CN109400937B - Preparation method of high-conductivity gas sensor material based on nano-fibers - Google Patents
Preparation method of high-conductivity gas sensor material based on nano-fibers Download PDFInfo
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Abstract
The invention discloses a preparation method of a high-conductivity gas sensor material based on nanofibers, and belongs to the technical field of sensing materials. The preparation method comprises the steps of sequentially and respectively adopting polydopamine and polyethyleneimine to carry out surface modification on a substrate material to prepare a modified substrate material, then growing metal organic framework nano fibers on the surface of the modified substrate material in situ, and carrying out high-temperature carbonization treatment to prepare the high-conductivity gas sensor material. The gas sensor material takes the polydopamine coating layer as a conducting layer through high-temperature carbonization on the basis of keeping the good three-dimensional network structure of the metal organic framework nanofiber, and the prepared material has the advantages of high sensitivity, high selectivity and high response speed.
Description
Technical Field
The invention relates to a gas sensor, belongs to the technical field of sensing materials, and particularly relates to a preparation method of a high-conductivity gas sensor material based on nanofibers.
Background
The electrochemical gas sensor is a material device which can convert information such as concentration, components and the like of gas into corresponding electric signals to realize sensing of different gas molecules, and has wide application in the fields of environmental monitoring, scientific research and the like.
At present, the stable, sensitive and high-selectivity sensing detection of a sensor on target gas can be realized by regulating and controlling the aperture structure and the surface chemical structure of a material. Oxides of metals such as zinc and tin have been used as key materials of gas sensors for a long time because of their excellent gas sensing properties due to their unique surface chemical properties. However, metal oxides generally do not have a porous structure, and the adsorption and enrichment effects of the materials prepared from the metal oxides on gas are not high enough, so that the sensing sensitivity and selectivity are reduced.
On the other hand, the metal organic framework material is a material which is formed by combining a rigid chain organic ligand and metal salt through a chemical bond and has a porous structure, the pore size of the material is adjustable, the specific surface area is large, the porosity is high, the permeation and the diffusion of gas molecules in the material are facilitated, the good pre-enrichment effect on low-concentration gas is realized, specific molecules can be selectively adsorbed, and the sensitivity and the selectivity of the sensor for detecting the low-concentration gas are further improved. Therefore, in recent years, metal organic framework materials have been increasingly used for gas sensing and detection. However, the metal organic framework material is usually in a granular form, and especially when the size of the metal organic framework material is in a nanometer level, the granules are easy to agglomerate and difficult to process, and the advantage of high specific surface area of the metal organic framework material is difficult to effectively exert. In addition, the response speed thereof has been difficult to reach the level of the conventional metal oxide at present.
In summary, the material structure design enables the metal organic framework material to have the advantages of high sensitivity and selectivity of the metal organic framework material to gas sensing, response speed of metal oxide and easiness in processing, and therefore the metal organic framework material has very important significance and great challenge.
Disclosure of Invention
In order to solve the technical problems, the invention provides a preparation method of a high-conductivity gas sensor material based on nano-fibers. According to the preparation method, the polydopamine coating is obtained through in-situ polymerization on the surface of the base material, and then cross-linked with PEI, the in-situ growth of the metal organic framework nanofiber on the surface of the base material is guaranteed, and the prepared gas sensor material has the advantages of high sensitivity, high selectivity and high corresponding speed for gas sensing.
In order to achieve the aim, the invention discloses a preparation method of a high-conductivity gas sensor material based on nanofibers, which comprises the steps of sequentially and respectively adopting polydopamine and polyethyleneimine to carry out surface modification on a base material to prepare a modified base material, then growing metal organic framework nanofibers on the surface of the modified base material in situ, and carrying out high-temperature carbonization treatment to prepare the high-conductivity gas sensor material.
Further, the process of surface modification of the base material is as follows:
cleaning and drying a base material, then placing the base material in a dopamine solution for treatment to obtain a polydopamine surface-modified base material, repeatedly washing the polydopamine surface-modified base material with deionized water, then placing the polydopamine surface-modified base material in a polyethyleneimine solution for treatment, taking out the polydopamine surface-modified base material, repeatedly washing with deionized water, drying to obtain a modified base material, and sealing and storing the modified base material.
Preferably, the dopamine solution is prepared by dissolving dopamine into a Tri-HCl buffer solution with a pH value of 8.5 (tris hydrochloride buffer solution).
Most preferably, the concentration of the dopamine solution is 20 g/L.
Most preferably, the concentration of the polyethyleneimine solution is 1 g/L.
Preferably, the temperature of the solution at the time of surface modification is controlled to 37 ℃.
Furthermore, the fiber diameter of the metal organic framework nano fiber is 50 nm-1 μm, and the fiber length is 5 μm-100 μm.
Further, the metal organic framework nanofiber is prepared from lanthanide metal salt and an organic ligand.
Further, the lanthanide metal salt includes a compound of one element or a mixture of two or more elements selected from Eu (europium), Gd (gadolinium), Tb (terbium), Sm (samarium), and Yb (ytterbium).
Further, the organic ligand comprises trimesic acid, citric acid, nitrilotriacetic acid, 2'; at least one of 6,2 "-bipyridine or diethylenetriamine.
Further, the process of in-situ growing the metal organic framework nanofiber on the surface of the modified base material is as follows:
and (2) treating the modified matrix material in a lanthanide metal salt solution for a period of time, taking out, washing with water, then placing in an organic ligand solution, reacting at room temperature or at elevated temperature, repeatedly washing with ethanol and deionized water, soaking in ethanol, taking out, and drying to obtain the matrix material with the surface in-situ grown metal-organic framework nanofibers.
Preferably, the water washing is also deionized water washing.
Preferably, the room-temperature reaction is a constant-temperature reaction at 20-30 ℃ for 24-72 hours.
Preferably, the temperature rise reaction is carried out for 6-24 hours at a constant temperature by slowly raising the temperature to 90-160 ℃ at a temperature rise speed of 10 ℃/min.
Preferably, the drying is carried out under vacuum condition, the temperature is controlled to be 100 ℃, and the optimal drying time is 3 h.
Preferably, the lanthanide metal salt solution is a solution prepared by placing a compound of one element or a mixture of two or more compounds of Eu, Gd, Tb, Sm or Yb in a mixed solvent composed of an organic solvent and water. Preferably, the volume ratio of the organic solvent to the water is 1: 23.
Preferably, the organic solvent is at least one of ethanol, tert-butanol or isopropanol.
Preferably, the concentration of the lanthanide metal salt solution is 0.02-0.1 mol/L.
Preferably, the organic ligand solution is trimesic acid, citric acid, nitrilotriacetic acid, 2'; at least one of 6, 2' -bipyridine or diethylenetriamine is placed in a mixed solvent composed of an organic solvent and water to prepare a solution. Preferably, the volume ratio of the organic solvent to the water is 2: 1.
Preferably, the organic solvent is at least one of ethanol, tert-butanol or isopropanol.
Preferably, the concentration of the organic ligand solution is 0.08-0.4 mol/L.
Further, the high-temperature carbonization treatment is to carbonize and pyrolyze the polydopamine into a graphene lamellar structure, wherein the graphene lamellar structure can form a high-conductivity layer.
Further, the conditions of the high-temperature carbonization treatment are as follows:
raising the temperature from room temperature to 800-1200 ℃ at the temperature raising rate of 20-50 ℃ in the nitrogen atmosphere, and keeping the temperature for 30-60 min.
Further, the base material is one of a polymer nanofiber self-supporting film, a polymer nanofiber/non-woven fabric coating composite film, an interdigital electrode, a metal net film or an inorganic non-metal net film.
Preferably, the polymer nanofiber self-supporting film is obtained by coating a polymer nanofiber suspension on a non-woven fabric substrate, drying and then stripping.
Preferably, the polymer nanofiber/non-woven fabric coating composite film is obtained by coating a polymer nanofiber suspension on a non-woven fabric substrate and drying. Preferably, the polymer nanofiber suspension is coated on the nonwoven fabric substrate using a high pressure air-flow forming technique.
Most preferably, the polymer nanofiber suspension is formed by dispersing polymer nanofibers prepared by melt blending phase separation in a solvent.
Most preferably, the polymer nanofiber is at least one of ethylene-vinyl alcohol copolymer, polyethylene terephthalate, polyethylene octene co-elastomer, nylon 6, polypropylene, polystyrene, polyvinyl chloride or polyvinylidene fluoride.
Preferably, the interdigital electrode is: ceramic, PET, alumina, aluminum nitride based gold electrodes; preferably, the inter-digital line spacing is 3-10 μm, and the inter-digital electrode metal layer thickness is 0.3-1 μm.
Preferably, the metal mesh film is: the net membrane is preferably made of stainless steel, aluminum and copper, wherein the net mesh length of the net membrane is 20-100 mu m, and the thickness of the metal net membrane is 10-200 mu m.
Preferably, the inorganic non-metallic net film is: the net film is preferably made of ceramic, aluminum oxide, aluminum nitride and carbon fiber, wherein the mesh size of the net film is 3-50 mu m, and the thickness of the inorganic non-metal net film is 7-200 mu m.
The invention also discloses a gas sensor material prepared by the preparation method, which comprises a base material, a polydopamine coating polymerized on the surface of the base material, polyethyleneimine crosslinked with the polydopamine coating, and metal organic framework nano fibers grown in situ on the surface of the base material, wherein the polydopamine coating is treated at high temperature to obtain a conductive layer, and the metal organic framework nano fibers form a three-dimensional network structure in space, so that the gas sensing performance of the material can be fully exerted.
The beneficial effects of the invention are mainly embodied as follows:
the preparation method provided by the invention realizes effective combination of the metal organic framework nanofiber and the polydopamine coating, and the polydopamine coating is carbonized into a conductive layer at high temperature on the basis of keeping a good three-dimensional network structure of the metal organic framework nanofiber, so that the prepared material has the advantages of high sensitivity, high selectivity and high response speed.
Drawings
FIG. 1 is a schematic structural diagram of a highly conductive gas sensor material according to the present invention;
wherein, each reference number in fig. 1 is as follows:
the graphene composite material comprises a metal organic framework nanofiber layer 1, a graphene conducting layer 2 and a base material 3.
Detailed Description
In order to better explain the invention, the following further illustrate the main content of the invention in connection with specific examples, but the content of the invention is not limited to the following examples.
Example 1
Carrying out ultrasonic treatment on the ethylene-vinyl alcohol copolymer nanofiber prepared by melting, blending and phase separation for 30min by using a 1mol/L NaOH solution, then washing the nanofiber by using deionized water, ethanol and deionized water in sequence, and then drying the nanofiber.
Preparing 20g/L of Dopamine (DA) solution, and dissolving the Dopamine (DA) in 100mL of tris (hydroxymethyl) aminomethane hydrochloride (Tri-HCl) buffer solution with the pH value of 8.5 in the preparation process, wherein the concentration of the Tri-HCl buffer solution is 10 mol/L.
And (3) putting the cleaned ethylene-vinyl alcohol copolymer nanofiber into a DA solution, oscillating for 24h at 37 ℃, repeatedly washing with deionized water after complete reaction to obtain the PDA surface modified substrate.
The PDA surface modified substrate is placed in 1g/L Polyethyleneimine (PEI) solution (aqueous solution, the same is applied below), oscillated for 3 hours at 37 ℃ and washed by deionized water to obtain the PEI-PDA surface modified substrate.
Soaking the PEI-PDA surface modified substrate in 0.02mol/L europium nitrate hexahydrate solution for treatment for 1h, taking out the substrate, washing the substrate with deionized water for 3 times, then placing the substrate in a reaction kettle containing 0.08mol/L trimesic acid solution, and reacting for 48h at 100 ℃ (the organic ligand and the solvent of the metal salt solution are both mixed solvents of alcohol and water, preferably the alcohol is ethanol) to obtain the membrane material. And taking out after the reaction is completed, repeatedly cleaning the membrane material for 3 times by using deionized water and ethanol, soaking the membrane material in the ethanol for 12 hours, taking out, and drying in vacuum for 3 hours to obtain the composite base material with the metal organic framework fibers growing on the surface. And controlling the temperature to be 800 ℃ under the protection of nitrogen, and carbonizing the composite base material with the metal organic framework fibers growing on the surface to obtain the nanofiber-based high-conductivity gas sensing device material.
As can be seen from fig. 1, the prepared gas sensor material includes a base material 3, a polydopamine coating polymerized on the surface of the base material 3, and polyethyleneimine crosslinked with the polydopamine coating, the polydopamine coating is carbonized at high temperature to form a graphene conductive layer 2, and porous metal oxide nanofibers are further grown in situ on the surface of the base material through the crosslinking effect of the polyethyleneimine to obtain a metal organic framework nanofiber layer 1, so that a three-dimensional network structure is formed in space, and the material with the structure can fully exert gas sensing performance.
Example 2
Carrying out ultrasonic treatment on polyethylene glycol terephthalate nano-fibers prepared by melt blending phase separation for 30min by using a 1mol/L NaOH solution, then washing the fibers by using deionized water, ethanol and deionized water in sequence, and then drying the fibers.
Preparing 20g/L of Dopamine (DA) solution, and dissolving the Dopamine (DA) in 100mL of tris (hydroxymethyl) aminomethane hydrochloride) (Tri-HCl) buffer solution with the pH value of 8.5 in the preparation process, wherein the concentration of the Tri-HCl buffer solution is 11 mol/L.
And (3) putting the cleaned polyethylene glycol terephthalate nano-fiber into a DA solution, oscillating for 24h at 37 ℃, repeatedly washing with deionized water after complete reaction to obtain the PDA surface modified substrate.
And (3) placing the PDA surface modified substrate in 1g/L Polyethyleneimine (PEI) solution, oscillating for 3h at 37 ℃, and washing with deionized water to obtain the PEI-PDA surface modified substrate.
Soaking the PEI-PDA surface modified substrate in 0.03mol/L gadolinium nitrate hexahydrate solution for treatment for 2h, taking out the PEI-PDA surface modified substrate, washing the PEI-PDA surface modified substrate with deionized water for 3 times, placing the PEI-PDA surface modified substrate in a reaction kettle containing 0.08mol/L citric acid solution, and reacting for 24h (the organic ligand and the metal salt solution are both mixed solvents of alcohol and water, preferably isopropanol) at 100 ℃ to obtain the membrane material. And taking out after the reaction is completed, repeatedly cleaning the membrane material for 3 times by using deionized water and ethanol, soaking the membrane material in the ethanol for 12 hours, taking out, and drying in vacuum for 3 hours to obtain the composite base material with the metal organic framework fibers growing on the surface. And controlling the temperature to be 850 ℃ under the protection of nitrogen, and carbonizing the composite base material with the metal organic framework fibers growing on the surface to obtain the nanofiber-based high-conductivity gas sensing device material.
Example 3
Carrying out ultrasonic treatment on the polyethylene octene co-elastomer nano-fiber prepared by melting, blending and phase separation for 30min by using a 1mol/L NaOH solution, then washing the nano-fiber by using deionized water, ethanol and deionized water in sequence, and then drying the washed nano-fiber.
Preparing 20g/L of Dopamine (DA) solution, and dissolving the Dopamine (DA) in 100mL of tris (hydroxymethyl) aminomethane hydrochloride) (Tri-HCl) buffer solution with the pH value of 8.5 in the preparation process, wherein the concentration of the Tri-HCl buffer solution is 12 mol/L.
And (3) putting the cleaned polyethylene octene co-elastomer nano-fiber into DA solution, oscillating for 24h at 37 ℃, and repeatedly washing with deionized water after complete reaction to obtain the PDA surface modified substrate.
And (3) placing the PDA surface modified substrate in 1g/L Polyethyleneimine (PEI) solution, oscillating for 3h at 37 ℃, and washing with deionized water to obtain the PEI-PDA surface modified substrate.
Soaking the PEI-PDA surface modified substrate in a terbium nitrate hexahydrate solution with the concentration of 0.05mol/L for treating for 1h, taking out the substrate, washing with deionized water for 4 times, placing the substrate in a reaction kettle containing a nitrilotriacetic acid solution with the concentration of 0.12mol/L, and reacting for 72h at 110 ℃ (the organic ligand and the solvent of the metal salt solution are both mixed solvents of alcohol and water, preferably the alcohol is ethanol) to obtain the membrane material. And taking out after the reaction is completed, repeatedly cleaning the membrane material for 3 times by using deionized water and ethanol, soaking the membrane material in the ethanol for 12 hours, taking out, and drying in vacuum for 3 hours to obtain the composite base material with the metal organic framework fibers growing on the surface. And controlling the temperature to be 900 ℃ under the protection of nitrogen, and carbonizing the composite base material with the metal organic framework fibers growing on the surface to obtain the nanofiber-based high-conductivity gas sensing device material.
Example 4
Carrying out ultrasonic treatment on nylon 6 nano-fibers prepared by melt blending phase separation for 30min by using a 1mol/L NaOH solution, then washing the nano-fibers by using deionized water, ethanol and deionized water in sequence, and then drying the washed nano-fibers.
Preparing 20g/L of Dopamine (DA) solution, and dissolving the Dopamine (DA) in 100mL of tris (hydroxymethyl) aminomethane hydrochloride) (Tri-HCl) buffer solution with the pH value of 8.5 in the preparation process, wherein the concentration of the Tri-HCl buffer solution is 13 mol/L.
And (3) putting the cleaned nylon 6 nano-fiber into a DA solution, oscillating for 24h at 37 ℃, and repeatedly washing with deionized water after complete reaction to obtain the PDA surface modified substrate.
And (3) placing the PDA surface modified substrate in 1g/L Polyethyleneimine (PEI) solution, oscillating for 3h at 37 ℃, and washing with deionized water to obtain the PEI-PDA surface modified substrate.
Soaking the PEI-PDA surface modified substrate in a samarium nitrate hexahydrate solution with the concentration of 0.05mol/L for treating for 1h, taking out the substrate, washing the substrate with deionized water for 5 times, and then placing the substrate in a solution containing 2,2' with the concentration of 0.14 mol/L; and (3) reacting the solution of 6, 2' -terpyridine in a reaction kettle at 90 ℃ for 24 hours (the organic ligand and the solvent of the metal salt solution are both mixed solvents of alcohol and water, and preferably, the alcohol is ethanol) to obtain the membrane material. And taking out after the reaction is completed, repeatedly cleaning the membrane material for 3 times by using deionized water and ethanol, soaking the membrane material in the ethanol for 12 hours, taking out, and drying in vacuum for 3 hours to obtain the composite base material with the metal organic framework fibers growing on the surface. And controlling the temperature to be 950 ℃ under the protection of nitrogen, and carbonizing the composite base material with the metal organic framework fibers grown on the surface to obtain the nanofiber-based high-conductivity gas sensing device material.
Example 5
And (2) carrying out ultrasonic treatment on the polypropylene nano-fiber prepared by melting, blending and phase separation for 30min by using a 1mol/L NaOH solution, then washing the polypropylene nano-fiber by using deionized water, ethanol and deionized water in sequence, and then drying the washed polypropylene nano-fiber.
Preparing 20g/L of Dopamine (DA) solution, and dissolving the Dopamine (DA) in 100mL of tris (hydroxymethyl) aminomethane hydrochloride) (Tri-HCl) buffer solution with the pH value of 8.5 in the preparation process, wherein the concentration of the Tri-HCl buffer solution is 14 mol/L.
And (3) putting the polypropylene nano fiber subjected to cleaning treatment into a DA solution, oscillating for 24h at 37 ℃, repeatedly washing with deionized water after complete reaction, and thus obtaining the PDA surface modified substrate.
And (3) placing the PDA surface modified substrate in 1g/L Polyethyleneimine (PEI) solution, oscillating for 3h at 37 ℃, and washing with deionized water to obtain the PEI-PDA surface modified substrate.
Soaking the PEI-PDA surface modified substrate in a 0.06mol/L ytterbium nitrate hexahydrate solution for treatment for 5h, taking out the substrate, washing the substrate with deionized water for 5 times, placing the substrate in a reaction kettle containing a 0.16mol/L diethylenetriamine solution, and reacting for 6h at 90 ℃ (the organic ligand and the solvent of the metal salt solution are both mixed solvents of alcohol and water, preferably ethanol) to obtain the membrane material. And taking out after the reaction is completed, repeatedly cleaning the membrane material for 3 times by using deionized water and ethanol, soaking the membrane material in the ethanol for 12 hours, taking out, and drying in vacuum for 3 hours to obtain the composite base material with the metal organic framework fibers growing on the surface. And controlling the temperature to be 1000 ℃ under the protection of nitrogen, and carbonizing the composite base material with the metal organic framework fibers growing on the surface to obtain the nanofiber-based high-conductivity gas sensing device material.
Example 6
And (2) carrying out ultrasonic treatment on the polystyrene nano-fiber prepared by melting, blending and phase separation for 30min by using a 1mol/L NaOH solution, then washing the polystyrene nano-fiber by using deionized water, ethanol and deionized water in sequence, and then drying the washed polystyrene nano-fiber.
Preparing 20g/L of Dopamine (DA) solution, and dissolving the Dopamine (DA) in 100mL of tris (hydroxymethyl) aminomethane hydrochloride (Tri-HCl) buffer solution with the pH value of 8.5 in the preparation process, wherein the concentration of the Tri-HCl buffer solution is 10 mol/L.
And (3) putting the cleaned ethylene-vinyl alcohol copolymer nanofiber into a DA solution, oscillating for 24h at 37 ℃, repeatedly washing with deionized water after complete reaction to obtain the PDA surface modified substrate.
And (3) placing the PDA surface modified substrate in 1g/L Polyethyleneimine (PEI) solution, oscillating for 3h at 37 ℃, and washing with deionized water to obtain the PEI-PDA surface modified substrate.
Soaking the PEI-PDA surface modified substrate in a ruthenium nitrate hexahydrate solution with the concentration of 0.07mol/L for treating for 1h, taking out the substrate, washing with deionized water for 3 times, then placing the substrate in a reaction kettle containing a 0.18mol/L trimesic acid solution, and reacting for 72h at 20 ℃ (the organic ligand and the solvent of the metal salt solution are both mixed solvents of alcohol and water, preferably the alcohol is ethanol) to obtain the membrane material. And taking out after the reaction is completed, repeatedly cleaning the membrane material for 3 times by using deionized water and ethanol, soaking the membrane material in the ethanol for 12 hours, taking out, and drying in vacuum for 3 hours to obtain the composite base material with the metal organic framework fibers growing on the surface. And controlling the temperature to 1050 ℃ under the protection of nitrogen, and carbonizing the composite base material with the metal organic framework fibers grown on the surface to obtain the nanofiber-based high-conductivity gas sensing device material.
Example 7
And (2) carrying out ultrasonic treatment on the polyvinyl chloride nano-fiber prepared by melting, blending and phase separation for 30min by using a 1mol/L NaOH solution, then washing the polyvinyl chloride nano-fiber by using deionized water, ethanol and deionized water in sequence, and then drying the polyvinyl chloride nano-fiber.
Preparing 20g/L of Dopamine (DA) solution, and dissolving the Dopamine (DA) in 100mL of tris (hydroxymethyl) aminomethane hydrochloride) (Tri-HCl) buffer solution with the pH value of 8.5 in the preparation process, wherein the concentration of the Tri-HCl buffer solution is 11 mol/L.
And (3) putting the cleaned ethylene-vinyl alcohol copolymer nanofiber into a DA solution, oscillating for 24h at 37 ℃, repeatedly washing with deionized water after complete reaction to obtain the PDA surface modified substrate.
And (3) placing the PDA surface modified substrate in 1g/L Polyethyleneimine (PEI) solution, oscillating for 3h at 37 ℃, and washing with deionized water to obtain the PEI-PDA surface modified substrate.
Soaking the PEI-PDA surface modified substrate in 0.08mol/L europium nitrate hexahydrate solution for treatment for 1h, taking out the substrate, washing the substrate with deionized water for 3 times, and then placing the substrate in a reaction kettle containing 0.10mol/L trimesic acid solution and 0.10mol/L nitrilotriacetic acid solution mixed solution for reaction for 6h at 90 ℃ (organic ligands and metal salt solution solvents are mixed solvents of alcohol and water, preferably alcohol is ethanol) to obtain the membrane material. And taking out after the reaction is completed, repeatedly cleaning the membrane material for 3 times by using deionized water and ethanol, soaking the membrane material in the ethanol for 12 hours, taking out, and drying in vacuum for 3 hours to obtain the composite base material with the metal organic framework fibers growing on the surface. And controlling the temperature to be 1100 ℃ under the protection of nitrogen, and carbonizing the composite base material with the metal organic framework fibers growing on the surface to obtain the nanofiber-based high-conductivity gas sensing device material.
Example 8
Carrying out ultrasonic treatment on the ethylene-vinyl alcohol copolymer nanofiber prepared by melting, blending and phase separation for 30min by using a 1mol/L NaOH solution, then washing the nanofiber by using deionized water, ethanol and deionized water in sequence, and then drying the nanofiber.
Preparing 20g/L of Dopamine (DA) solution, and dissolving the Dopamine (DA) in 100mL of tris (hydroxymethyl) aminomethane hydrochloride) (Tri-HCl) buffer solution with the pH value of 8.5 in the preparation process, wherein the concentration of the Tri-HCl buffer solution is 12 mol/L.
And (3) putting the cleaned ethylene-vinyl alcohol copolymer nanofiber into a DA solution, oscillating for 24h at 37 ℃, repeatedly washing with deionized water after complete reaction to obtain the PDA surface modified substrate.
And (3) placing the PDA surface modified substrate in 1g/L Polyethyleneimine (PEI) solution, oscillating for 3h at 37 ℃, and washing with deionized water to obtain the PEI-PDA surface modified substrate.
Soaking the PEI-PDA surface modified substrate in a 0.09mol/L gadolinium nitrate hexahydrate solution for treatment for 1h, taking out the substrate, washing the substrate with deionized water for 3 times, and then placing the substrate in a 0.11mol/L trimesic acid solution and 0.11 mol/L2, 2'; and (3) reacting the mixed solution of 6, 2' -terpyridine for 72 hours at 100 ℃ (the organic ligand and the solvent of the metal salt solution are both mixed solvents of alcohol and water, preferably ethanol) to obtain the membrane material. And taking out after the reaction is completed, repeatedly cleaning the membrane material for 3 times by using deionized water and ethanol, soaking the membrane material in the ethanol for 12 hours, taking out, and drying in vacuum for 3 hours to obtain the composite base material with the metal organic framework fibers growing on the surface. And controlling the temperature to 1150 ℃ under the protection of nitrogen, and carbonizing the composite base material with the metal organic framework fibers grown on the surface to obtain the nanofiber-based high-conductivity gas sensing device material.
Example 9
The polymer nanofiber self-supporting membrane (ethylene-vinyl alcohol copolymer) prepared by melt blending phase separation is subjected to ultrasonic treatment for 30min by using 1mol/L NaOH solution, and then is sequentially washed by deionized water, ethanol and deionized water and then is dried.
Preparing 20g/L of Dopamine (DA) solution, and dissolving the Dopamine (DA) in 100mL of tris (hydroxymethyl) aminomethane hydrochloride) (Tri-HCl) buffer solution with the pH value of 8.5 in the preparation process, wherein the concentration of the Tri-HCl buffer solution is 13 mol/L.
And (3) putting the cleaned ethylene-vinyl alcohol copolymer nanofiber into a DA solution, oscillating for 24h at 37 ℃, repeatedly washing with deionized water after complete reaction to obtain the PDA surface modified substrate.
And (3) placing the PDA surface modified substrate in 1g/L Polyethyleneimine (PEI) solution, oscillating for 3h at 37 ℃, and washing with deionized water to obtain the PEI-PDA surface modified substrate.
Soaking the PEI-PDA surface modified substrate in 0.10mol/L europium nitrate hexahydrate solution for treatment for 2h, taking out the substrate, washing the substrate with deionized water for 4 times, and then placing the substrate in a reaction kettle containing 0.13mol/L trimesic acid solution and 0.11mol/L diethylenetriamine solution mixed solution for reaction for 24h at 40 ℃ (organic ligands and metal salt solution solvents are mixed solvents of alcohol and water, preferably alcohol is ethanol) to obtain the membrane material. And taking out after the reaction is completed, repeatedly cleaning the membrane material for 3 times by using deionized water and ethanol, soaking the membrane material in the ethanol for 12 hours, taking out, and drying in vacuum for 3 hours to obtain the composite base material with the metal organic framework fibers growing on the surface. And controlling the temperature to be 1200 ℃ under the protection of nitrogen, and carbonizing the composite base material with the metal organic framework fibers growing on the surface to obtain the nanofiber-based high-conductivity gas sensing device material.
Example 10
Carrying out ultrasonic treatment on the interdigital electrode (ceramic) prepared by melting, blending and phase separation for 30min by using a 1mol/L NaOH solution, then washing the interdigital electrode (ceramic) by using deionized water, ethanol and deionized water in sequence, and then drying the interdigital electrode.
Preparing 20g/L of Dopamine (DA) solution, and dissolving the Dopamine (DA) in 100mL of tris (hydroxymethyl) aminomethane hydrochloride) (Tri-HCl) buffer solution with the pH value of 8.5 in the preparation process, wherein the concentration of the Tri-HCl buffer solution is 14 mol/L.
And (3) putting the cleaned ethylene-vinyl alcohol copolymer nanofiber into a DA solution, oscillating for 24h at 37 ℃, repeatedly washing with deionized water after complete reaction to obtain the PDA surface modified substrate.
And (3) placing the PDA surface modified substrate in 1g/L Polyethyleneimine (PEI) solution, oscillating for 3h at 37 ℃, and washing with deionized water to obtain the PEI-PDA surface modified substrate.
Soaking the PEI-PDA surface modified substrate in 0.26mol/L europium nitrate hexahydrate solution for treatment for 2h, taking out the substrate, washing the substrate with deionized water for 4 times, and then placing the substrate in 0.02mol/L trimesic acid solution and 0.03 mol/L2, 2'; and (3) reacting the mixed solution of the 6, 2' -bipyridine solution at 100 ℃ for 5 hours in a reaction kettle (the organic ligand and the solvent of the metal salt solution are both mixed solvents of alcohol and water, preferably ethanol) to obtain the membrane material. And taking out after the reaction is completed, repeatedly cleaning the membrane material for 3 times by using deionized water and ethanol, soaking the membrane material in the ethanol for 12 hours, taking out, and drying in vacuum for 3 hours to obtain the composite base material with the metal organic framework fibers growing on the surface. And controlling the temperature to be 800 ℃ under the protection of nitrogen, and carbonizing the composite base material with the metal organic framework fibers growing on the surface to obtain the nanofiber-based high-conductivity gas sensing device material.
Example 11
And (3) carrying out ultrasonic treatment on the metal net membrane prepared by melting, blending and phase separation for 30min by using 1mol/L NaOH solution, then washing the metal net membrane by using deionized water, ethanol and deionized water in sequence, and then drying the metal net membrane.
Preparing 20g/L of Dopamine (DA) solution, and dissolving the Dopamine (DA) in 100mL of tris (hydroxymethyl) aminomethane hydrochloride (Tri-HCl) buffer solution with the pH value of 8.5 in the preparation process, wherein the concentration of the Tri-HCl buffer solution is 10 mol/L.
And (3) putting the cleaned ethylene-vinyl alcohol copolymer nanofiber into a DA solution, oscillating for 24h at 37 ℃, repeatedly washing with deionized water after complete reaction to obtain the PDA surface modified substrate.
And (3) placing the PDA surface modified substrate in 1g/L Polyethyleneimine (PEI) solution, oscillating for 3h at 37 ℃, and washing with deionized water to obtain the PEI-PDA surface modified substrate.
Soaking the PEI-PDA surface modified base material in 0.28mol/L europium nitrate hexahydrate solution for treatment for 2h, taking out the base material, washing the base material with deionized water for 4 times, and then placing the base material in a reaction kettle containing 0.04mol/L citric acid solution and 0.03mol/L diethylenetriamine solution mixed solution to react for 48h at the temperature of 30 ℃ (organic ligands and solvents of metal salt solutions are mixed solvents of alcohol and water, preferably alcohol is ethanol) to obtain the membrane material. And taking out after the reaction is completed, repeatedly cleaning the membrane material for 3 times by using deionized water and ethanol, soaking the membrane material in the ethanol for 12 hours, taking out, and drying in vacuum for 3 hours to obtain the composite base material with the metal organic framework fibers growing on the surface. And controlling the temperature to be 900 ℃ under the protection of nitrogen, and carbonizing the composite base material with the metal organic framework fibers growing on the surface to obtain the nanofiber-based high-conductivity gas sensing device material.
Example 12
And (2) carrying out ultrasonic treatment on the inorganic non-metallic net film prepared by melting, blending and phase separation for 30min by using 1mol/L NaOH solution, then washing the inorganic non-metallic net film by using deionized water, ethanol and deionized water in sequence, and then drying the inorganic non-metallic net film.
Preparing 20g/L of Dopamine (DA) solution, and dissolving the Dopamine (DA) in 100mL of tris (hydroxymethyl) aminomethane hydrochloride) (Tri-HCl) buffer solution with the pH value of 8.5 in the preparation process, wherein the concentration of the Tri-HCl buffer solution is 13 mol/L.
And (3) putting the cleaned ethylene-vinyl alcohol copolymer nanofiber into a DA solution, oscillating for 24h at 37 ℃, repeatedly washing with deionized water after complete reaction to obtain the PDA surface modified substrate.
And (3) placing the PDA surface modified substrate in 1g/L Polyethyleneimine (PEI) solution, oscillating for 3h at 37 ℃, and washing with deionized water to obtain the PEI-PDA surface modified substrate.
Soaking the PEI-PDA surface modified substrate in a ruthenium nitrate hexahydrate solution with the concentration of 0.30mol/L for treatment for 2h, taking out the substrate, washing the substrate with deionized water for 4 times, and then placing the substrate in a nitrilotriacetic acid solution with the concentration of 0.03mol/L and 2,2' with the concentration of 0.03 mol/L; and (3) reacting the mixed solution of 6, 2' -terpyridine at 120 ℃ for 10 hours in a reaction kettle to obtain the membrane material (the organic ligand and the solvent of the metal salt solution are both mixed solvents of alcohol and water, and preferably, the alcohol is ethanol). And taking out after the reaction is completed, repeatedly cleaning the membrane material for 3 times by using deionized water and ethanol, soaking the membrane material in the ethanol for 12 hours, taking out, and drying in vacuum for 3 hours to obtain the composite base material with the metal organic framework fibers growing on the surface. And controlling the temperature to be 1000 ℃ under the protection of nitrogen, and carbonizing the composite base material with the metal organic framework fibers growing on the surface to obtain the nanofiber-based high-conductivity gas sensing device material.
According to the preparation method provided by the invention, the polydopamine coating is obtained by in-situ polymerization on the surface of the base material, and after the polydopamine coating is crosslinked with PEI, the in-situ growth of the metal organic framework nanofiber on the surface of the base material is ensured, and the prepared gas sensor has the advantages of high sensitivity, high selectivity and high corresponding speed for gas sensing.
The above examples are merely preferred examples and are not intended to limit the embodiments of the present invention. In addition to the above embodiments, the present invention has other embodiments. All technical solutions formed by adopting equivalent substitutions or equivalent transformations fall within the protection scope of the claims of the present invention.
Claims (7)
1. A preparation method of a high-conductivity gas sensor material based on nanofibers is characterized by comprising the following steps: respectively adopting polydopamine and polyethyleneimine to carry out surface modification on a substrate material in sequence to prepare a modified substrate material, then growing metal organic framework nano fibers on the surface of the modified substrate material in situ, and carrying out high-temperature carbonization treatment to prepare the high-conductivity gas sensor material; the process of in-situ growth of the metal organic framework nanofiber on the surface of the modified base material is as follows: placing the modified matrix material in a lanthanide metal salt solution for treatment, taking out water, washing, placing in an organic ligand solution, reacting at room temperature or at elevated temperature, washing with ethanol and deionized water, soaking in ethanol, taking out, and drying to obtain the matrix material with the surface in-situ grown metal-organic framework nanofiber;
the high-temperature carbonization treatment is to carbonize and pyrolyze polydopamine into a graphene lamellar structure; the conditions of the high-temperature carbonization treatment are as follows: raising the temperature from room temperature to 800-1200 ℃ under the nitrogen atmosphere, and keeping the constant temperature for 30-60 min.
2. The method for preparing the nanofiber-based highly conductive gas sensor material as claimed in claim 1, wherein: the fiber diameter of the metal organic framework nanofiber is 50 nm-1 mu m, and the fiber length is 5 mu m-100 mu m.
3. The method for preparing the nanofiber-based highly conductive gas sensor material as claimed in claim 2, wherein: the metal organic framework nanofiber is prepared from lanthanide metal salt and an organic ligand.
4. The method for preparing a nanofiber-based highly conductive gas sensor material as claimed in claim 3, wherein: the lanthanide metal salt comprises an inorganic compound consisting of one element or a mixture of at least two elements selected from Eu, Gd, Tb, Sm and Yb.
5. The method for preparing a nanofiber-based highly conductive gas sensor material as claimed in claim 3, wherein: the organic ligand comprises trimesic acid, citric acid, nitrilotriacetic acid and 2, 2'; at least one of 6,2 "-bipyridine or diethylenetriamine.
6. The method for preparing the nanofiber-based highly conductive gas sensor material as claimed in claim 1, wherein: the matrix material is one of a polymer nanofiber self-supporting film, a polymer nanofiber/non-woven fabric coating composite film, an interdigital electrode, a metal net film or an inorganic non-metal net film.
7. The method for preparing the nanofiber-based highly conductive gas sensor material as claimed in claim 1, wherein: the surface modification process of the base material is as follows: cleaning and drying a base material, then placing the base material in a dopamine solution for treatment to obtain a polydopamine surface modified base material, washing the polydopamine surface modified base material with deionized water, then placing the polydopamine surface modified base material in a polyethyleneimine solution for treatment, taking out the polydopamine surface modified base material, washing with deionized water, drying to obtain a modified base material, and sealing for storage.
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