure, which would fall within the scope of the present disclosure.
Claims (6)
1. The method for preparing the MOF film by the in-situ phase inversion method is characterized by comprising the following main steps:
(1) Preparing NU-906 particles;
(2) Polishing the surface of a self-made silicon dioxide carrier by sand paper to be smooth, coating 50nm silicon dioxide particles, and calcining at 550 ℃ for 5 hours to obtain a silicon dioxide carrier with a smooth and flat surface;
(3) Dispersing the prepared NU-906 seed crystal in a solvent, and assembling the seed crystal on a modified silicon dioxide carrier in a wet coating mode to form a compact NU-906 layer for later use;
(4) Placing a carrier loaded with NU-906 particles into a polytetrafluoroethylene lining with a bracket, adding formic acid, controlling time and temperature, generating a compact MOF film by in-situ phase transformation of the NU-906 particles assisted by formic acid steam, and soaking the obtained MOF film in acetone for later use 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) SEM characterizes the surface morphology and thickness of the MOF film, XRD reflects the orientation of the MOF film, AFM observes the surface roughness of the MOF film, water contact angle tests the hydrophilicity of the MOF film at different times, further illustrates the structural characteristics and separation performance of the oriented MOF film;
the NU-906 load amount in the step (3) is 5-500mg/cm 2 ；
The reaction temperature of the MOF film in the step (4) is 50-150 ℃;
the reaction time of the MOF film in the step (4) is 2-48h;
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-diethylformamide, N-dimethylacetamide, water, a lower alkane alcohol containing C1 to C6, acetonitrile, acetone or ethyl acetate.
3. The method of claim 1, wherein the MOF film of step (4) is prepared by in situ phase inversion.
4. The method of claim 1, wherein the permeation evaluation system of step (5) is 20wt% to 95wt% ethanol/water, respectively, and the operating temperature is 20 to 120 ℃; 20-95 wt% butanol/water, and the operation temperature is 20-120 ℃.
5. The method according to claim 1, wherein the step (1) is specifically:
and (3) solution A: 58.5mg of zirconium chloride, 24mg of benzoic acid were dissolved in 1.8mLN, N-dimethylformamide, heated at 80℃for 1h, and cooled to room temperature; and (2) liquid B: 36mg of 1, 4-dibromo-2, 3,5, 6-tetracarboxylic acid phenyl-substituted benzene was dissolved in 1.8mL of N, N-dimethylformamide; uniformly mixing the prepared solution A, solution B and 288mg of benzoic acid, and heating at 100 ℃ for 2-72h to obtain white powdery NU-906 particles.
6. The MOF film prepared by the method of any one of claims 1 to 5 is applied to ethanol/water or butanol/water separation.
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