CN113024829A - In-situ rapid preparation method of metal organic coordination polymer film suitable for various void-rich substrates - Google Patents
In-situ rapid preparation method of metal organic coordination polymer film suitable for various void-rich substrates Download PDFInfo
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- CN113024829A CN113024829A CN202110258152.1A CN202110258152A CN113024829A CN 113024829 A CN113024829 A CN 113024829A CN 202110258152 A CN202110258152 A CN 202110258152A CN 113024829 A CN113024829 A CN 113024829A
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- 239000002184 metal Substances 0.000 title claims abstract description 31
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- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
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- 238000000034 method Methods 0.000 claims description 23
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- 239000010949 copper Substances 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 16
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- 229910052742 iron Inorganic materials 0.000 claims description 12
- 239000003365 glass fiber Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
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- 239000004745 nonwoven fabric Substances 0.000 claims description 7
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- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 6
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- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
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- 229920000877 Melamine resin Polymers 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
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- 238000012983 electrochemical energy storage Methods 0.000 claims description 2
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- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 2
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- 229910021381 transition metal chloride Inorganic materials 0.000 claims description 2
- 229910002001 transition metal nitrate Inorganic materials 0.000 claims description 2
- 229910000385 transition metal sulfate Inorganic materials 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002759 woven fabric Substances 0.000 claims description 2
- 239000010408 film Substances 0.000 abstract description 55
- 239000010409 thin film Substances 0.000 abstract description 3
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- 229960002089 ferrous chloride Drugs 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
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- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 2
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- 238000006555 catalytic reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
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- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
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- 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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- 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C26/00—Coating not provided for in groups C23C2/00 - C23C24/00
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/37—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/40—Fibres of carbon
Abstract
The invention provides an in-situ rapid preparation method of a metal organic coordination polymer film suitable for surfaces of various void-rich substrates, which mainly comprises the following steps: by utilizing the void structure of the various void-rich materials themselves, the materials themselves can be first wetted by the reaction solution containing the metal ions and organic ligands and be integrally encapsulated. And then, the reaction liquid is volatilized and concentrated by hot air flow, so that the reaction liquid can be subjected to a dewetting phenomenon under the guidance of the three-dimensional structure of the base material. Along with the gradual volatilization of the components with lower boiling points and viscosity in the mixed solution, the components with higher boiling points and high viscosity in the residual solution can be close to the surface of the self structure of the substrate to form a liquid film. Under the combined action of the confinement effect of the liquid film and heat, metal ions and organic ligands in the liquid film can further perform coordination reaction, so that the generated metal-organic coordination polymer is constructed on the surface of the substrate in situ in the form of a thin film after the solution is completely volatilized.
Description
Technical Field
The invention relates to the technical field of coordination polymer materials, in particular to an in-situ rapid preparation method of a metal organic coordination polymer film suitable for various void-rich substrates.
Background
The coordination polymer material is a hybrid material formed by metal ions and organic ligands, and the structure and the composition of the coordination polymer material have high flexibility and diversity. The special property of the catalyst has abundant application potential in the fields of adsorption, separation, catalysis, energy storage and the like. However, most of the materials directly synthesized from various metal-organic coordination polymer materials are solid powder materials, which lack plasticity and ductility and are difficult to be molded into devices required in practical use through the traditional processing technology for use.
To achieve practical use of metal-organic coordination polymer materials, one effective approach is to synthesize them in situ on the desired substrate surface. And the actual processability is achieved by processing the substrate. The continuous metal organic coordination polymer film layer constructed in situ on the needed base material can effectively enhance the firmness of the adhesion on the surface of the base material and promote the performance to be fully exerted, thereby having strong practical value. Particularly, for various commonly used void-rich substrates such as nets, non-woven fabrics, foams and the like, the materials have good permeability, flexibility and other properties, can effectively promote mass transfer effect, and enhance the performance of coordination polymer materials in actual use. However, the existing processing technologies such as hydrothermal synthesis, layer-by-layer self-assembly, electrochemical methods, etc. often require long time and raw material consumption, depend on complex processing equipment, have great influence on production efficiency and cost, and are difficult to realize mass production. The method has important practical significance for developing a preparation method of a rapid in-situ structure metal organic coordination polymer film layer suitable for various commonly used void-rich materials.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an in-situ rapid preparation method of a metal organic coordination polymer film suitable for the surfaces of various void-rich substrates. And then the reaction solution is evaporated and concentrated by hot air flow, so that the reaction solution can be subjected to dewetting phenomenon under the guide of the three-dimensional structure of the base material. Along with the gradual volatilization of the lower boiling point component of the organic solvent, the higher boiling point and high viscosity component of the residual solution can be close to the surface of the self structure of the substrate to form a liquid film. Under the combined action of the confinement effect of the liquid film and heat, metal ions and organic ligands in the liquid film can further perform coordination reaction, so that the generated metal-organic coordination polymer is constructed on the surface of the substrate in situ in the form of a thin film after the solution is completely volatilized.
The technical scheme of the invention is realized as follows:
an in-situ rapid preparation method of a metal organic coordination polymer film suitable for the surfaces of various void-rich substrates comprises the following steps: by utilizing the gap structure of the gap-rich base material, the reaction liquid is adopted to soak the gap-rich base material and the whole body is wrapped; the reaction solution is an organic solution containing metal ions and organic ligands; the hot air flow is adopted to initiate evaporation and concentration of the reaction liquid, the reaction liquid is subjected to a dewetting phenomenon under the guidance of the self three-dimensional structure of the void-rich base material, and along with gradual volatilization of the lower boiling point and viscosity components in the mixed liquid, the high boiling point and viscosity components of the remaining solution can be close to the surface of the branched structure of the base material to form a liquid film; under the combined action of the confinement effect of the liquid film and heat, metal ions and organic ligands in the liquid film can further perform coordination reaction, so that the generated metal-organic coordination polymer is constructed on the surface of the substrate in situ in the form of a thin film after the solution is completely volatilized.
Further, the metal ions are one or more of transition metal chloride, nitrate and sulfate; the organic ligand is one or more of terephthalic acid, trimesic acid and 2-amino terephthalic acid; the organic solution is selected from two of N, N-dimethylformamide, ethanol, diethylene glycol, triethylene glycol and glycerol, wherein the organic solution with relatively high boiling point and viscosity and the organic solution with relatively low boiling point and viscosity have a volume ratio of 1: 1-15 to form a mixed solution.
Preferably, the transition metal is iron, cobalt, nickel, copper.
Further, the metal ions are dispersed in the organic solution at a concentration ranging from 10 to 100 millimoles per liter; the concentration range of the organic ligand dispersed in the organic solution is 10-100 millimoles per liter; mixing the metal ion solution and the organic ligand solution in a ratio of 1: 1-4 of the above-mentioned components are mixed to form the reaction solution.
Furthermore, the manner of wetting the void-rich substrate is to immerse the void-rich substrate in the reaction solution, so that the void-rich substrate can be wetted by the reaction solution.
Further, the manner of wetting the void-rich substrate is to spray the reaction solution on the surface of the void-rich substrate by means of spraying, so that the void-rich substrate can be wetted by the reaction solution.
Further, the amount of impregnating solution wetting the void-rich substrate is from about 10 to about 150 microliters per square centimeter.
Further, the base material with rich gaps is any one of nets, woven fabrics, non-woven fabrics and foams; the net type gap-rich base material is a copper net, an iron net or a nylon net; the woven cloth type gap-rich base material is carbon cloth, glass fiber cloth or nylon cloth; the non-woven fabric type gap-rich base material is nylon non-woven fabric or carbon fiber felt fabric; the foam type gap-rich base material is foamed copper, foamed nickel, foamed iron or melamine foam.
Furthermore, the hot air flow is heated air or heated inert gas, and the temperature of the hot air flow is 100-300 ℃.
Further, the wetted void-rich substrate may be subjected to the hot gas stream at a constant velocity through the gas flow-through zone or for a fixed time period of 8 to 15 seconds in the hot convection heating zone.
Further, the metal organic coordination polymer membrane prepared on various void-rich substrates is used for electrochemical energy storage, energy conversion, gas separation, water purification and organic dye removal.
The invention has the following beneficial effects:
(1) the metal organic coordination polymer film layers obtained on various substrate materials with rich gaps have rich varieties and strong adaptability, not only can be realized on various substrate materials, but also can obtain different crystallization properties by using different metal ions and organic ligands to combine as raw materials, obtain film layers with different surface appearances, and can exert the self properties of different metal organic coordination polymer materials.
(2) The method has the advantages of high utilization rate of raw materials, less consumption of film forming raw materials per unit area, high film forming efficiency, typical film forming processing process of less than 30 seconds and high production efficiency.
(3) The metal organic coordination polymer film prepared on various substrates by the method has controllable thickness, and the thickness can be accurately regulated from hundred nanometers to micron.
(4) The metal organic coordination polymer film obtained by the method has higher firmness, and the processing of bending, twisting, cutting and the like of the base material can not cause the falling off.
Drawings
FIG. 1 the present invention is loaded with Fe-BDC-NH2The macro photograph (1) and the magnified microscope photograph (2) of the iron mesh of the metal organic coordination polymer film.
FIG. 2 the present invention is loaded with Fe-BDC-NH2Scanning electron microscope photograph of iron net of metal organic coordination polymer film.
FIG. 3 shows the Fe-BDC-NH load of the present invention2Scanning electron microscope picture of the section of the iron net of the metal organic coordination polymer film.
FIG. 4 is a photomicrograph (1) and magnified photomicrograph (2) of a copper mesh of the present invention loaded with a Cu-BDC metal-organic coordination polymer film.
FIG. 5 scanning electron microscope photomicrograph of a copper mesh loaded with Cu-BDC metal organic coordination polymer film of the present invention.
FIG. 6 is a photomicrograph (1) and an enlarged photomicrograph (2) of a Co-BTC metal-organic coordination polymer film-loaded copper foam of the present invention.
FIG. 7 SEM photograph of Co-BTC metal-organic coordination polymer film loaded copper foam of the present invention.
FIG. 8 Fe-BDC-NH loaded on the present invention2The macro photograph (1) and the magnified microscope photograph (2) of the carbon cloth of the metal-organic coordination polymer film.
FIG. 9 Fe-BDC-NH loaded with the present invention2Scanning electron microscope photograph of carbon cloth of metal organic coordination polymer film.
FIG. 10 Fe-BDC-NH loaded with the present invention2The macro photograph (1) and the magnified microscope photograph (2) of the glass fiber cloth of the metal-organic coordination polymer film.
FIG. 11 Fe-BDC-NH loaded with the present invention2Scanning electron microscope photograph of glass fiber cloth of metal organic coordination polymer film.
Detailed Description
For a more clear understanding of the technical features, objects and advantages of the present invention, reference is now made to the following detailed description of the embodiments of the present invention taken in conjunction with the accompanying drawings, which are included to illustrate and not to limit the scope of the present invention.
Example 1
Fe-BDC-NH on surface of iron net2The preparation process of the metal organic coordination polymer film is as follows:
1. 0.5mmol of ferrous chloride and 0.5mmol of 2-aminoterephthalic acid were dissolved together in a solvent of 10ml of PEG/DMF (V: V ═ 1:10) to prepare a mixed solution.
2. The iron net was wetted by dipping it in the mixed solution in an amount of 10. mu.l/cm.
3. The wetted iron mesh was then transferred to a hot air stream at 220 c for about 10 seconds, the mixture was allowed to dry,as the solution is evaporated and dried, uniform Fe-BDC-NH can be formed on the surface of the steel mesh2A metal organic coordination polymer film.
As shown in figure 1, the obtained iron net has a uniform layer of color film stuck on the surface, and the color film is uniformly distributed and has good consistency.
As shown in fig. 2, the surface of the obtained film was flat, uniform and continuous as observed by using a scanning electron microscope.
As shown in fig. 3, the resulting film thickness was about 500 nm in cross section.
Example 2
The preparation process of the Cu-BDC metal organic coordination polymer film on the surface of the copper mesh is as follows:
1. 0.5mmol of copper nitrate and 0.5mmol of phthalic acid were dissolved together in 10mL of a solvent of ethanol/DMF (V: V ═ 1:1) to prepare a mixed solution.
2. The copper mesh was wetted by dipping it in the mixed solution and then taken out, the amount of dipping solution being about 15 microliters per square centimeter.
3. The wetted copper mesh was then transferred to a hot gas stream at 110 ℃ for about 10 seconds, and the mixture was allowed to dry, which allowed a uniform Cu-BDC metal organic coordination polymer film to form on the copper surface as the solution evaporated.
As shown in FIG. 4, a uniform blue film layer exists on the surface of the obtained copper mesh, and the copper mesh is uniformly distributed and has good consistency.
As shown in fig. 5, the obtained film layer was uniformly continuous over the entire surface from the lamellar structure to the combined surface, as observed by a scanning electron microscope.
Example 3
The preparation process of the Co-BTC metal organic coordination polymer film on the surface of the foam copper is as follows:
1. 0.6mmol of cobalt chloride and 0.4mmol of trimesic acid were dissolved together in 10mL of a solvent of glycerol/DMF (V: V ═ 1:10) to prepare a mixed solution.
2. The copper foam is wetted by the mixed liquor by immersing the copper foam in the mixed liquor in an amount of about 120 microliters per square centimeter.
3. The wetted copper foam was then exposed to a hot air stream at 220 c for about 15 seconds to dry the mixture and dry as the solution evaporated, a uniform Co-BTC metal organic coordination polymer film was formed on the carbon cloth surface.
As shown in FIG. 6, the obtained copper foam has a uniform light purple film layer on the surface, and the distribution is uniform and has good consistency.
As shown in fig. 7, the surface of the copper foam was observed to have a granular material composition using a scanning electron microscope, and the surface structure of the obtained film was uniform and continuous.
Example 4
Fe-BDC-NH on surface of carbon cloth2The preparation process of the metal organic coordination polymer film is as follows:
1. a mixture was prepared by dissolving 0.5mmol of ferrous chloride and 0.5mmol of 2-aminoterephthalic acid in 10mL of a solvent of diethylene glycol/DMF (V: V ═ 1: 15).
2. The mixed solution is sprayed on the surface of the carbon cloth by using a spraying mode, so that the carbon cloth can be wetted by the mixed solution, and the amount of the dipping solution is about 25 microliters per square centimeter.
3. Then exposing the soaked carbon cloth to a hot air stream at 220 deg.C, maintaining the temperature for about 15 seconds, drying the mixture, and drying the solution to form uniform Fe-BDC-NH on the surface of the carbon cloth2A metal organic coordination polymer film.
As shown in fig. 8, the surface color of the obtained carbon cloth is biased to yellowish brown and is uniformly distributed.
As shown in fig. 9, the surface of the obtained film on the surface of the carbon cloth was flat, uniform and continuous as observed by using a scanning electron microscope.
Example 5
Fe-BDC-NH on surface of glass fiber cloth2The preparation process of the metal organic coordination polymer film is as follows:
1. a mixture was prepared by dissolving 0.5mmol of ferrous chloride and 0.5mmol of 2-aminoterephthalic acid in 10mL of a solvent of diethylene glycol/DMF (V: V ═ 1: 15).
2. The mixed solution is sprayed on the surface of the glass fiber cloth by using a spraying mode, so that the glass fiber cloth can be wetted by the mixed solution, and the amount of the dipping solution is about 30 microliters per square centimeter.
3. The wetted glass fiber cloth was then exposed to a hot air stream at 220 deg.C for about 15 seconds to form uniform Fe-BDC-NH on the surface of the glass fiber cloth as the solution evaporated and dried2A metal organic coordination polymer film.
As shown in fig. 10, the surface of the obtained glass fiber became reddish brown and was uniformly distributed.
As shown in fig. 11, the resulting film layer on the surface of the glass fiber was covered with the film layer, as observed using a scanning electron microscope.
The above embodiments are merely provided to help understand the method and core principle of the present invention, and the main steps and embodiments of the present invention are described in detail by using specific examples. To those skilled in the art, the various conditions and parameters may be varied as desired in a particular implementation in accordance with the principles of the invention, and in view of the foregoing, the description is not to be taken as limiting the invention.
Claims (10)
1. An in-situ rapid preparation method of a metal organic coordination polymer film suitable for the surfaces of various void-rich substrates is characterized by comprising the following steps: the method comprises the following steps: by utilizing the gap structure of the gap-rich substrate, the reaction liquid is adopted to wet the gap-rich substrate and wrap the entire substrate; the reaction solution is an organic solution containing metal ions and organic ligands; the reaction solution is evaporated and concentrated by adopting hot air flow, the reaction solution is subjected to dewetting phenomenon under the guidance of the three-dimensional structure of the substrate with rich gaps, and the reaction solution is close to the surface of the self structure of the substrate to form a liquid film; under the combined action of the confinement effect of the liquid film and heat, metal ions in the liquid film and organic ligands perform a coordination reaction to generate a metal-organic coordination polymer which is in-situ constructed on the surface of the substrate in the form of a film.
2. The method for rapidly preparing the metal-organic coordination polymer film suitable for the surfaces of various void-rich substrates in situ according to claim 1, wherein the method comprises the following steps: the metal ions are one or more of transition metal chloride, nitrate and sulfate; the organic ligand is one or more of terephthalic acid, trimesic acid and 2-amino terephthalic acid; the organic solution is selected from two of N, N-dimethylformamide, ethanol, diethylene glycol, triethylene glycol and glycerol, wherein the organic solution with relatively high boiling point and viscosity and the organic solution with relatively low boiling point and viscosity have a volume ratio of 1: 1-15 to form a mixed solution.
3. The method for rapidly preparing the metal-organic coordination polymer film suitable for the surfaces of various void-rich substrates in situ according to claim 1, wherein the method comprises the following steps: the concentration range of the metal ions dispersed in the organic solution is 10-100 millimoles per liter; the concentration range of the organic ligand dispersed in the organic solution is 10-100 millimoles per liter; mixing the metal ion solution and the organic ligand solution in a ratio of 1: 1-4 of the above-mentioned components are mixed to form the reaction solution.
4. The method for rapidly preparing the metal-organic coordination polymer film suitable for the surfaces of various void-rich substrates in situ according to claim 1, wherein the method comprises the following steps: the manner of wetting the void-rich substrate is to immerse the void-rich substrate in the reaction solution, which can be wetted by the reaction solution.
5. The method for rapidly preparing the metal-organic coordination polymer film suitable for the surfaces of various void-rich substrates in situ according to claim 1, wherein the method comprises the following steps: the manner of wetting the substrate with the gap is to spray the reaction solution on the surface of the substrate with the gap, so that the substrate with the gap can be wetted by the reaction solution.
6. The method for rapidly preparing the metal-organic coordination polymer film suitable for the surfaces of various void-rich substrates in situ according to claim 1, wherein the method comprises the following steps: the amount of impregnating solution wetting the void-rich substrate is from 10 to 150 microliters per square centimeter.
7. The method for rapidly preparing the metal-organic coordination polymer film suitable for the surfaces of various void-rich substrates in situ according to claim 1, wherein the method comprises the following steps: the base material with rich gaps is any one of nets, woven fabrics, non-woven fabrics and foams; the net type gap-rich base material is a copper net, an iron net or a nylon net; the woven cloth type gap-rich base material is carbon cloth, glass fiber cloth or nylon cloth; the non-woven fabric type gap-rich base material is nylon non-woven fabric or carbon fiber felt fabric; the foam type gap-rich base material is foamed copper, foamed nickel, foamed iron or melamine foam.
8. The method for rapidly preparing the metal-organic coordination polymer film suitable for the surfaces of various void-rich substrates in situ according to claim 1, wherein the method comprises the following steps: the hot air flow is heated air or heated inert gas, and the temperature of the hot air flow is 100-300 ℃.
9. The method for rapidly preparing the metal-organic coordination polymer film suitable for the surfaces of various void-rich substrates in situ according to claim 1, wherein the method comprises the following steps: the wetted void-rich substrate is subjected to a hot gas stream for a fixed time period of 8 to 15 seconds in the hot convection heating zone.
10. Use of the metal-organic coordination polymer films prepared on a variety of void-rich substrates according to claims 1-9, characterized by: the metal organic coordination polymer membrane prepared on various void-rich substrates is used for electrochemical energy storage, energy conversion, gas separation, water purification and organic dye removal.
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