CN108467502A - A kind of preparation method of porous-polynanofilm material - Google Patents
A kind of preparation method of porous-polynanofilm material Download PDFInfo
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Abstract
A kind of preparation method of porous-polynanofilm material, belongs to thin-film material technical field.The present invention prepares composite nano film using the method for fractional steps, it is primarily based on LB membrane formation process and makes ultrathin membrane in substrate, since organic ligand is assembled during gas-liquid interface is sprawled in the form of monolayer, it can be assembled into the monolayer rank ultrathin membrane with ordered nano-structure after compressed organic ligand molecule, therefore porous structure MOFs films are obtained after being reacted with metal ion；Then ultra-thin porous MOFs films are placed in gas phase conducting polymer monomer and gaseous oxidizing agent atmosphere, by the way of full gas-phase polymerization, oxidizer molecule induces monomer molecule to polymerize by way of colliding and polymerizeing in reaction process, to by controlling oxidant and monomer atmosphere come so that the successive sedimentation of ultra-thin conductive polymer in the intrinsic structures of MOFs, and then ensures not destroying its porous structure while effectively promoting the electric conductivity of MOFs.
Description
Technical field
The invention belongs to thin-film material technical field, more particularly to a kind of preparation side of porous-polynanofilm material
Method.
Background technology
Metal organic framework (metal-organic frameworks, MOFs) is passed through by metal ion and organic ligand
The holey frame structure material that coordination is formed.The structure of MOFs is metal cation and organic electron donors by classics
Coordination key connection composition crystalline material, hole made of self assembly is very firm in the solution, have certain machinery
Intensity, and due to existing while inorganic constituents and organic principle, make to cut out cavity dimensions and chemistry is changed commanders to reach specific
Function is possibly realized.The close phase of geometry that the topological structure of MOFs is formed with metallic ion coordination environment and organic linking
Close, be different from conventional microporous structural inorganic object, these features distinguish MOFs and other kinds of porous material, make its
The various fields such as electrochemistry, catalysis, separation, photovoltaic, sensing have extremely important application value.
In recent years, porous MOFs and derivative are gradually applied to electrochemical energy storage field, such as lithium ion battery, fuel electricity
Pond and ultracapacitor etc..Largely studies have shown that abundant meso-hole structure and the active site of surface height exposure make to be based on
MOFs has high specific capacity as the ultracapacitor of electrode；Meanwhile by selecting different metal salt to be closed with organic ligand
At different MOFs structures, charge delivering path can be regulated and controled to promote the capacity characteristic and stability of electrode.Therefore, with MOFs
The electrode material of high-specific surface area and abundant active site can be built as basis material, effectively promote the energy storage effect of energy storage material
Rate.However, due to the energy gap of organic ligand in MOFs it is usually wider (>3eV), cause the level-density parameter of itself and metal node
Property is poor, then causes the delocalized ability of carrier in MOFs materials weak, macro manifestations are poorly conductive.Now currently, MOFs itself
Poorly conductive not only becomes the matter of utmost importance for inhibiting its electricity and electrochemical energy storage performance boost, equally also significantly limits it
Practical application in electronics and electrochemical energy storing device field.Therefore, how to solve the problems, such as that the low electric conductivity of MOFs materials becomes
It is existing ensure at present MOFs materials electronics and electrochemical energy storage field fast-developing key.
For now, the method in the prior art to promote MOFs material conductivities mainly has the following two kinds：One
It is to realize by adjusting the level-density parameter of organic ligand and metal ion, this method needs are adjusted from molecular structure
Control, and suitable metal ion is found to match, difficulty is very big；It is another to be (such as to lead using the preferable material of electric conductivity
Electric polymer) with MOFs is compound realizes, this method by porous structure successive sedimentation conducting polymer improve material
Expect whole electric conductivity.The methods of hydrothermal synthesis, liquid phase fabricated in situ are generally selected in the industry to realize conducting polymer and MOFs
Two kinds of materials it is compound.But these methods can destroy the porous structure of MOFs materials, and then lead to compound obtained porous material
The pore radiuses and distribution of material is uncontrollable, and adjusts the dimension of hole and be exactly further to control relative adsorption rate and hole percent of pass
Construct the important foundation of its application.Therefore, conductive material is used to modify MOFs materials effectively to promote material whole conductivity
Meanwhile how to ensure the intrinsic structure of MOFs, its porous structure is not destroyed, becomes this field technical problem urgently to be resolved hurrily.
Invention content
It is an object of the invention to：Existed using conductive material modification MOFs material method therefors for the prior art and is destroyed
The intrinsic structures of MOFs cause that the uncontrollable problem of composite material hole dimension is made, provide a kind of porous-polynanofilm material
The preparation method of material, this method can ensure that the intrinsic structures of MOFs are not destroyed, and then reach controllable adjustment composite material hole
Purpose.
To achieve the goals above, the present invention provides the following technical solutions：
A kind of preparation method of porous-polynanofilm material, which is characterized in that include the following steps：
Step A：Organic ligand molecule layer is sprawled on the gas-liquid interface that water and air is formed, is forced into solid phase membrane pressure；So
Metal cation salt is added in water phase afterwards so that metal cation salt, which is mixed in water, forms metal ion salt solution, metal ion
It is reacted with organic ligand and generates molecular layer rank porous metal-organic framework film, it is heavy that porous metal-organic framework film is shifted
Product is in substrate surface；
Step B：There is the substrate of porous metal-organic framework to be placed in gas phase conducting polymer monomer the deposition that step A is obtained
With gaseous oxidation dosage form at mixed atmosphere in carry out chemical gaseous phase polymerisation so that conducting polymer is deposited on porous metals
The porous-polynanofilm material is formed on organic backbone film.
Further, in the step A organic ligand be it is any can form unimolecular layer membrane in gas-liquid interface, and can be with
The organic ligand molecule that metal ion chemically reacts, including but not limited to：Equal phthalic acid and its formic acid derivates, equal benzene
Tricarboxylic acid and its formic acid derivates, 2,6- naphthalenedicarboxylic acids and its formic acid derivates, 2,2'- bipyridyl -4,4'- dioctyl phthalate and its first
Acid derivative.
Further, in the step A metal ion include transition metal element formed ion, specifically include but unlimited
In iron ion, manganese ion and zinc ion any one or it is a variety of.
Further, in the step A in metal ion salt solution metal ion a concentration of 1mg/mL~10mg/mL.
Further, metal ion and organic ligand reaction time are 20min~80min in the step A.
Further, LB film build methods are liquid level reduction method, horizontal film forming hair or vertical membrane formation process in the step A.
Further, conducting polymer monomer is any one in thiophene, pyrroles and aniline or more in the step B
Kind.
Further, in the step B gas phase conducting polymer monomer a concentration of 50~100ppm.Further, institute
It includes but not limited to ferric trichloride, toluenesulfonic acid iron or ammonium persulfate to state oxidant in step B.
Further, in the step B gaseous oxidizing agent a concentration of 200~400ppm.
Further, the response parameter of chemical gaseous phase polymerisation is in the step B：50 DEG C~100 DEG C of reaction temperature,
Reaction pressure is 0.02~0.08MPa, reaction time 10min~40min.
The principle of the invention is：Composite nano film is prepared using the method for fractional steps, LB membrane formation process is primarily based on and is made in substrate
Make ultrathin membrane, it is compressed organic since organic ligand is assembled during gas-liquid interface is sprawled in the form of monolayer
The monolayer rank ultrathin membrane with ordered nano-structure can be assembled into after ligand molecular, therefore after being reacted with metal ion
Obtain the porous structure MOFs ultrathin membranes of monolayer rank；Porous MOFs ultrathin membranes are then placed in gas phase conducting polymer list
In body and gaseous oxidizing agent atmosphere, by the way of full gas-phase polymerization, oxidizer molecule is by colliding polymerization in reaction process
Mode induces monomer molecule to polymerize, and enables to the ultra-thin conductive polymer continuous by controlling oxidant and monomer atmosphere
It is deposited in the intrinsic structures of MOFs, and then ensures not destroying its porous structure while effectively promoting the electric conductivity of MOFs.
The beneficial effects of the invention are as follows：
(1) hole that can accurately regulate and control MOFs and conducting polymer formation composite material with the preparation method of the present invention is tied
Structure also maintains the intrinsic structure of MOFs while effectively promoting conductive characteristic, advantageously ensures that the stability of its performance.
(2) the large area porous nanometer thin films of MOFs molecular assemblies arrangement can be obtained with the preparation method of the present invention,
It is beneficial to the migration of carrier from structure feature, is formed for conventional composite materials with conducting polymer compared to MOFs and more helped
In its conductive characteristic of promotion.
(3) preparation method operations proposed by the present invention are controllable, environmentally protective, are suitable for industrialized production,
Specific implementation mode
Specific embodiments of the present invention are described below in detail, the principle of the present invention and its practical application are explained with this, from
And make others skilled in the art it will be appreciated that various embodiments of the present invention and suitable for the various of specific intended application
Modification.
The present invention is intended to provide a kind of preparation method of porous-polynanofilm material, the present invention is prepared using substep
MOFs ultrathin membranes and conducting polymer ultrathin membrane so that conducting polymer monomer is deposited under oxidant induction through LB membrane formation process
On obtained monolayer rank MOFs ultrathin membranes, ultra-thin conductive polymeric layer forms a film in the intrinsic body structure surfaces of MOFs, to keep away
Exempt from based on conventional hydrothermal synthesis or liquid phase fabricated in situ using porous caused by conducting polymer materials modification MOFs materials
The problem of structure is destroyed.
Embodiment 1：
A kind of preparation method of porous-polynanofilm material, specifically includes following operation：
Step 1：
It is the sample bottle of 30mL to take 1 volume, is first cleaned with cleaning agent, flowing water is used in combination to rinse well, then be sequentially placed into second
It is cleaned by ultrasonic respectively in alcohol and deionized water 15 minutes, is then dried up with nitrogen spare；
Step 2：
The present embodiment dissolves trimesic acid using dimethylformamide as solvent, described molten according to common sense in the field
Agent is not limited to one kind in the present embodiment, and the present invention does not limit this, can be according to practical specific choice；
125mg trimesic acids are dissolved in 49.3mL dimethylformamides, the solution that total volume is 50mL is made, this
The solution is added to ultrasonic disperse 3 hours in sample bottle, obtained by a concentration of 2.5mg/mL of trimesic acid in sample solution
Trimesic acid dispersion liquid is spare；
Step 3：
22.5mg ferric nitrates are dissolved in, the iron nitrate solution that total volume is 50mL, such solution are made in the super waters of 47.5mL
The solution is added to ultrasonic disperse 3 hours in sample bottle, obtains ferric nitrate salinity by a concentration of 4.5mg/mL of middle ferric nitrate
Dispersion liquid is spare；
Step 4：
10mL step 2 obtained solutions are measured using microsyringe, the ultrapure water surface in LB film slots is added dropwise, is waited for
After solvent volatilizees 30 minutes, organic ligand is assembled during gas-liquid interface is sprawled with either as singular molecular entities；Mobile sliding barrier pressure
Contracting trimesic acid Langmuir films are to certain solid phase membrane pressure (35~40mN/m), and persistent oscillation 30 minutes, by being compressed with
Machine ligand molecular can form ultrathin membrane；
Step 5：
30mL step 3 obtained solutions are measured using microsyringe, are added dropwise in the ultra-pure water in LB film slots, equal benzene
Tricarboxylic acid is reacted with iron ion can obtain porous structure, and the reaction time is 40 minutes, at this point, gas-liquid interface ultrathin membrane is still tieed up
It holds other in monolayer；Then trimesic acid iron MOFs ultrathin membranes obtained by the reaction are deposited on by substrate using liquid level descent method
Surface, specifically, the liquid level descent method is after MOFs ultrathin membranes are adsorbed on substrate surface first, then using reducing liquid level
MOFs ultrathin membranes are deposited on substrate surface by method, and substrate surface thickness is basically when organic ligand molecule is sprawled at this time
Thickness；
Step 6：
Deposition there is into the closed environment that the substrate of trimesic acid iron MOFs ultrathin membranes is placed in thiophene and ferric trichloride atmosphere
Middle progress chemical gaseous phase aggregation deposition, air pressure is 0.04MPa in the closed environment, and polymerization temperature is 60 DEG C, oxidizer molecule
Monomer molecule is induced to polymerize by colliding polymerization methods, polymerization time is 15 minutes, final obtained polythiophene modification
Porous trimesic acid iron MOFs materials.
Embodiment 2：
A kind of preparation method of porous-polynanofilm material, specifically includes following operation：
Step 1：
It is the sample bottle of 30mL to take 1 volume, is first cleaned with cleaning agent, flowing water is used in combination to rinse well, then be sequentially placed into second
It is cleaned by ultrasonic respectively in alcohol and deionized water 15 minutes, is then dried up with nitrogen spare；
Step 2：
The present embodiment dissolves trimesic acid using dimethylformamide as solvent, described molten according to common sense in the field
Agent is not limited to one kind in the present embodiment, and the present invention does not limit this, can be according to practical specific choice；
75mg trimesic acids are dissolved in 49.8mL dimethylformamides, the solution that total volume is 50mL is made, in this way
The solution is added to ultrasonic disperse 3 hours in sample bottle by a concentration of 1.5mg/mL of trimesic acid in solution, is obtained
Benzenetricarboxylic acid dispersion liquid is spare；
Step 3：
175mg ferric nitrates are dissolved in, the iron nitrate solution that total volume is 50mL, such solution are made in the super waters of 45.3mL
The solution is added to ultrasonic disperse 3 hours in sample bottle, obtains ferric nitrate salinity by a concentration of 3.5mg/mL of middle ferric nitrate
Dispersion liquid is spare；
Step 4：
10mL step 2 obtained solutions are measured using microsyringe, the ultrapure water surface in LB film slots is added dropwise, is waited for
After solvent volatilizees 30 minutes, organic ligand is assembled during gas-liquid interface is sprawled with either as singular molecular entities；Mobile sliding barrier pressure
Contracting trimesic acid Langmuir films are to certain solid phase membrane pressure (35~40mN/m), and persistent oscillation 30 minutes, by being compressed with
Machine ligand molecular can form ultrathin membrane；
Step 5：
30mL step 3 obtained solutions are measured using microsyringe, are added dropwise in the ultra-pure water in LB film slots, equal benzene
Tricarboxylic acid is reacted with iron ion can obtain porous structure, and the reaction time is 60 minutes, at this point, gas-liquid interface ultrathin membrane is still tieed up
It holds other in monolayer；Then trimesic acid iron MOFs ultrathin membranes obtained by the reaction are deposited on by substrate using liquid level descent method
Surface, specifically, the liquid level descent method is after MOFs ultrathin membranes are adsorbed on substrate surface first, then using reducing liquid level
MOFs ultrathin membranes are deposited on substrate surface by method, and substrate surface thickness is basically when organic ligand molecule is sprawled at this time
Thickness；
Step 6：
There is the substrate of trimesic acid iron MOFs ultrathin membranes to be placed in 3,4- ethene dioxythiophenes and ferric trichloride gas deposition
Chemical gaseous phase aggregation deposition is carried out in the closed environment of atmosphere, air pressure is 0.05MPa, polymerization temperature 50 in the closed environment
DEG C, oxidizer molecule induces monomer molecule to polymerize by colliding polymerization methods, and polymerization time is 30 minutes, final to be made
The porous trimesic acid iron MOFs materials of poly- 3,4- ethene dioxythiophenes modification.
Embodiment 3：
A kind of preparation method of porous-polynanofilm material, specifically includes following operation：
Step 1：
It is the sample bottle of 30mL to take 1 volume, is first cleaned with cleaning agent, flowing water is used in combination to rinse well, then be sequentially placed into second
It is cleaned by ultrasonic respectively in alcohol and deionized water 15 minutes, is then dried up with nitrogen spare；
Step 2：
The present embodiment dissolves trimesic acid using dimethylformamide as solvent, described molten according to common sense in the field
Agent is not limited to one kind in the present embodiment, and the present invention does not limit this, can be according to practical specific choice；
200mg trimesic acids are dissolved in 48.6mL dimethylformamides, the solution that total volume is 50mL is made, this
The solution is added to ultrasonic disperse 3 hours in sample bottle, obtained by a concentration of 4.0mg/mL of trimesic acid in sample solution
Trimesic acid dispersion liquid is spare；
Step 3：
325mg ferric nitrates are dissolved in, the iron nitrate solution that total volume is 50mL, such solution are made in the super waters of 42.7mL
The solution is added to ultrasonic disperse 3 hours in sample bottle, obtains ferric nitrate salinity by a concentration of 6.5mg/mL of middle ferric nitrate
Dispersion liquid is spare；
Step 4：
10mL step 2 obtained solutions are measured using microsyringe, the ultrapure water surface in LB film slots is added dropwise, is waited for
After solvent volatilizees 30 minutes, organic ligand is assembled during gas-liquid interface is sprawled with either as singular molecular entities；Mobile sliding barrier pressure
Contracting trimesic acid Langmuir films are to certain solid phase membrane pressure (35~40mN/m), and persistent oscillation 30 minutes, by being compressed with
Machine ligand molecular can form ultrathin membrane；
Step 5：
30mL step 3 obtained solutions are measured using microsyringe, are added dropwise in the ultra-pure water in LB film slots, equal benzene
Tricarboxylic acid is reacted with iron ion can obtain porous structure, and the reaction time is 80 minutes, at this point, gas-liquid interface ultrathin membrane is still tieed up
It holds other in monolayer；Then trimesic acid iron MOFs ultrathin membranes obtained by the reaction are deposited on by substrate using liquid level descent method
Surface, specifically, the liquid level descent method is after MOFs ultrathin membranes are adsorbed on substrate surface first, then using reducing liquid level
MOFs ultrathin membranes are deposited on substrate surface by method, and substrate surface thickness is basically when organic ligand molecule is sprawled at this time
Thickness；
Step 6：
Deposition there is into the closed environment that the substrate of trimesic acid iron MOFs ultrathin membranes is placed in pyrroles and ammonium persulfate atmosphere
Middle progress chemical gaseous phase aggregation deposition, air pressure is 0.02MPa in the closed environment, and polymerization temperature is 70 DEG C, oxidizer molecule
Monomer molecule is induced to polymerize by colliding polymerization methods, polymerization time is 20 minutes, final obtained polypyrrole modifying
Porous trimesic acid iron MOFs materials.
Embodiment 4：
A kind of preparation method of porous-polynanofilm material, specifically includes following operation：
Step 1：
It is the sample bottle of 30mL to take 1 volume, is first cleaned with cleaning agent, flowing water is used in combination to rinse well, then be sequentially placed into second
It is cleaned by ultrasonic respectively in alcohol and deionized water 15 minutes, is then dried up with nitrogen spare；
Step 2：
The present embodiment dissolves equal phthalic acid using dimethylformamide as solvent, described molten according to common sense in the field
Agent is not limited to one kind in the present embodiment, and the present invention does not limit this, can be according to practical specific choice；
300mg trimesic acids are dissolved in 47.3mL dimethylformamides, the solution that total volume is 50mL is made, this
A concentration of 6.0mg/mL of equal phthalic acid in sample solution, is added to ultrasonic disperse 3 hours in sample bottle by the solution, obtains
Equal phthalic acid dispersion liquid is spare；
Step 3：
475mg ferric nitrates are dissolved in, the iron nitrate solution that total volume is 50mL is made in the super waters of 38.9mL, measured respectively
Ferric nitrate and ultra-pure water prepare to obtain the solution that total volume is 50mL, a concentration of 9.5mg/mL of ferric nitrate in such solution, will
The solution is added to ultrasonic disperse 3 hours in sample bottle, and it is spare to obtain nitric acid iron salt dispersion；
Step 4：
10mL step 2 obtained solutions are measured using microsyringe, the ultrapure water surface in LB film slots is added dropwise, is waited for
After solvent volatilizees 30 minutes, organic ligand is assembled during gas-liquid interface is sprawled with either as singular molecular entities；Mobile sliding barrier pressure
Equal phthalic acid Langmuir films contract to certain solid phase membrane pressure (35~40mN/m), and persistent oscillation 30 minutes, by being compressed with
Machine ligand molecular can form ultrathin membrane；
Step 5：
30mL step 3 obtained solutions are measured using microsyringe, are added dropwise in the ultra-pure water in LB film slots, equal benzene
Dioctyl phthalate is reacted with iron ion can obtain porous structure, and the reaction time is 50 minutes, at this point, gas-liquid interface ultrathin membrane is still tieed up
It holds other in monolayer；Then equal phthalic acid iron MOFs ultrathin membranes obtained by the reaction are deposited on by substrate using liquid level descent method
Surface, specifically, the liquid level descent method is after MOFs ultrathin membranes are adsorbed on substrate surface first, then using reducing liquid level
MOFs ultrathin membranes are deposited on substrate surface by method, and substrate surface thickness is basically when organic ligand molecule is sprawled at this time
Thickness；
Step 6：
Deposition there is into the closed environment that the substrate of equal phthalic acid iron MOFs ultrathin membranes is placed in thiophene and ferric trichloride atmosphere
Middle progress chemical gaseous phase aggregation deposition, air pressure is 0.08MPa in the closed environment, and polymerization temperature is 60 DEG C, oxidizer molecule
Monomer molecule is induced to polymerize by colliding polymerization methods, polymerization time is 30 minutes, final obtained polythiophene modification
Porous equal phthalic acid iron MOFs materials.
Embodiment 5：
A kind of preparation method of porous-polynanofilm material, specifically includes following operation：
Step 1：
It is the sample bottle of 30mL to take 1 volume, is first cleaned with cleaning agent, flowing water is used in combination to rinse well, then be sequentially placed into second
It is cleaned by ultrasonic respectively in alcohol and deionized water 15 minutes, is then dried up with nitrogen spare；
Step 2：
The present embodiment dissolves equal phthalic acid using dimethylformamide as solvent, described molten according to common sense in the field
Agent is not limited to one kind in the present embodiment, and the present invention does not limit this, can be according to practical specific choice；
300mg trimesic acids are dissolved in 47.3mL dimethylformamides, the solution that total volume is 50mL is made, it will
The solution is added to ultrasonic disperse 3 hours in sample bottle, and it is spare to obtain equal phthalic acid dispersion liquid；
Step 3：
150mg manganese nitrates are dissolved in 48.2mL ultra-pure waters, nitric acid in the such solution of solution that total volume is 50mL is made
The solution is added to ultrasonic disperse 3 hours in sample bottle, it is standby to obtain manganese nitrate salt dispersion liquid by a concentration of 3.0mg/mL of manganese
With；
Step 4：
10mL step 2 obtained solutions are measured using microsyringe, the ultrapure water surface in LB film slots is added dropwise, is waited for
After solvent volatilizees 30 minutes, organic ligand is assembled during gas-liquid interface is sprawled with either as singular molecular entities；Mobile sliding barrier pressure
Equal phthalic acid Langmuir films contract to certain solid phase membrane pressure (35~40mN/m), and persistent oscillation 30 minutes, by being compressed with
Machine ligand molecular can form ultrathin membrane；
Step 5：
30mL step 3 obtained solutions are measured using microsyringe, are added dropwise in the ultra-pure water in LB film slots, equal benzene
Dioctyl phthalate is reacted with manganese ion can obtain porous structure, and the reaction time is 70 minutes, at this point, gas-liquid interface ultrathin membrane is still tieed up
It holds other in monolayer；Then equal phthalic acid manganese MOFs ultrathin membranes obtained by the reaction are deposited on by substrate using liquid level descent method
Surface, specifically, the liquid level descent method is after MOFs ultrathin membranes are adsorbed on substrate surface first, then using reducing liquid level
MOFs ultrathin membranes are deposited on substrate surface by method, and substrate surface thickness is basically when organic ligand molecule is sprawled at this time
Thickness；
Step 6：
Deposition there is into the closed environment that the substrate of equal phthalic acid manganese MOFs ultrathin membranes is placed in thiophene and manganic chloride atmosphere
Middle progress chemical gaseous phase aggregation deposition, air pressure 0.07MPa in the closed environment, polymerization temperature are 80 DEG C, and oxidizer molecule is logical
Collision polymerization methods are crossed to induce monomer molecule to polymerize, polymerization time is 25 minutes, and final obtained polythiophene is modified more
The equal phthalic acid manganese MOFs materials in hole.
Embodiment 6：
A kind of preparation method of porous-polynanofilm material, specifically includes following operation：
Step 1：
It is the sample bottle of 30mL to take 1 volume, is first cleaned with cleaning agent, flowing water is used in combination to rinse well, then be sequentially placed into second
It is cleaned by ultrasonic respectively in alcohol and deionized water 15 minutes, is then dried up with nitrogen spare；
Step 2：
The present embodiment dissolves 2,6-naphthalenedicarboxylic acid using dimethylformamide as solvent, described according to common sense in the field
Solvent is not limited to one kind in the present embodiment, and the present invention does not limit this, can be according to practical specific choice；
125mg 2,6-naphthalenedicarboxylic acid is dissolved in 46.9mL dimethylformamides, the solution that total volume is 50mL is made,
The solution is added to ultrasonic disperse 3 hours in sample bottle by a concentration of 2.5mg/mL of 2,6-naphthalenedicarboxylic acid in this way in solution,
It is spare to obtain 2,6- naphthalenedicarboxylic acid dispersion liquids；
Step 3：
22.5mg ferric nitrates are dissolved in, the iron nitrate solution that total volume is 50mL, such solution are made in the super waters of 47.5mL
The solution is added to ultrasonic disperse 3 hours in sample bottle, obtains ferric nitrate salinity by a concentration of 4.5mg/mL of middle ferric nitrate
Dispersion liquid is spare；
Step 4：
10mL step 2 obtained solutions are measured using microsyringe, the ultrapure water surface in LB film slots is added dropwise, is waited for
After solvent volatilizees 30 minutes, organic ligand is assembled during gas-liquid interface is sprawled with either as singular molecular entities；Mobile sliding barrier pressure
Contracting 2,6-naphthalenedicarboxylic acid Langmuir films are to certain solid phase membrane pressure (35~40mN/m), and persistent oscillation 30 minutes, pass through compression
Organic ligand molecule can form ultrathin membrane；
Step 5：
30mL step 3 obtained solutions are measured using microsyringe, are added dropwise in the ultra-pure water in LB film slots, 2,6-
Naphthalenedicarboxylic acid is reacted with iron ion can obtain porous structure, and the reaction time is 40 minutes, at this point, gas-liquid interface ultrathin membrane is still
It is other to maintain monolayer；Then 2,6- naphthalenedicarboxylic acids iron MOFs ultrathin membranes obtained by the reaction are deposited on using liquid level descent method
Substrate surface, specifically, the liquid level descent method is after MOFs ultrathin membranes are adsorbed on substrate surface first, then using reducing liquid
MOFs ultrathin membranes are deposited on substrate surface by the method in face, and substrate surface thickness is basically that organic ligand molecule is sprawled at this time
When thickness；
Step 6：
Deposition there is into the closed loop that the substrate of 2,6- naphthalenedicarboxylic acid iron MOFs ultrathin membranes is placed in thiophene and ferric trichloride atmosphere
Chemical gaseous phase aggregation deposition is carried out in border, air pressure is 0.06MPa in the closed environment, and polymerization temperature is 60 DEG C, oxidant point
Son induces monomer molecule to polymerize by colliding polymerization methods, and polymerization time is 15 minutes, finally obtained polythiophene modification
Porous 2,6- naphthalenedicarboxylic acids iron MOFs materials.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement etc., should all be included in the protection scope of the present invention made by within refreshing and principle.
Claims (10)
1. a kind of preparation method of porous-polynanofilm material, which is characterized in that include the following steps：
Step A：Organic ligand molecule layer is sprawled on the gas-liquid interface that water and air is formed, is forced into solid phase membrane pressure；Then exist
Metal cation salt is added in water phase so that metal cation salt, which is mixed in water, forms metal ion salt solution, metal ion with have
Machine ligand reaction generates molecular layer rank porous metal-organic framework film, and the transfer of porous metal-organic framework film is deposited on
Substrate surface；
Step B：There is the substrate of porous metal-organic framework to be placed in gas phase conducting polymer monomer the deposition that step A is obtained gentle
Phase oxidation dosage form at mixed atmosphere in carry out chemical gaseous phase polymerisation so that it is organic that conducting polymer is deposited on porous metals
The porous-polynanofilm material is formed on skeleton film.
2. a kind of preparation method of porous-polynanofilm material according to claim 1, which is characterized in that the step
Organic ligand can form unimolecular layer membrane to be any in gas-liquid interface in rapid A, and can be chemically reacted with metal ion
Organic ligand molecule.
3. a kind of preparation method of porous-polynanofilm material according to claim 1, which is characterized in that the step
Organic ligand includes equal phthalic acid and its formic acid derivates, trimesic acid and its formic acid derivates, 2,6- naphthalene diformazans in rapid A
Acid and its formic acid derivates, 2,2'- bipyridyl -4,4'- dioctyl phthalate and its formic acid derivates.
4. a kind of preparation method of porous-polynanofilm material according to claim 1, which is characterized in that the step
Metal ion includes the ion that transition metal element is formed in rapid A.
5. a kind of preparation method of porous-polynanofilm material according to claim 1, which is characterized in that the step
In rapid A in metal ion salt solution metal ion a concentration of 1mg/mL~10mg/mL.
6. a kind of preparation method of porous-polynanofilm material according to claim 1, which is characterized in that the step
Metal ion and organic ligand reaction time are 20min~80min in rapid A.
7. a kind of preparation method of porous-polynanofilm material according to claim 1, which is characterized in that the step
LB film build methods, which are liquid level, in rapid A reduces method, horizontal film forming hair or vertical membrane formation process.
8. a kind of preparation method of porous-polynanofilm material according to claim 1, which is characterized in that the step
Conducting polymer monomer is any one in thiophene, pyrroles and aniline or a variety of in rapid B, the conducting polymer monomer it is dense
Degree is 50~100ppm.
9. a kind of preparation method of porous-polynanofilm material according to claim 1, which is characterized in that the step
Oxidant includes ferric trichloride, toluenesulfonic acid iron or ammonium persulfate in rapid B, the oxidant a concentration of 200~
400ppm。
10. a kind of preparation method of porous-polynanofilm material according to claim 1, which is characterized in that described
The response parameter of chemical gaseous phase polymerisation is in step B：50 DEG C~100 DEG C of reaction temperature, reaction pressure be 0.02~
0.08MPa, reaction time 10min~40min.
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