CN114288870A - Synthetic method of MOFs-organic silicon hybrid membrane - Google Patents
Synthetic method of MOFs-organic silicon hybrid membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 59
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- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 claims description 25
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- IZRJPHXTEXTLHY-UHFFFAOYSA-N triethoxy(2-triethoxysilylethyl)silane Chemical compound CCO[Si](OCC)(OCC)CC[Si](OCC)(OCC)OCC IZRJPHXTEXTLHY-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
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- 238000005406 washing Methods 0.000 claims description 4
- FOSPKRPCLFRZTR-UHFFFAOYSA-N zinc;dinitrate;hydrate Chemical compound O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FOSPKRPCLFRZTR-UHFFFAOYSA-N 0.000 claims description 4
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- 229910003158 γ-Al2O3 Inorganic materials 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
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- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
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- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 1
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- 238000007796 conventional method Methods 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
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- 229910010272 inorganic material Inorganic materials 0.000 description 1
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- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000004941 mixed matrix membrane Substances 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
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- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- CPUDPFPXCZDNGI-UHFFFAOYSA-N triethoxy(methyl)silane Chemical compound CCO[Si](C)(OCC)OCC CPUDPFPXCZDNGI-UHFFFAOYSA-N 0.000 description 1
- 239000013172 zeolitic imidazolate framework-7 Substances 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Abstract
The invention belongs to the technical field of composite membrane preparation, and particularly relates to a synthesis method of an MOFs-organic silicon hybrid membrane. The method comprises the following steps: s1, mixing MOFs material with precursor sol containing organic silicon to obtain mixed sol; s2, coating the mixed sol on a porous carrier, and calcining; s3, repeating the step S2 for 1-5 times to obtain the MOFs-organic silicon hybrid membrane, introducing an MOF material serving as a filling material into the precursor sol containing organic silicon to obtain the MOFs-organic silicon hybrid membrane, so that the MOFs-organic silicon hybrid membrane obtains additional selective adsorption sites and preferential diffusion paths, and the flux and the separation performance of the MOFs-organic silicon hybrid membrane are improved to a certain extent.
Description
Technical Field
The invention belongs to the technical field of composite membrane preparation, and particularly relates to a synthesis method of an MOFs-organic silicon hybrid membrane.
Background
The separation mechanism of the polymer membrane follows the dissolution-diffusion mechanism of gas molecules in the polymer and is limited by the Upper robinson limit (Robeson Upper Bound), i.e. the mutual restriction between permeability and selectivity, and if the permeability is high, the selectivity is low, while the inorganic material and the metal organic framework material are not limited by the Upper robinson limit and can provide good gas separation performance.
The conventional method is as follows: porous materials are dispersed in polymer membranes to form Mixed Matrix Membranes (MMM) or hybrid membranes.
As pervaporation hybrid membranes are widely used, higher requirements are put on the performance of the hybrid membranes, and among the numerous hybrid membranes for pervaporation, silica hybrid membranes have very high hydrothermal stability, acid resistance and excellent separation performance, but the application of silica is greatly limited due to low flux.
Metal organic framework Materials (MOFs) are a class of compounds consisting of metal ions or clusters, which are coordinated with organic ligands to form one-, two-or three-dimensional structures.
However, how to construct hybrid membranes with high flux remains a great challenge.
Disclosure of Invention
The application provides a synthesis method of an MOFs-organic silicon hybrid membrane, which aims to solve the technical problem of low flux of a silicon dioxide hybrid membrane.
In a first aspect, the present application provides a method for synthesizing a MOFs-silicone hybrid membrane, comprising the steps of:
s1, mixing MOFs material with precursor sol containing organic silicon to obtain mixed sol;
s2, coating the mixed sol on a porous carrier, and calcining;
and S3, repeating the step S2 for 1-5 times to obtain the MOFs-organic silicon hybrid membrane.
Optionally, the MOFs material comprises a material ZIF-8.
Optionally, the preparation method of the material ZIF-8 comprises: respectively dissolving zinc nitrate hydrate and 2-methylimidazole in an organic solvent, mixing, centrifuging, washing and drying to obtain the material ZIF-8.
Optionally, the mol ratio of the MOFs material to the precursor sol is 0.5-2: 0.5 to 2.
Optionally, the precursor sol is prepared by a sol-gel method, and the precursor sol comprises the following components: ethanol, 1, 2-bis (triethoxysilyl) ethane, monobasic acid and water.
Optionally, the molar ratio of the 1, 2-bis (triethoxysilyl) ethane to the ethanol to the monobasic acid to the water is 0.5: 8-10: 0.1-0.5: 6-12.
Optionally, the coating is performed by a vacuum coating method, and the coating time is 15-60 s.
Optionally, the calcining temperature is 200-300 ℃, the temperature rise rate of the calcining is 0.5-2 ℃/min, and the calcining time is 30-180 min.
Optionally, the porous support comprises a defect-modified support tube, the defect modification comprising a macroporous modification of the support tube.
Optionally, the porous support comprises:
and modifying the initial carrier tube by using more boehmite sol than macropores of the initial carrier tube, and calcining at 200-300 ℃ for 30-180 min to obtain the defect-modified carrier tube.
Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:
according to the method provided by the embodiment of the application, MOFs materials are mixed with precursor sol containing organic silicon to obtain mixed sol; and coating the mixed sol on a porous carrier, and calcining to obtain the MOFs-organic silicon hybrid membrane. The MOF material is introduced, the MOF material has the advantages of high specific surface area, high porosity, low density and the like, and the guest molecules to be separated do not generate structural change when being discharged from the pore canal of the MOF material, and the MOF material is introduced into precursor sol containing organic silicon as a filling material to obtain the MOFs-organic silicon hybrid membrane, so that the MOFs-organic silicon hybrid membrane obtains additional selective adsorption sites and preferential diffusion paths, and the flux and the separation performance of the MOFs-organic silicon hybrid membrane are improved to a certain extent.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments or technical solutions in the prior art of the present invention, the drawings used in the description of the embodiments or prior art will be briefly described below, and it is obvious for those skilled in the art to obtain other drawings without inventive exercise.
Fig. 1 is a schematic flow chart of a method for synthesizing a MOFs-silicone hybrid film provided in an embodiment of the present application;
FIG. 2 is an SEM image of ZIF-8 powder provided in the examples of the present application;
fig. 3 is an SEM plan view of the MOF-silicone hybrid film provided in the application examples.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention. For example, the room temperature may be a temperature within a range of 10 to 35 ℃.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
according to an exemplary embodiment of the present invention, there is provided a method for synthesizing a MOFs-silicone hybrid film, as shown in fig. 1, the method comprising the steps of:
s1, mixing MOFs material with precursor sol containing organic silicon to obtain mixed sol;
s2, coating the mixed sol on a porous carrier, and calcining;
and S3, repeating the step S2 for 1-5 times to obtain the MOFs-organic silicon hybrid membrane.
In particular, the MOFs have the advantages of adjustable pore size, high specific surface area, high porosity and stable chemical properties; the precursor sol containing the organic silicon has the advantages of good hydrothermal stability and high affinity with a ceramic carrier, a MOFs-organic silicon hybrid membrane which can be used for pervaporation and has good performance is synthesized by combining the two types of sol and the ceramic carrier, and the prepared MOFs-organic silicon hybrid membrane can be used for separating a system including but not limited to isopropanol/water or ethanol/water.
In general, the porous support is a defect-modified porous support, and boehmite sol (. gamma. -Al) can be used2O3Particles) and placing the modified porous carrier into a muffle furnace to calcine for 30-180 min to obtain the defect modified porous carrier.
Specifically, organosilanes include, but are not limited to, 1, 2 bis (triethoxysilyl) ethane, tetraethyl silicate, and methyltriethoxysilane.
In some embodiments, the MOFs material includes material ZIF-8.
Specifically, the MOFs material also comprises any one of ZIF-8, ZIF-7 and ZIF-67.
In some embodiments, the method of preparing the material ZIF-8 comprises: respectively dissolving zinc nitrate hydrate and 2-methylimidazole in an organic solvent, mixing, centrifuging, washing and drying to obtain the material ZIF-8.
Specifically, zinc nitrate hydrate includes, but is not limited to, zinc nitrate hexahydrate, cobalt nitrate hexahydrate, and anhydrous copper nitrate, and organic solvents include, but are not limited to, methanol.
In some embodiments, the mol ratio of the MOFs material to the precursor sol is 0.5-2: 0.5 to 2.
Controlling the mol ratio of the MOFs material to the precursor sol to be 0.5-2: 0.5-2, the reason is that the sol with proper MOFs content is beneficial to obtaining a composite membrane material with excellent performance, and the positive effect of improving the performance of a single membrane material is achieved; when the molar ratio is more than 4: 1, the composite sol has the adverse effect of blocking membrane pores by agglomeration; when the molar ratio is less than 1: 4, the adverse effect that the performance of a single membrane material cannot be improved is achieved;
in some embodiments, the precursor sol is prepared by a sol-gel process, the components of the precursor sol comprising: ethanol, 1, 2-bis (triethoxysilyl) ethane, monobasic acid and water.
In the components of the precursor sol, ethanol is selected because the ethanol is a good organic solvent and has a positive effect of dissolving organosilane, and monoacid is selected because H + with proper content can effectively promote the hydrolysis of organosilane and has a favorable effect of further promoting the formation of a network structure;
in some embodiments, the molar ratio of the 1, 2-bis (triethoxysilyl) ethane, the ethanol, the monobasic acid, and the water is from 0.5:8 to 10:0.1 to 0.5:6 to 12.
The reason why the molar ratio of the 1, 2-bis (triethoxysilyl) ethane to the ethanol to the monoacid to the water is controlled to be 0.5: 8-10: 0.1-0.5: 6-12 is that water molecules are related to the size of silica sol colloidal particles, so that the positive effect of synthesizing a compact, uniform and stable membrane material is achieved, and when the molar ratio is not in the range, the negative effect that the colloidal particles with larger colloidal particles cause defects of a membrane layer is achieved.
In some embodiments, the coating is performed by a vacuum coating method, and the coating time is 15-60 s.
In the embodiment of the application, a vacuum coating method is adopted, so that the positive effect of enabling the sol to be uniformly coated at constant pressure is achieved, the time is 15-60 seconds, and the positive effect of enabling the thickness of a film layer to be appropriate is achieved; more than 60 seconds, the adverse effects of lower flux due to larger film thickness and cracking of the film material due to excessively thick film; less than 15 seconds has the adverse effect of coating the sol too little.
In some embodiments, the temperature of the calcination is 200 to 300 ℃, the temperature rise rate of the calcination is 0.5 to 2 ℃/min, and the time of the calcination is 30 to 180 min.
In the embodiment of the application, the calcining temperature is controlled to be 200-300 ℃, so that the positive effect of reducing the film layer fracture probability caused by overhigh temperature is achieved; the heating rate has the positive effect of ensuring that the sol is better and tightly combined with the carrier; the calcination time has the positive effect of forming a uniform and stable compact film material; if not, there are adverse effects that the binding force of the membrane material to the carrier is weak and the temperature and time are too high or too low to cause defects in the membrane material.
In some embodiments, the porous support comprises a defect-modified support tube, the defect modification comprising a macroporous modification of the support tube.
The reason for choosing the porous carrier to comprise a defect modified carrier tube is that: the hybrid membrane generated by the porous carrier has uniform pores and no sporadic macroporous distribution, thereby affecting the performance of the hybrid membrane.
In some embodiments, the porous support comprises:
and modifying the initial carrier tube by using more boehmite sol than macropores of the initial carrier tube, and calcining at 200-300 ℃ for 30-180 min to obtain the defect-modified carrier tube.
Specifically, the surface defect of the carrier tube is modified by adopting gamma-Al2O3The method is characterized in that the particles fill up and modify macroporous defects on the surface of the carrier tube, and the method comprises the following specific steps:
(1) preparation of boehmite sol: mixing gamma-Al2O3Dissolving the particles in a certain amount of deionized water, dropwise adding hydrochloric acid after uniformly stirring, continuously stirring, and then continuously hydrolyzing and aging at room temperature;
(2) surface defect modification of a carrier tube: drying moisture in a carrier tube which is processed for at least half an hour in ultrasonic, sealing one end of the carrier tube, and uniformly coating the prepared boehmite sol on the surface of the carrier in a vacuum coating mode for 15-30 s.
(3) And (3) putting the dried carrier tube into a muffle furnace for calcining and curing, and calcining for 30-180 min at 500-600 ℃, wherein the heating rate is 1-2 ℃/min.
The process of the present invention will be described in detail below with reference to examples, comparative examples and experimental data.
Example one
This example provides a method for synthesizing a MOFs-silicone hybrid membrane, as shown in fig. 1, the method includes the following steps:
s1, mixing MOFs material with precursor sol containing organic silicon to obtain mixed sol;
s2, coating the mixed sol on a porous carrier, and calcining;
and S3, repeating the step S2 for 1-5 times to obtain the MOFs-organic silicon hybrid membrane.
The porous carrier is a carrier tube modified by surface defects, and gamma-Al is adopted2O3The method is characterized in that the particles fill up and modify macroporous defects on the surface of the carrier tube, and the method comprises the following specific steps:
(1) preparation of boehmite sol: weighing 18g of gamma-Al2O3Dissolving the particles in 480mL of deionized water, stirring vigorously for 3 hours, then adding 15mL of 1.6mol/L hydrochloric acid dropwise, continuing stirring for 1 hour, and then continuing hydrolytic aging at room temperature;
(2) surface defect modification of a carrier tube: drying water in a carrier tube which is treated in ultrasonic for at least half an hour, sealing one end of the carrier tube, and uniformly coating the prepared boehmite sol on the surface of the carrier in a vacuum coating mode for 15 s;
(3) and (3) putting the dried carrier tube into a muffle furnace, calcining and curing, and calcining at 600 ℃ for 180min at the heating rate of 1 ℃/min.
The MOFs material is a ZIF-8 material, and the synthesis mode of the ZIF-8 material is as follows: weighing 258g Zn (NO)3)2·6H2And dissolving O and 263g of 2-methylimidazole in 15mL of methanol respectively, slowly dropwise adding the 2-methylimidazole solution into the zinc nitrate solution, stirring at room temperature for 5min, centrifuging at 4000r/min for 30min, washing, and drying to obtain the ZIF-8 material.
Preparation of precursor sol containing organosilicon: weighing 12g of BTESE solution, dissolving the BTESE solution in 55mL of absolute ethyl alcohol, then adding 3g of ionized water and 3 drops of hydrochloric acid into the BTESE solution, oscillating the BTESE solution on a constant-temperature oscillator at 200r/min for 1h, and then adding 72mL of deionized water to oscillate for 3h to promote the BTESE solution to be continuously hydrolyzed; measuring 70mL of precursor sol, and carrying out the following steps: adding absolute ethyl alcohol into the mixture according to the proportion of 1 for dilution, then weighing 0.4g of ZIF-8 crystal, adding the crystal into the diluted precursor sol, and carrying out ultrasonic treatment for at least half an hour to uniformly mix the two.
Uniformly coating ZZIF-8/precursor sol, namely mixed sol, on gamma-Al-coated sol in a vacuum coating mode2O3The treated support surface was coated for 30s and then calcined at 250 ℃ for 180 min.
And repeating the operations of the vacuum coating and calcining steps for 1-5 times, and coating the mixed sol for a small number of times until a uniform and compact ZIF-8/organosilicon hybrid membrane is formed, wherein the number of the membrane tube is 1-5.
Example two
The difference between this embodiment and the first embodiment is: measuring 70mL of precursor sol, and carrying out the following steps: adding absolute ethyl alcohol into the mixed solution according to the proportion of 1 for dilution, then weighing 0.2g, 0.4g, 0.6g, 0.8g and 1g of ZIF-8 crystals, respectively adding the crystals into the diluted precursor sol, and carrying out ultrasonic treatment for at least half an hour to uniformly mix the crystals and the precursor sol.
Respectively and uniformly coating 5 ZZIF-8/precursor sols with different proportions, namely mixed sols, on gamma-Al-coated substrate by vacuum coating2O3The treated support surface was coated for 30s and then calcined at 250 ℃ for 180 min.
The operations of vacuum coating and calcining steps are repeated for 3 times, and the uniform and compact ZIF-8/organosilicon hybrid membrane can be formed by coating the mixed sol for a small number of times, wherein the serial number of the membrane tube is 6-10.
EXAMPLE III
The difference between this embodiment and the first embodiment is: the ZIF-8/precursor sol, namely the mixed sol, is uniformly coated on the gamma-Al-coated substrate in a vacuum coating mode2O3Coating the surface of the treated carrier for 30s, and calcining at 200-300 ℃ for 180 min.
The operations of vacuum coating and calcining steps are repeated for 3 times, and the uniform and compact ZIF-8/organosilicon hybrid membrane can be formed by coating the mixed sol for a small number of times, wherein the serial number of the membrane tube is 11-15.
Comparative example 1
The comparative example differs from example one in that: and (4) obtaining the hybrid membrane without adding MOFs materials. The performance of the obtained hybrid membrane is detected as follows: the water content of the permeation side is low, the flux is not high, and the industrialization is not facilitated.
Performance detection
The MOFs-organic silicon hybrid membranes with compact surfaces obtained in the examples 1 to 3 are subjected to pervaporation performance testing. The testing method is a pervaporation test, and specifically comprises the steps of placing a membrane material in a raw material liquid, sealing one end of the membrane material, sucking the membrane material at one end by using a vacuum pump, and condensing liquid nitrogen at a permeation side to obtain a penetrating fluid; the results obtained after the test are shown in tables 1 to 3.
Table 1 example 1 gives the MOFs-silicone hybrid film performance parameters.
Table 2 example 2 gives the MOFs-silicone hybrid film performance parameters.
Table 3 example 3 gives the MOFs-silicone hybrid film performance parameters.
As can be seen from Table 1, the water content, flux and separation factor on the permeation side of the hybrid membrane can be effectively controlled by controlling the coating times of the MOFs material and the precursor sol on the porous carrier, and the water content and the separation factor on the permeation side have optimal performance when the MOFs material and the precursor sol are coated for 3 times; the flux of the hybrid membrane is optimal when the membrane is coated once.
As can be seen from Table 2, the control of the addition of the MOFs material can effectively control the water content, flux and separation factor on the permeate side of the hybrid membrane; when 0.4g of ZIF-8 is added, the water content of the permeation side and the performance of a separation factor are optimal; when 0.2g of ZIF-8 was added, the flux of the hybrid membrane was optimal.
As can be seen from Table 3, the water content, flux and separation factor on the permeate side of the hybrid membrane can be effectively controlled by controlling the calcination temperature of the precursor sol; when the calcining temperature is 200 ℃, the water content, flux and separation factor performance of the permeation side are optimal; the performance of permeate side water content, flux and separation factor at a calcination temperature of 300 ℃ is the worst of the three sets of data.
Detailed description of the drawings 2-3:
referring to FIG. 2, a Scanning Electron Microscope (SEM) image of ZIF-8 powder provided in the examples is shown, wherein the ZIF-8 powder is in the form of regular particles, which illustrates the successful synthesis of ZIF-8 particles.
As shown in fig. 3, a Scanning Electron Microscope (SEM) plan view of the MOF-silicone hybrid film provided in the example is shown, wherein in the drawing, the surface of the film material is smooth, uniform and dense, which illustrates that the stable MOFs-silicone hybrid film material is successfully prepared.
It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A synthesis method of MOFs-organic silicon hybrid membrane is characterized by comprising the following steps:
s1, mixing MOFs material with precursor sol containing organic silicon to obtain mixed sol;
s2, coating the mixed sol on a porous carrier, and calcining;
and S3, repeating the step S2 for 1-5 times to obtain the MOFs-organic silicon hybrid membrane.
2. The method according to claim 1, characterized in that said MOFs material comprises the material ZIF-8.
3. The method according to claim 1, characterized in that the material ZIF-8 is prepared by a method comprising: respectively dissolving zinc nitrate hydrate and 2-methylimidazole in an organic solvent, mixing, centrifuging, washing and drying to obtain the material ZIF-8.
4. The method according to claim 1, wherein the molar ratio of the MOFs material to the precursor sol is 0.5-2: 0.5 to 2.
5. The method of claim 1, wherein the precursor sol is prepared by a sol-gel process, and the components of the precursor sol comprise: ethanol, 1, 2-bis (triethoxysilyl) ethane, monobasic acid and water.
6. The method according to claim 5, wherein the molar ratio of the 1, 2-bis (triethoxysilyl) ethane to the ethanol to the monobasic acid to the water is 0.5:8 to 10:0.1 to 0.5:6 to 12.
7. The method according to claim 5, wherein the coating is performed by a vacuum coating method, and the coating time is 15-60 s.
8. The method according to claim 1, wherein the temperature of the calcination is 200 to 300 ℃, the temperature rise rate of the calcination is 0.5 to 2 ℃/min, and the calcination time is 30 to 180 min.
9. The method of claim 1, wherein the porous support comprises a defect-modified support tube, the defect modification comprising a macroporous modification of the support tube.
10. The method of claim 1, wherein the porous support comprises:
and modifying the initial carrier tube by using more boehmite sol than macropores of the initial carrier tube, and calcining at 200-300 ℃ for 30-180 min to obtain the defect-modified carrier tube.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103816814A (en) * | 2014-03-06 | 2014-05-28 | 北京工业大学 | Porous granule MCM-41-ZIF-8/PDMS pervaporation hybrid membrane, preparation and application |
| CN107042067A (en) * | 2017-05-24 | 2017-08-15 | 天津大学 | Polysiloxanes metal-organic framework material hybrid pervaporation composite membrane and its preparation and application |
| CN108525526A (en) * | 2017-03-06 | 2018-09-14 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of composite membrane |
| US20180272288A1 (en) * | 2017-03-24 | 2018-09-27 | Korea University Research And Business Foundation | Method of preparing perm-selective porous membrane and method of separating gases using porous membrane prepared thereby |
| CN111298665A (en) * | 2020-02-25 | 2020-06-19 | 常州大学 | UIO-66-NH2Doped organic silicon high-salt wastewater treatment membrane and preparation method thereof |
-
2021
- 2021-12-31 CN CN202111667825.5A patent/CN114288870A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103816814A (en) * | 2014-03-06 | 2014-05-28 | 北京工业大学 | Porous granule MCM-41-ZIF-8/PDMS pervaporation hybrid membrane, preparation and application |
| CN108525526A (en) * | 2017-03-06 | 2018-09-14 | 中国科学院宁波材料技术与工程研究所 | A kind of preparation method of composite membrane |
| US20180272288A1 (en) * | 2017-03-24 | 2018-09-27 | Korea University Research And Business Foundation | Method of preparing perm-selective porous membrane and method of separating gases using porous membrane prepared thereby |
| CN107042067A (en) * | 2017-05-24 | 2017-08-15 | 天津大学 | Polysiloxanes metal-organic framework material hybrid pervaporation composite membrane and its preparation and application |
| CN111298665A (en) * | 2020-02-25 | 2020-06-19 | 常州大学 | UIO-66-NH2Doped organic silicon high-salt wastewater treatment membrane and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 谢昆等: "《纳米技术在水污染控制中的应用》", 31 July 2014, 武汉大学出版社 * |
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