CN108467502B - Preparation method of porous composite nano film material - Google Patents
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Abstract
A preparation method of a porous composite nano film material belongs to the technical field of film materials. The preparation method adopts a step-by-step method to prepare the composite nano film, firstly, the ultrathin film is prepared on a substrate based on an LB film forming method, and as the organic ligand is assembled in a monomolecular layer form in the spreading process of a gas-liquid interface, the ultrathin film can be assembled into a monomolecular layer-level ultrathin film with an ordered nano structure after the molecules of the organic ligand are compressed, so that the MOFs film with a porous structure is obtained after the reaction with metal ions; and then placing the ultrathin porous MOFs film in the atmosphere of a gas-phase conductive polymer monomer and a gas-phase oxidant, and adopting an all-gas-phase polymerization mode, wherein the oxidant molecules induce the monomer molecules to polymerize in a collision polymerization mode in the reaction process, so that the ultrathin conductive polymer is continuously deposited on the MOFs intrinsic structure by controlling the oxidant and the monomer atmosphere, and the porous structure of the MOFs is not damaged while the conductivity of the MOFs is effectively improved.
Description
Technical Field
The invention belongs to the technical field of film materials, and particularly relates to a preparation method of a porous composite nano film material.
Background
Metal-organic frameworks (MOFs) are materials with a porous network framework structure formed by coordination of metal ions and organic ligands. The structure of the MOFs is a crystalline material composed of metal cations and organic electron donors connected by classical coordination bonds, the self-assembled pores of which are very strong in solution, have a certain mechanical strength, and due to the simultaneous presence of inorganic and organic components, it is possible to tailor the size of the holes and chemical exchange to achieve specific functions. The topological structure of the MOFs is closely related to the metal ion coordination environment and the geometric structure formed by organic connection, and different from the traditional microporous structure inorganic matter, the characteristics distinguish the MOFs from other types of porous materials, so that the MOFs have extremely important application values in numerous fields such as electrochemistry, catalysis, separation, photovoltaics, sensing and the like.
In recent years, porous MOFs and derivatives are gradually applied to the field of electrochemical energy storage, such as lithium ion batteries, fuel cells, supercapacitors and the like. A large number of researches show that the super capacitor based on the MOFs as the electrode has extremely high specific capacity due to the abundant mesoporous structure and the active sites with high surface exposure; meanwhile, different MOFs structures are synthesized by selecting different metal salts and organic ligands, and the capacity characteristic and stability of the electrode can be improved by regulating and controlling a charge transmission path. Therefore, the MOFs can be used as a base material to construct an electrode material with high specific surface area and rich active sites, and the energy storage efficiency of the energy storage material is effectively improved. However, the energy level matching between the organic ligand and the metal node is poor due to the generally wide forbidden band width (>3eV) of the organic ligand in the MOFs, and then the carrier delocalization capability in the MOFs material is weak, and the macroscopic appearance is poor in conductivity. At present, the poor conductivity of the MOFs not only becomes the first problem of inhibiting the improvement of the electrical and electrochemical energy storage performance of the MOFs, but also greatly limits the practical application of the MOFs in the fields of electrons and electrochemical energy storage devices. Therefore, how to solve the problem of low conductivity of the MOFs material becomes a key to ensure the rapid development of the MOFs material in the fields of electrons and electrochemical energy storage.
Currently, there are two methods for improving the conductivity of MOFs materials in the prior art: the first method is realized by adjusting the energy level matching of the organic ligand and the metal ions, and the method needs to be regulated and controlled from a molecular structure and finds proper metal ions for matching, so that the difficulty is very high; another is to use a material with better conductivity (such as conductive polymer) to compound with the MOFs, and this method improves the conductivity of the whole material by continuously depositing the conductive polymer in the porous structure. In the industry, hydrothermal synthesis, liquid-phase in-situ synthesis and other methods are usually selected to realize the compounding of two materials, namely conductive polymer and MOFs. However, these methods can destroy the porous structure of the MOFs material, and further cause the pore size and distribution of the composite porous material to be uncontrollable, and adjusting the dimension of the pores to further control the relative adsorption rate and the pore passage rate is an important basis for constructing the application thereof. Therefore, how to ensure the intrinsic structure of the MOFs without destroying the porous structure thereof while effectively improving the overall conductivity of the material by modifying the MOFs material with a conductive material becomes a technical problem to be solved in the field.
Disclosure of Invention
The invention aims to: aiming at the problem that the dimension of the pores of the prepared composite material is uncontrollable due to the damage of the MOFs intrinsic structure in the method for modifying the MOFs material by adopting a conductive material in the prior art, the preparation method of the porous composite nano-film material is provided, and the method can ensure that the MOFs intrinsic structure is not damaged, so that the purpose of controllably adjusting the pores of the composite material is achieved.
In order to achieve the above purpose, the invention provides the following technical scheme:
the preparation method of the porous composite nano film material is characterized by comprising the following steps:
step A: spreading an organic ligand molecular layer on a gas-liquid interface formed by water and air, and pressurizing to a solid-phase membrane pressure; then adding metal ion salt into the water phase, so that the metal ion salt is mixed in the water to form a metal ion salt solution, the metal ions react with the organic ligand to generate a molecular layer level porous metal organic framework film, and the porous metal organic framework film is transferred and deposited on the surface of the substrate;
and B: and D, placing the substrate deposited with the porous metal organic framework obtained in the step A in a mixed atmosphere formed by a gas-phase conductive polymer monomer and a gas-phase oxidant for carrying out chemical gas-phase polymerization reaction, so that the conductive polymer is deposited on the porous metal organic framework film to form the porous composite nano film material.
Further, the organic ligand in step a is any organic ligand molecule capable of forming a monolayer film at a gas-liquid interface and chemically reacting with a metal ion, including but not limited to: pyromellitic acid and its formic acid derivative, trimesic acid and its formic acid derivative, 2, 6-naphthalenedicarboxylic acid and its formic acid derivative, and 2,2 '-bipyridine-4, 4' -dicarboxylic acid and its formic acid derivative.
Further, the metal ions in step a include ions formed by transition metal elements, specifically including, but not limited to, any one or more of iron ions, manganese ions, and zinc ions.
Further, the concentration of the metal ions in the metal ion salt solution in the step A is 1 mg/mL-10 mg/mL.
Further, the reaction time of the metal ions and the organic ligand in the step A is 20 min-80 min.
Further, the LB film forming method in the step a is a liquid level lowering method, a horizontal film forming method, or a vertical film forming method.
Further, the conductive polymer monomer in the step B is any one or more of thiophene, pyrrole and aniline.
Further, the concentration of the gas-phase conductive polymer monomer in the step B is 50-100 ppm. Further, the oxidant in step B includes, but is not limited to, iron trichloride, iron methylbenzenesulfonate or ammonium persulfate.
Further, the concentration of the gas-phase oxidant in the step B is 200-400 ppm.
Further, the reaction parameters of the chemical gas phase polymerization reaction in the step B are as follows: the reaction temperature is 50-100 ℃, the reaction pressure is 0.02-0.08 MPa, and the reaction time is 10-40 min.
The principle of the invention is as follows: preparing a composite nano film by adopting a step method, firstly preparing an ultrathin film on a substrate based on an LB film forming method, assembling an organic ligand in a monomolecular layer form in the spreading process of a gas-liquid interface, and compressing organic ligand molecules to assemble the ultrathin film into the monomolecular layer-level ultrathin film with an ordered nano structure, so that the MOFs ultrathin film with the monomolecular layer-level porous structure is obtained after the ultrathin film reacts with metal ions; and then placing the porous MOFs ultrathin film in the atmosphere of a gas-phase conductive polymer monomer and a gas-phase oxidant, adopting an all-gas-phase polymerization mode, inducing the monomer molecules to polymerize by the oxidant molecules in a collision polymerization mode in the reaction process, and controlling the oxidant and the monomer atmosphere to enable the ultrathin conductive polymer to be continuously deposited on the MOFs intrinsic structure, thereby ensuring that the conductivity of the MOFs is effectively improved and the porous structure of the MOFs is not damaged.
The invention has the beneficial effects that:
(1) the preparation method can accurately regulate and control the MOFs and the conductive polymer to form the pore structure of the composite material, effectively improve the conductive property, maintain the intrinsic structure of the MOFs and be beneficial to ensuring the performance stability of the MOFs.
(2) The preparation method can obtain the large-area porous nano film with orderly arranged MOFs molecules, is beneficial to the migration of current carriers from the structural characteristics, and is more beneficial to improving the conductive property of the composite material compared with the traditional composite material formed by the MOFs and the conductive polymer.
(3) The preparation method provided by the invention has controllable operation, is green and environment-friendly, is suitable for industrial production,
Detailed Description
The following detailed description of specific embodiments is provided to explain the principles of the invention and its practical application to thereby enable others skilled in the art to understand the invention for various embodiments and with various modifications as are suited to the particular use contemplated.
The invention aims to provide a preparation method of a porous composite nano-film material, which adopts step-by-step preparation of an MOFs ultrathin film and a conductive polymer ultrathin film, so that a conductive polymer monomer is deposited on the monomolecular-layer-level MOFs ultrathin film obtained by an LB film-forming method under the induction of an oxidant, and an ultrathin conductive polymer layer is formed on the surface of an MOFs intrinsic structure, thereby avoiding the problem of porous structure damage caused by modification of the MOFs material by using a conductive polymer material based on traditional hydrothermal synthesis or liquid-phase in-situ synthesis.
Example 1:
a preparation method of a porous composite nano film material specifically comprises the following operations:
step 1:
taking 1 sample bottle with the volume of 30mL, cleaning with a cleaning agent, washing with running water, sequentially placing into ethanol and deionized water, respectively ultrasonically cleaning for 15 minutes, and then drying with nitrogen for later use;
step 2:
in this embodiment, dimethylformamide is used as a solvent to dissolve trimesic acid, and according to the general knowledge in the art, the solvent is not limited to one of the embodiments, and the invention is not limited thereto, and can be specifically selected according to the actual conditions;
dissolving 125mg of trimesic acid in 49.3mL of dimethylformamide to prepare a solution with a total volume of 50mL, wherein the concentration of the trimesic acid in the solution is 2.5mg/mL, and adding the solution into a sample bottle for ultrasonic dispersion for 3 hours to obtain a trimesic acid dispersion solution for later use;
and step 3:
dissolving 22.5mg of ferric nitrate in 47.5mL of excess water to prepare a ferric nitrate solution with a total volume of 50mL, wherein the concentration of ferric nitrate in the solution is 4.5mg/mL, and adding the solution into a sample bottle for ultrasonic dispersion for 3 hours to obtain a ferric nitrate salt dispersion solution for later use;
and 4, step 4:
measuring 10mL of the solution prepared in the step 2 by using a microsyringe, dropwise adding the solution on the surface of ultrapure water in an LB (Langmuir-Blodgett) film tank, and assembling the organic ligand in a monomolecular manner in the spreading process of a gas-liquid interface after the solvent is volatilized for 30 minutes; moving the sliding barrier to compress the Langmuir membrane to a certain solid phase membrane pressure (35-40 mN/m), continuously oscillating for 30 minutes, and compressing organic ligand molecules to form an ultrathin membrane;
and 5:
measuring 30mL of the solution prepared in the step 3 by using a microsyringe, dropwise adding the solution into ultrapure water in an LB (Langmuir-Blodgett) membrane tank, reacting trimesic acid with iron ions to obtain a porous structure, wherein the reaction time is 40 minutes, and at the moment, the gas-liquid interface ultrathin membrane is still maintained at the monomolecular level; depositing the MOFs ultrathin film obtained by the reaction on the surface of a substrate by adopting a liquid level descent method, wherein the liquid level descent method is to adsorb the MOFs ultrathin film on the surface of the substrate and then deposit the MOFs ultrathin film on the surface of the substrate by adopting a liquid level descent method, and the thickness of the surface of the substrate is basically the thickness of organic ligand molecules when the organic ligand molecules are spread;
step 6:
and (2) placing the substrate deposited with the ferric trimesate MOFs ultrathin film in a closed environment of thiophene and ferric trichloride atmosphere for chemical vapor polymerization deposition, wherein the air pressure in the closed environment is 0.04MPa, the polymerization temperature is 60 ℃, the oxidant molecules induce monomer molecules to polymerize in a collision polymerization mode, and the polymerization time is 15 minutes, so that the porous ferric trimesate MOFs material modified by polythiophene is finally prepared.
Example 2:
a preparation method of a porous composite nano film material specifically comprises the following operations:
step 1:
taking 1 sample bottle with the volume of 30mL, cleaning with a cleaning agent, washing with running water, sequentially placing into ethanol and deionized water, respectively ultrasonically cleaning for 15 minutes, and then drying with nitrogen for later use;
step 2:
in this embodiment, dimethylformamide is used as a solvent to dissolve trimesic acid, and according to the general knowledge in the art, the solvent is not limited to one of the embodiments, and the invention is not limited thereto, and can be specifically selected according to the actual conditions;
dissolving 75mg of trimesic acid in 49.8mL of dimethylformamide to prepare a solution with a total volume of 50mL, wherein the concentration of the trimesic acid in the solution is 1.5mg/mL, and adding the solution into a sample bottle for ultrasonic dispersion for 3 hours to obtain a trimesic acid dispersion solution for later use;
and step 3:
dissolving 175mg of ferric nitrate in 45.3mL of excess water to prepare a ferric nitrate solution with a total volume of 50mL, wherein the concentration of the ferric nitrate in the solution is 3.5mg/mL, and adding the solution into a sample bottle for ultrasonic dispersion for 3 hours to obtain a ferric nitrate salt dispersion liquid for later use;
and 4, step 4:
measuring 10mL of the solution prepared in the step 2 by using a microsyringe, dropwise adding the solution on the surface of ultrapure water in an LB (Langmuir-Blodgett) film tank, and assembling the organic ligand in a monomolecular manner in the spreading process of a gas-liquid interface after the solvent is volatilized for 30 minutes; moving the sliding barrier to compress the Langmuir membrane to a certain solid phase membrane pressure (35-40 mN/m), continuously oscillating for 30 minutes, and compressing organic ligand molecules to form an ultrathin membrane;
and 5:
measuring 30mL of the solution prepared in the step 3 by using a microsyringe, dropwise adding the solution into ultrapure water in an LB (Langmuir-Blodgett) membrane tank, reacting trimesic acid with iron ions to obtain a porous structure, wherein the reaction time is 60 minutes, and at the moment, the gas-liquid interface ultrathin membrane is still maintained at the monomolecular level; depositing the MOFs ultrathin film obtained by the reaction on the surface of a substrate by adopting a liquid level descent method, wherein the liquid level descent method is to adsorb the MOFs ultrathin film on the surface of the substrate and then deposit the MOFs ultrathin film on the surface of the substrate by adopting a liquid level descent method, and the thickness of the surface of the substrate is basically the thickness of organic ligand molecules when the organic ligand molecules are spread;
step 6:
and (2) placing the substrate deposited with the ferric trimesate MOFs ultrathin film in a closed environment of 3, 4-ethylenedioxythiophene and ferric trichloride atmosphere for chemical vapor polymerization deposition, wherein the air pressure in the closed environment is 0.05MPa, the polymerization temperature is 50 ℃, oxidant molecules induce monomer molecules to polymerize in a collision polymerization mode, and the polymerization time is 30 minutes, so that the porous ferric trimesate MOFs material modified by the poly-3, 4-ethylenedioxythiophene is finally prepared.
Example 3:
a preparation method of a porous composite nano film material specifically comprises the following operations:
step 1:
taking 1 sample bottle with the volume of 30mL, cleaning with a cleaning agent, washing with running water, sequentially placing into ethanol and deionized water, respectively ultrasonically cleaning for 15 minutes, and then drying with nitrogen for later use;
step 2:
in this embodiment, dimethylformamide is used as a solvent to dissolve trimesic acid, and according to the general knowledge in the art, the solvent is not limited to one of the embodiments, and the invention is not limited thereto, and can be specifically selected according to the actual conditions;
dissolving 200mg of trimesic acid in 48.6mL of dimethylformamide to prepare a solution with a total volume of 50mL, wherein the concentration of the trimesic acid in the solution is 4.0mg/mL, and adding the solution into a sample bottle for ultrasonic dispersion for 3 hours to obtain a trimesic acid dispersion solution for later use;
and step 3:
dissolving 325mg of ferric nitrate in 42.7mL of excess water to prepare a ferric nitrate solution with a total volume of 50mL, wherein the concentration of the ferric nitrate in the solution is 6.5mg/mL, and adding the solution into a sample bottle for ultrasonic dispersion for 3 hours to obtain a ferric nitrate salt dispersion liquid for later use;
and 4, step 4:
measuring 10mL of the solution prepared in the step 2 by using a microsyringe, dropwise adding the solution on the surface of ultrapure water in an LB (Langmuir-Blodgett) film tank, and assembling the organic ligand in a monomolecular manner in the spreading process of a gas-liquid interface after the solvent is volatilized for 30 minutes; moving the sliding barrier to compress the Langmuir membrane to a certain solid phase membrane pressure (35-40 mN/m), continuously oscillating for 30 minutes, and compressing organic ligand molecules to form an ultrathin membrane;
and 5:
measuring 30mL of the solution prepared in the step 3 by using a microsyringe, dropwise adding the solution into ultrapure water in an LB (Langmuir-Blodgett) membrane tank, reacting trimesic acid with iron ions to obtain a porous structure, wherein the reaction time is 80 minutes, and at the moment, the gas-liquid interface ultrathin membrane is still maintained at the monomolecular level; depositing the MOFs ultrathin film obtained by the reaction on the surface of a substrate by adopting a liquid level descent method, wherein the liquid level descent method is to adsorb the MOFs ultrathin film on the surface of the substrate and then deposit the MOFs ultrathin film on the surface of the substrate by adopting a liquid level descent method, and the thickness of the surface of the substrate is basically the thickness of organic ligand molecules when the organic ligand molecules are spread;
step 6:
and (2) placing the substrate deposited with the ferric-trimesate MOFs ultrathin film in a closed environment with pyrrole and ammonium persulfate atmosphere for chemical vapor polymerization deposition, wherein the air pressure in the closed environment is 0.02MPa, the polymerization temperature is 70 ℃, the oxidant molecules induce monomer molecules to polymerize in a collision polymerization mode, and the polymerization time is 20 minutes, so that the polypyrrole-modified porous ferric-trimesate MOFs material is finally prepared.
Example 4:
a preparation method of a porous composite nano film material specifically comprises the following operations:
step 1:
taking 1 sample bottle with the volume of 30mL, cleaning with a cleaning agent, washing with running water, sequentially placing into ethanol and deionized water, respectively ultrasonically cleaning for 15 minutes, and then drying with nitrogen for later use;
step 2:
in this embodiment, dimethylformamide is used as a solvent to dissolve the isophthalic acid, and according to the general knowledge in the art, the solvent is not limited to one of the embodiments, and the invention is not limited thereto, and can be specifically selected according to the actual situation;
dissolving 300mg of trimesic acid in 47.3mL of dimethylformamide to prepare a solution with a total volume of 50mL, wherein the concentration of the pyromellitic acid in the solution is 6.0mg/mL, and adding the solution into a sample bottle for ultrasonic dispersion for 3 hours to obtain a pyromellitic acid dispersion solution for later use;
and step 3:
dissolving 475mg of ferric nitrate in 38.9mL of ultra-pure water to prepare a ferric nitrate solution with a total volume of 50mL, respectively measuring ferric nitrate and ultra-pure water to prepare a solution with a total volume of 50mL, so that the concentration of ferric nitrate in the solution is 9.5mg/mL, adding the solution into a sample bottle, and performing ultrasonic dispersion for 3 hours to obtain a ferric nitrate salt dispersion liquid for later use;
and 4, step 4:
measuring 10mL of the solution prepared in the step 2 by using a microsyringe, dropwise adding the solution on the surface of ultrapure water in an LB (Langmuir-Blodgett) film tank, and assembling the organic ligand in a monomolecular manner in the spreading process of a gas-liquid interface after the solvent is volatilized for 30 minutes; moving the sliding barrier to compress the Langmuir to a certain solid phase film pressure (35-40 mN/m), continuously oscillating for 30 minutes, and compressing organic ligand molecules to form an ultrathin film;
and 5:
measuring 30mL of the solution prepared in the step 3 by using a microsyringe, dropwise adding the solution into ultrapure water in an LB (Langmuir-Blodgett) membrane tank, reacting the pyromellitic acid with iron ions to obtain a porous structure, wherein the reaction time is 50 minutes, and at the moment, the gas-liquid interface ultrathin membrane is still maintained at the monomolecular level; depositing the MOFs ultrathin film obtained by the reaction on the surface of a substrate by adopting a liquid level descent method, wherein the liquid level descent method is to adsorb the MOFs ultrathin film on the surface of the substrate and then deposit the MOFs ultrathin film on the surface of the substrate by adopting a liquid level reduction method, and the thickness of the surface of the substrate is basically the thickness of organic ligand molecules when the organic ligand molecules are spread;
step 6:
and (2) placing the substrate deposited with the ferric-pyromellitic-phthalate MOFs ultrathin film in a closed environment of thiophene and ferric trichloride atmosphere for chemical vapor polymerization deposition, wherein the air pressure in the closed environment is 0.08MPa, the polymerization temperature is 60 ℃, the oxidant molecules induce monomer molecules to polymerize in a collision polymerization mode, and the polymerization time is 30 minutes, so that the porous ferric-pyromellitic-phthalate MOFs material modified by polythiophene is finally prepared.
Example 5:
a preparation method of a porous composite nano film material specifically comprises the following operations:
step 1:
taking 1 sample bottle with the volume of 30mL, cleaning with a cleaning agent, washing with running water, sequentially placing into ethanol and deionized water, respectively ultrasonically cleaning for 15 minutes, and then drying with nitrogen for later use;
step 2:
in this embodiment, dimethylformamide is used as a solvent to dissolve the isophthalic acid, and according to the general knowledge in the art, the solvent is not limited to one of the embodiments, and the invention is not limited thereto, and can be specifically selected according to the actual situation;
dissolving 300mg of trimesic acid in 47.3mL of dimethylformamide to prepare a solution with a total volume of 50mL, adding the solution into a sample bottle, and performing ultrasonic dispersion for 3 hours to obtain a phthalic acid dispersion solution for later use;
and step 3:
dissolving 150mg of manganese nitrate in 48.2mL of ultrapure water to prepare a solution with a total volume of 50mL, wherein the concentration of the manganese nitrate in the solution is 3.0mg/mL, and adding the solution into a sample bottle for ultrasonic dispersion for 3 hours to obtain a manganese nitrate salt dispersion liquid for later use;
and 4, step 4:
measuring 10mL of the solution prepared in the step 2 by using a microsyringe, dropwise adding the solution on the surface of ultrapure water in an LB (Langmuir-Blodgett) film tank, and assembling the organic ligand in a monomolecular manner in the spreading process of a gas-liquid interface after the solvent is volatilized for 30 minutes; moving the sliding barrier to compress the Langmuir to a certain solid phase film pressure (35-40 mN/m), continuously oscillating for 30 minutes, and compressing organic ligand molecules to form an ultrathin film;
and 5:
measuring 30mL of the solution prepared in the step 3 by using a microsyringe, dropwise adding the solution into ultrapure water in an LB (Langmuir-Blodgett) membrane tank, reacting the pyromellitic acid with manganese ions to obtain a porous structure, wherein the reaction time is 70 minutes, and at the moment, the gas-liquid interface ultrathin membrane is still maintained at the monomolecular level; depositing the MOFs ultrathin film obtained by the reaction on the surface of a substrate by adopting a liquid level descent method, specifically, adsorbing the MOFs ultrathin film on the surface of the substrate by adopting the liquid level descent method, and depositing the MOFs ultrathin film on the surface of the substrate by adopting a liquid level descent method, wherein the thickness of the surface of the substrate is basically the thickness of organic ligand molecules when the molecules are spread;
step 6:
and (2) placing the substrate deposited with the manganese pyromellitate MOFs ultrathin film in a closed environment of thiophene and manganese trichloride atmosphere for chemical vapor polymerization deposition, wherein the air pressure in the closed environment is 0.07MPa, the polymerization temperature is 80 ℃, the oxidant molecules induce monomer molecules to polymerize in a collision polymerization mode, and the polymerization time is 25 minutes, so that the polythiophene-modified porous manganese pyromellitate MOFs material is finally prepared.
Example 6:
a preparation method of a porous composite nano film material specifically comprises the following operations:
step 1:
taking 1 sample bottle with the volume of 30mL, cleaning with a cleaning agent, washing with running water, sequentially placing into ethanol and deionized water, respectively ultrasonically cleaning for 15 minutes, and then drying with nitrogen for later use;
step 2:
in this embodiment, dimethylformamide is used as a solvent to dissolve 2, 6-naphthalenedicarboxylic acid, and according to the general knowledge in the art, the solvent is not limited to one of the embodiments, but the invention is not limited thereto and can be specifically selected according to the actual conditions;
dissolving 125mg of 2, 6-naphthalenedicarboxylic acid in 46.9mL of dimethylformamide to prepare a solution with a total volume of 50mL, wherein the concentration of 2, 6-naphthalenedicarboxylic acid in the solution is 2.5mg/mL, adding the solution into a sample bottle, and performing ultrasonic dispersion for 3 hours to obtain a 2, 6-naphthalenedicarboxylic acid dispersion liquid for later use;
and step 3:
dissolving 22.5mg of ferric nitrate in 47.5mL of excess water to prepare a ferric nitrate solution with a total volume of 50mL, wherein the concentration of ferric nitrate in the solution is 4.5mg/mL, and adding the solution into a sample bottle for ultrasonic dispersion for 3 hours to obtain a ferric nitrate salt dispersion solution for later use;
and 4, step 4:
measuring 10mL of the solution prepared in the step 2 by using a microsyringe, dropwise adding the solution on the surface of ultrapure water in an LB (Langmuir-Blodgett) film tank, and assembling the organic ligand in a monomolecular manner in the spreading process of a gas-liquid interface after the solvent is volatilized for 30 minutes; moving the sliding barrier to compress the Langmuir 2, 6-naphthalene dicarboxylic acid film to a certain solid phase film pressure (35-40 mN/m), continuously oscillating for 30 minutes, and compressing organic ligand molecules to form an ultrathin film;
and 5:
measuring 30mL of the solution prepared in the step 3 by using a microsyringe, dropwise adding the solution into ultrapure water in an LB (Langmuir-Blodgett) membrane tank, reacting 2, 6-naphthalene dicarboxylic acid with iron ions to obtain a porous structure, wherein the reaction time is 40 minutes, and at the moment, the gas-liquid interface ultrathin membrane is still maintained at the monomolecular level; depositing the 2, 6-naphthalene dicarboxylic acid iron MOFs ultrathin film obtained by reaction on the surface of a substrate by adopting a liquid level descent method, specifically, adsorbing the MOFs ultrathin film on the surface of the substrate by adopting the liquid level descent method, and depositing the MOFs ultrathin film on the surface of the substrate by adopting a liquid level descent method, wherein the thickness of the surface of the substrate is basically the thickness of organic ligand molecules when the organic ligand molecules are spread;
step 6:
and (2) placing the substrate deposited with the 2, 6-naphthalene dicarboxylic acid iron MOFs ultrathin film in a closed environment of thiophene and ferric trichloride atmosphere for chemical vapor polymerization deposition, wherein the air pressure in the closed environment is 0.06MPa, the polymerization temperature is 60 ℃, oxidant molecules induce monomer molecules to polymerize in a collision polymerization mode, and the polymerization time is 15 minutes, so that the polythiophene modified porous 2, 6-naphthalene dicarboxylic acid iron MOFs material is finally prepared.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. The preparation method of the porous composite nano film material is characterized by comprising the following steps:
step A: spreading an organic ligand molecular layer on a gas-liquid interface formed by water and air, and pressurizing to a solid-phase membrane pressure; then adding metal ion salt into the water phase, so that the metal ion salt is mixed in the water to form a metal ion salt solution, the metal ions react with the organic ligand to generate a molecular layer level porous metal organic framework film, and the porous metal organic framework film is transferred and deposited on the surface of the substrate;
and B: and D, placing the substrate deposited with the porous metal organic framework obtained in the step A in a mixed atmosphere formed by a gas-phase conductive polymer monomer and a gas-phase oxidant for carrying out chemical gas-phase polymerization reaction, so that the conductive polymer is deposited on the porous metal organic framework film to form the porous composite nano film material.
2. The method according to claim 1, wherein the organic ligand in step a is any organic ligand molecule capable of forming a monolayer film on a gas-liquid interface and chemically reacting with metal ions.
3. The method as claimed in claim 1, wherein the organic ligand in step a comprises pyromellitic acid and its formic acid derivative, trimesic acid and its formic acid derivative, 2, 6-naphthalene dicarboxylic acid and its formic acid derivative, and 2,2 '-bipyridine-4, 4' -dicarboxylic acid and its formic acid derivative.
4. The method according to claim 1, wherein the metal ions in step a include ions formed from transition metal elements.
5. The method for preparing a porous composite nano film material according to claim 1, wherein the concentration of the metal ions in the metal ion salt solution in the step A is 1 mg/mL-10 mg/mL.
6. The method for preparing a porous composite nano film material according to claim 1, wherein the reaction time of the metal ions and the organic ligands in the step A is 20-80 min.
7. The method for preparing a porous composite nano thin film material according to claim 1, wherein the LB film forming method in the step A is a liquid level lowering method, a horizontal film forming method or a vertical film forming method.
8. The method for preparing a porous composite nano thin film material according to claim 1, wherein the conductive polymer monomer in the step B is any one or more of thiophene, pyrrole and aniline, and the concentration of the conductive polymer monomer is 50-100 ppm.
9. The method for preparing a porous composite nano thin film material according to claim 1, wherein an oxidant in the step B comprises ferric trichloride, ferric methyl benzene sulfonate or ammonium persulfate, and the concentration of the oxidant is 200-400 ppm.
10. The method for preparing a porous composite nano thin film material according to claim 1, wherein the reaction parameters of the chemical vapor phase polymerization reaction in the step B are as follows: the reaction temperature is 50-100 ℃, the reaction pressure is 0.02-0.08 MPa, and the reaction time is 10-40 min.
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