CN114481339B - Metal oxide nanofiber sensor, preparation method thereof and application thereof in formaldehyde detection - Google Patents
Metal oxide nanofiber sensor, preparation method thereof and application thereof in formaldehyde detection Download PDFInfo
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- CN114481339B CN114481339B CN202210089789.7A CN202210089789A CN114481339B CN 114481339 B CN114481339 B CN 114481339B CN 202210089789 A CN202210089789 A CN 202210089789A CN 114481339 B CN114481339 B CN 114481339B
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0061—Electro-spinning characterised by the electro-spinning apparatus
- D01D5/0076—Electro-spinning characterised by the electro-spinning apparatus characterised by the collecting device, e.g. drum, wheel, endless belt, plate or grid
- D01D5/0084—Coating by electro-spinning, i.e. the electro-spun fibres are not removed from the collecting device but remain integral with it, e.g. coating of prostheses
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/0007—Electro-spinning
- D01D5/0015—Electro-spinning characterised by the initial state of the material
- D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
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- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
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- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- G01N5/02—Analysing materials by weighing, e.g. weighing small particles separated from a gas or liquid by absorbing or adsorbing components of a material and determining change of weight of the adsorbent, e.g. determining moisture content
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Abstract
The invention discloses a metal oxide nanofiber sensor, a preparation method thereof and application thereof in formaldehyde detection, wherein the method comprises the following steps: dissolving a water-insoluble high molecular polymer in a solvent to obtain an electrospinning raw material; adding metal salt into the electrospinning raw material to obtain the electrospinning raw material doped with metal ions; inputting the electrospinning raw material doped with metal ions onto a spinneret and connecting the spinneret with a power supply for electrostatic spinning to obtain fibers; and depositing the fiber on an electrode of a quartz crystal microbalance, and then carrying out vacuum drying and calcining in the air atmosphere to obtain the metal oxide nanofiber sensor. The invention maintains the advantages of high surface area, porosity and the like of the nano-fiber, and realizes real-time, rapid, accurate and long-term formaldehyde detection by virtue of the advantages of low cost, high stability, simple working principle and the like of the metal oxide semiconductor material, the lowest detection limit can reach 26ppb, the nano-fiber can be continuously used for at least three weeks, and the stability is strong.
Description
Technical Field
The invention relates to the technical field of formaldehyde detection, in particular to a metal oxide nanofiber sensor, a preparation method thereof and application thereof in formaldehyde detection.
Background
Formaldehyde is a common indoor pollutant and was listed as the first class of human carcinogen by the international cancer research institute in 2004. The World Health Organization (WHO) sets a very strict 30-minute contact limit, namely 80ppb, and China also sets a standard of the maximum allowable concentration of 60ppb of formaldehyde in room air. Indoor formaldehyde has become a major health threat due to the increasing use of chemical binders.
Up to now, formaldehyde detection methods based on electrochemistry, high performance liquid chromatography, gas chromatography, spectrophotometry, polarography and fluorescence have been established. Although these methods have some applications, their large-scale application is still limited due to high cost, complicated operation, and poor adaptability to real-time detection in particular.
Therefore, it is very necessary to explore a small and portable instrument to monitor the formaldehyde concentration in the environment in real time and solve the problems of high detection limit, low sensitivity, complex operation, long measurement time and the like.
Disclosure of Invention
The invention aims to provide a metal oxide nanofiber sensor, a preparation method thereof and application thereof in formaldehyde detection, by constructing metal oxide nanofibers, the advantages of high surface area, porosity and the like of the nanofibers are kept, and meanwhile, by means of the advantages of low cost, high stability, simple working principle and the like of metal oxide semiconductor materials, real-time, rapid, accurate and long-term formaldehyde detection is realized, the lowest detection limit can reach 26ppb, the sensor can be continuously used for at least three weeks, and the stability is strong.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect of the present invention, there is provided a method of making a metal oxide nanofiber sensor, the method comprising:
dissolving a water-insoluble high molecular polymer in a solvent to obtain an electrospinning raw material;
adding metal salt into the electrospinning raw material to obtain the electrospinning raw material doped with metal ions; wherein the metal salt consists of a plurality of monometallic salts containing different metals;
inputting the electrospinning raw material doped with metal ions onto a spinneret and connecting the spinneret with a power supply for electrostatic spinning to obtain fibers;
and depositing the fiber on an electrode of a quartz crystal microbalance, and then carrying out vacuum drying and calcining in the air atmosphere to obtain the metal oxide nanofiber sensor.
In the technical scheme, the plurality of types are two or more.
Further, the metal salt is added into the electrospinning raw material at a concentration of 0.01-0.5 mol/L, and the metal salt comprises at least one of titanium tetrachloride, ferric hydroxide, ferric nitrate, copper acetate, copper carbonate, copper sulfate, zinc acetate, zinc carbonate, zinc sulfate, copper nitrate, copper chloride, zinc nitrate, zinc dihydrogen phosphate, tin methane sulfonate, tin ethane sulfonate, tin propane sulfonate, tin 2-propane sulfonate, cerium trichloride, cerium sulfate, ferric chloride, ferric sulfate, aluminum nitrate, aluminum chloride and aluminum sulfate.
Further, the mass fraction of the electrospinning raw material is 2% -20%.
Further, the water-insoluble high molecular polymer is one or a mixture of more than two of nylon 6, polypropylene, chitin, glucan, fibrin, silk protein, polyurethane, polyethylene terephthalate, polyvinylidene fluoride, polystyrene, cellulose acetate, cellulose, chitosan, ethylene-vinyl alcohol copolymer, polymethyl methacrylate, polyisobutylene, polycarbonate, polyacrylonitrile, polycaprolactone, polyvinyl acetate, epoxy resin, polysiloxane, hyaluronic acid and chondroitin sulfate;
the solvent is diethyl ether, dimethyl sulfoxide, benzene, chlorobenzene, acetonitrile, vinyl glycol, toluene, methylcyclohexane, N-dimethylformamide, ethanol, formic acid, xylene, cyclohexane, 2-methoxyethanol, 1,1,2-trichloroethylene, 1,2-dimethoxyethane, butyl acetate, isooctane, isopropyl ether, methyl isopropyl ketone, tributyl methyl ethyl ether, ethyl acetate, N-methylpyrrolidone, pentane, acetic acid, acetone, tetrahydrofuran and N, N-dimethylacetamide, 2-methyl-1-propanol, propyl acetate, 1,1-diethoxypropane, 1,1-dimethoxymethane, 2,2-dimethoxypropane, isopropyl acetate, methyl ethyl ketone, isopropyl benzene, methylene chloride, methanol, carbon tetrachloride, 1,2-dichloroethane, trichloroethane, 2-ethoxyethanol, sulfolane, pyrimidine, formamide, N-hexane, trichloroacetic acid, pyridine trifluoroacetate, 1,2-dichloroethylene, anisole, 1-propanol, 2-propanol, 1-butanol, 2-butanol, pentanol, ethyl formate, isobutyl acetate, methyl acetate, 3-methyl-1-butanol, methyl isobutyl ketone, methyltetrahydrofuran, and petroleum ether.
Further, the electrospinning raw material is input into a spinneret and input at a flow rate of 0.5-3 mL/h at a room temperature of 25 +/-2 ℃ and a humidity range of 35-65%.
Further, the fiber is deposited on an electrode of a quartz crystal microbalance, and the distance between the electrode and the spinneret is controlled to be 5-20 cm.
Further, the vacuum drying time is 1-3 h, the calcining temperature is 200-800 ℃, and the calcining time is 2-10 h.
In a second aspect of the invention, a metal oxide nanofiber sensor obtained by the method is provided.
In a third aspect of the present invention, there is provided a method for detecting formaldehyde using the metal oxide nanofiber sensor, the method comprising:
an air sample is injected into the test slot by a syringe,
placing the metal oxide nanofiber sensor in a detection tank, and reading the mass of formaldehyde in an air sample on the metal oxide nanofiber sensor;
obtaining the concentration of formaldehyde in the air by the mass of formaldehyde in the air sample and the following formula:
one or more technical solutions in the embodiments of the present invention have at least the following technical effects or advantages:
according to the metal oxide nanofiber sensor provided by the invention, through constructing the metal oxide nanofiber, the advantages of high surface area, high porosity and the like of the nanofiber are kept, and meanwhile, by means of the advantages of low cost, high stability, simple working principle and the like of a metal oxide semiconductor material, real-time, rapid, accurate and long-term formaldehyde detection is realized, the lowest detection limit can reach 50ppb, the sensor can be continuously used for at least three weeks, and the stability is strong. The metal oxide nanofiber sensor has the advantages of low detection limit, high sensitivity, good selectivity, strong stability and long service life.
Drawings
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings required to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the description below are some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on the drawings without creative efforts.
FIG. 1 is a schematic diagram of a process for preparing a metal oxide nanofiber sensor according to the present invention;
FIG. 2 is a scanning electron microscope image of the electrostatic spinning nanofibers before calcination (A) and after calcination in air atmosphere (B);
fig. 3 is a flowchart of a method for manufacturing a metal oxide nanofiber sensor according to the present invention.
Detailed Description
The present invention will be described in detail below with reference to specific embodiments and examples, and the advantages and various effects of the present invention will be more clearly apparent therefrom. It will be understood by those skilled in the art that these specific embodiments and examples are for the purpose of illustrating the invention and are not to be construed as limiting the invention.
Throughout the specification, unless otherwise specifically noted, terms used herein should be understood as having meanings as commonly used in the art. Accordingly, unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. If there is a conflict, the present specification will control.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be obtained by an existing method.
In order to solve the technical problems, the general idea of the embodiment of the application is as follows:
according to an exemplary embodiment of the present invention, there is provided a method of manufacturing a metal oxide nanofiber sensor, as shown in fig. 3, the method including:
s1, dissolving a water-insoluble high molecular polymer in a solvent to obtain an electrospinning raw material;
in the step S1, the first step is performed,
the water-insoluble high molecular polymer is one or a mixture of more than two of nylon 6, polypropylene, chitin, glucan, fibrin, silk protein, polyurethane, polyethylene glycol terephthalate, polyvinylidene fluoride, polystyrene, cellulose acetate, cellulose, chitosan, ethylene-vinyl alcohol copolymer, polymethyl methacrylate, polyisobutylene, polycarbonate, polyacrylonitrile, polycaprolactone, polyvinyl acetate, epoxy resin, polysiloxane, hyaluronic acid and chondroitin sulfate;
the solvent is diethyl ether, dimethyl sulfoxide, benzene, chlorobenzene, acetonitrile, vinyl glycol, toluene, methylcyclohexane, N-dimethylformamide, ethanol, formic acid, xylene, cyclohexane, 2-methoxyethanol, 1,1,2-trichloroethylene, 1,2-dimethoxyethane, butyl acetate, isooctane, isopropyl ether, methyl isopropyl ketone, tributyl methyl ethyl ether, ethyl acetate, N-methylpyrrolidone, pentane, acetic acid, acetone, tetrahydrofuran and N, N-dimethylacetamide, 2-methyl-1-propanol, propyl acetate, 1,1-diethoxypropane, 1,1-dimethoxymethane, 2,2-dimethoxypropane, isopropyl acetate, methyl ethyl ketone, isopropyl benzene, methylene chloride, methanol, carbon tetrachloride, 1,2-dichloroethane, trichloroethane, 2-ethoxyethanol, sulfolane, pyrimidine, formamide, N-hexane, trichloroacetic acid, pyridine trifluoroacetate, 1,2-dichloroethylene, anisole, 1-propanol, 2-propanol, 1-butanol, 2-butanol, pentanol, ethyl formate, isobutyl acetate, methyl acetate, 3-methyl-1-butanol, methyl isobutyl ketone, methyltetrahydrofuran, and petroleum ether.
In a preferred embodiment, the mass fraction of the electrospinning raw material is 2% to 20%. If the mass fraction of the electrospinning raw material is less than 2%, the adverse effect of a bead structure is easily generated; if the solution viscosity is too high, the electrospinning can not be carried out if the solution viscosity is more than 20 percent;
s2, adding metal salt into the electrospinning raw material to obtain the electrospinning raw material doped with metal ions; wherein the metal salt consists of a plurality of monometallic salts containing different metals;
in the step S2, the first step is performed,
the metal salt is added into the electrospinning raw material at the final concentration of 0.01-0.5 mol/L;
the reason or the advantage that the metal salt is added at the final concentration of 0.01-0.5 mol/L is as follows: can form sufficient and evenly distributed metal doped nano fiber membrane, and provide sufficient active sites for formaldehyde adsorption and detection; if the concentration of the metal salt is less than 0.01mol/L, the detection sensitivity of the sensor is reduced; if the concentration is more than 0.5mol/L, a sensor with uniform distribution and stable performance is difficult to form.
The metal salt includes two or more (and need to be metal salts containing different metals) of titanium tetrachloride, ferric hydroxide, ferric nitrate, copper acetate, copper carbonate, copper sulfate, zinc acetate, zinc carbonate, zinc sulfate, copper nitrate, copper chloride, zinc nitrate, zinc dihydrogen phosphate, tin methane sulfonate, tin ethane sulfonate, tin propane sulfonate, tin 2-propane sulfonate, cerium trichloride, cerium sulfate, ferric chloride, ferric sulfate, aluminum nitrate, aluminum chloride and aluminum sulfate. As shown by tests, the heterojunction structure can be formed only by adding two or more than two metals with different electron adsorption capacities together, so that the formaldehyde can be detected.
According to a large number of experiments, the metal salt is added into the electrospinning raw material in the step 2, then the metal salt is input to a spinneret and connected with a power supply to carry out electrostatic spinning and deposition, and finally the metal oxide nanofiber sensor is prepared.
S3, inputting the electrospinning raw material doped with metal ions to a spinneret and connecting a power supply to carry out electrostatic spinning to obtain fibers;
in the step S3, the first step is performed,
the electrospinning raw material is input into a spinneret and input at the flow rate of 0.5-3 mL/h under the conditions of room temperature of 25 +/-2 ℃ and humidity range of 35-65%. This condition facilitates better input of electrospinning raw materials to the spinneret. The power supply connected with the spinning nozzle is 5-30 kV.
And S4, depositing the fiber on an electrode of a quartz crystal microbalance, and then carrying out vacuum drying and calcining in the air atmosphere to obtain the metal oxide nanofiber sensor.
And depositing the fiber on an electrode of a quartz crystal microbalance, and controlling the distance between the electrode and the spinneret to be 5-20 cm. The arrangement is favorable for the rapid and sufficient volatilization of the organic solvent in the spinning process, and a porous nanofiber membrane is formed on the electrode;
the vacuum drying time is 1-3 h, the calcining temperature is 200-800 ℃, and the calcining time is 2-10 h.
According to another exemplary embodiment of the present invention, a metal oxide nanofiber sensor obtained by the method is provided.
According to another exemplary embodiment of the present invention, there is provided a method for detecting formaldehyde using the metal oxide nanofiber sensor, the method including:
an air sample is injected into the test slot by a syringe,
placing the metal oxide nanofiber sensor in a detection tank, and reading the mass of formaldehyde in an air sample on the metal oxide nanofiber sensor;
obtaining the concentration of formaldehyde in the air by the mass of formaldehyde in the air sample and the following formula:
a metal oxide nanofiber sensor of the present application, a method for manufacturing the same, and applications thereof will be described in detail with reference to examples, comparative examples, and experimental data.
Example 1
Stirring and dissolving 1g of cellulose acetate in 10g of a mixed solvent of dichloromethane and acetone (the weight ratio is 3:1) at the room temperature of 25 ℃ and at the rotating speed of 150rpm in a stirring kettle to obtain a cellulose acetate solution (0.01L) with the mass fraction of 10%; continuously adding 0.200g of copper acetate and 0.219g of zinc acetate into the cellulose acetate solution at the room temperature of 25 ℃ to obtain an electrospinning raw material doped with metal ions (the final concentration of metal salt is 0.2 mol/L); inputting the spinning solution to a spinneret at the flow rate of 1mL/h at the conditions of room temperature of 25 ℃ and humidity of 35%, and simultaneously connecting the spinneret to an 18kV power supply to carry out electrostatic spinning to prepare nanofibers; depositing the spun fiber on an electrode of a quartz crystal microbalance, and receiving a click, wherein the distance between the shot and a spinning nozzle is 8cm; vacuum drying the electrode of the quartz crystal microbalance deposited with the fibers for 1 hour at room temperature, and then calcining the electrode in air at 450 ℃ for 5 hours, wherein the preparation process flow is shown in figure 1; observing the nanofiber before calcination and after calcination in the air atmosphere by using a field emission electron scanning microscope, and finding that the nanofiber with a porous three-dimensional structure is successfully prepared, wherein the nanofiber is shown in a figure 2; injecting 0.5 mu L of air sample into the detection groove by an injector, placing a quartz crystal microbalance electrode in the detection groove, and reading the mass of formaldehyde in the air sample by 2.5 multiplied by 10 after the reading of the quartz crystal microbalance is stable -3 ng, the concentration of formaldehyde in the air was calculated to be 50ppb. The air sample is detected by using the quartz crystal microbalance electrode for 15 days continuously, and the calculated formaldehyde concentration does not change, which shows that the detection method has good stability and repeatability。
Example 2
Stirring and dissolving 1g of cellulose acetate in 10g of a mixed solvent of dichloromethane and acetone (the weight ratio is 2:1) at the room temperature of 25 ℃ and at the rotating speed of 500rpm in a stirring kettle to obtain a cellulose acetate solution (0.01L) with the mass fraction of 10%; continuously adding 0.100g of copper acetate and 0.219g of zinc acetate into the cellulose acetate solution at the room temperature of 25 ℃ to obtain an electrospinning raw material doped with metal ions (the final concentration of metal salt is 0.15 mol/L); inputting the spinning solution to a spinneret at the flow rate of 0.8mL/h at the conditions of room temperature of 25 ℃ and humidity of 35%, and simultaneously connecting the spinneret to a 16kV power supply to carry out electrostatic spinning to prepare nanofibers; depositing the spun fiber on an electrode of a quartz crystal microbalance, and receiving a click, wherein the distance between the shot and a spinning nozzle is 10cm; vacuum drying the electrode of the quartz crystal microbalance deposited with the fibers for 2 hours at room temperature, and then calcining the electrode in air at 450 ℃ for 5 hours; injecting 0.5 mu L of air sample into a detection groove through an injector, placing a quartz crystal microbalance electrode in the detection groove, and reading the mass of formaldehyde in the air sample by 5 multiplied by 10 after the reading of the quartz crystal microbalance is stable - 3 ng, the concentration of formaldehyde in the air was calculated to be 100ppb.
Example 3
Stirring and dissolving 0.75g of cellulose acetate in 10g of a mixed solvent of dichloromethane and acetone (the weight ratio is 1:1) at the room temperature of 25 ℃ at the rotating speed of 500rpm in a stirring kettle to obtain a cellulose acetate solution (0.01L) with the mass fraction of 7.5%; continuously adding 0.200g of copper acetate and 0.219g of zinc acetate into the cellulose acetate solution at the room temperature of 25 ℃ to obtain an electrospinning raw material doped with metal ions (the final concentration of metal salt is 0.2 mol/L); inputting the spinning solution to a spinneret at the flow rate of 1.2mL/h at the conditions of room temperature of 25 ℃ and humidity of 35%, and simultaneously connecting the spinneret to a 20kV power supply to carry out electrostatic spinning to prepare nanofibers; depositing the spun fiber on an electrode of a quartz crystal microbalance, and receiving a click, wherein the distance between the shot and a spinning nozzle is 10cm; vacuum drying the electrode of the quartz crystal microbalance deposited with the fibers at room temperature for 2 hours, and then calcining in air at 500 ℃ for 3 hours;injecting 0.5 mu L of air sample into the detection groove by an injector, placing a quartz crystal microbalance electrode in the detection groove, and reading the mass of formaldehyde in the air sample to be 7.5 multiplied by 10 after the reading of the quartz crystal microbalance is stable -3 ng, the concentration of formaldehyde in the air was calculated to be 150ppb.
Example 4
Stirring and dissolving 0.75g of cellulose acetate in 10g of a mixed solvent of dichloromethane and acetone (the weight ratio is 3:1) at the room temperature of 25 ℃ at the rotating speed of 500rpm in a stirring kettle to obtain a cellulose acetate solution (0.01L) with the mass fraction of 7.5%; continuously adding 0.200g of copper acetate and 0.219g of zinc acetate into the cellulose acetate solution at the room temperature of 25 ℃ to obtain an electrospinning raw material doped with metal ions (the final concentration of metal salt is 0.2 mol/L); inputting the spinning solution to a spinneret at the flow rate of 0.6mL/h at the conditions of room temperature of 25 ℃ and humidity of 35%, and simultaneously connecting the spinneret to a 18kV power supply to carry out electrostatic spinning to prepare nanofibers; depositing the spun fiber on an electrode of a quartz crystal microbalance, and receiving a click, wherein the distance between the click and a spinning nozzle is 5cm; vacuum drying the electrode of the quartz crystal microbalance deposited with the fibers at room temperature for 2 hours, and then calcining in air at 500 ℃ for 3 hours; injecting 0.5 mu L of air sample into the detection groove by an injector, placing a quartz crystal microbalance electrode in the detection groove, and reading the mass of formaldehyde in the air sample by 2.5 multiplied by 10 after the reading of the quartz crystal microbalance is stable -3 ng, the concentration of formaldehyde in the air was calculated to be 50ppb.
Example 5
Stirring and dissolving 1g of polyacrylonitrile in 10gN, N-dimethylformamide at the rotation speed of 200rpm in a stirring kettle at the room temperature of 25 ℃ to obtain a polyacrylonitrile solution (0.01L) with the mass fraction of 10%; continuously adding 0.200g of copper acetate and 0.219g of zinc acetate into the cellulose acetate solution at the room temperature of 25 ℃ to obtain an electrospinning raw material doped with metal ions (the final concentration of metal salt is 0.2 mol/L); inputting the spinning solution to a spinneret at the flow rate of 1mL/h at the conditions of room temperature of 25 ℃ and humidity of 35%, and simultaneously connecting the spinneret to an 18kV power supply to carry out electrostatic spinning to prepare nanofibers; depositing spun fibers onto quartz crystalsThe distance between the receiving click and the spinning nozzle on the electrode of the microbalance is 8cm; vacuum drying the electrode of the quartz crystal microbalance deposited with the fibers for 1 hour at room temperature, and then calcining the electrode in air at 450 ℃ for 5 hours; injecting 0.5 mu L of air sample into a detection groove through an injector, placing a quartz crystal microbalance electrode in the detection groove, and reading the mass of formaldehyde in the air sample by 20 multiplied by 10 after the reading of the quartz crystal microbalance is stable -3 ng, the concentration of formaldehyde in the air was calculated to be 400ppb.
Example 6
Stirring and dissolving 2g of polyamide 6 in 10g of formic acid at the room temperature of 25 ℃ at the rotating speed of 500rpm in a stirring kettle to obtain a polyamide 6 solution (0.01L) with the mass fraction of 20%; continuously adding 0.200g of copper acetate and 0.219g of zinc acetate into the cellulose acetate solution at the room temperature of 25 ℃ to obtain an electrospinning raw material doped with metal ions (the final concentration of metal salt is 0.2 mol/L); inputting the spinning solution to a spinneret at the flow rate of 0.8mL/h at the conditions of room temperature of 25 ℃ and humidity of 35%, and simultaneously connecting the spinneret to a 18kV power supply to carry out electrostatic spinning to prepare nanofibers; depositing the spun fiber on an electrode of a quartz crystal microbalance, and receiving a click, wherein the distance between the click and a spinning nozzle is 8cm; vacuum drying the electrode of the quartz crystal microbalance deposited with the fibers for 1 hour at room temperature, and then calcining the electrode in air at 500 ℃ for 5 hours; injecting 0.5 mu L of air sample into a detection groove through an injector, placing a quartz crystal microbalance electrode in the detection groove, and reading the mass of formaldehyde in the air sample by 25 multiplied by 10 after the reading of the quartz crystal microbalance is stable -3 ng, the concentration of formaldehyde in the air was calculated to be 500ppb.
Comparative example 1
Stirring and dissolving 1g of cellulose acetate in 10g of mixed solvent of dichloromethane and acetone (the weight ratio is 3:1) in a stirring kettle at the room temperature of 25 ℃ at the rotating speed of 150rpm to obtain an electrospinning raw material; inputting the spinning solution to a spinneret at the flow rate of 1mL/h at the conditions of room temperature of 25 ℃ and humidity of 35%, and simultaneously connecting the spinneret to an 18kV power supply to carry out electrostatic spinning to prepare nanofibers; depositing the spun fiber on an electrode of a quartz crystal microbalance, and receiving a click, wherein the distance between the shot and a spinning nozzle is 8cm; vacuum drying the electrode of the quartz crystal microbalance deposited with the fibers for 1 hour at room temperature, and then calcining the electrode in air at 450 ℃ for 5 hours; and injecting a 0.5 mu L air sample into the detection tank through an injector, and placing the quartz crystal microbalance electrode into the detection tank, wherein the reading of the quartz crystal microbalance is not changed, which indicates that the nanofiber which is not doped with the metal oxide can not respond to the formaldehyde gas.
Comparative example 2
Stirring and dissolving 1g of cellulose acetate in 10g of mixed solvent of dichloromethane and acetone (the weight ratio is 2:1) in a stirring kettle at the room temperature of 25 ℃ at the rotating speed of 500rpm to obtain an electrospinning raw material; inputting the spinning solution to a spinneret at the flow rate of 0.8mL/h at the conditions of room temperature of 25 ℃ and humidity of 35%, and simultaneously connecting the spinneret to a 16kV power supply to carry out electrostatic spinning to prepare nanofibers; depositing the spun fiber on an electrode of a quartz crystal microbalance, and receiving a click, wherein the distance between the shot and a spinning nozzle is 10cm; vacuum drying the electrode of the quartz crystal microbalance deposited with the fibers for 2 hours at room temperature, and then calcining the electrode in air at 450 ℃ for 5 hours; and injecting a 0.5 mu L air sample into the detection tank through an injector, and placing the quartz crystal microbalance electrode into the detection tank, wherein the reading of the quartz crystal microbalance is not changed, which indicates that the nanofiber which is not doped with the metal oxide can not respond to the formaldehyde gas.
Comparative example 3
Stirring and dissolving 0.75g of cellulose acetate in 10g of mixed solvent of dichloromethane and acetone (the weight ratio is 1:1) in a stirring kettle at the room temperature of 25 ℃ at the rotating speed of 500rpm to obtain an electrospinning raw material; inputting the spinning solution to a spinneret at the flow rate of 1.2mL/h at the conditions of room temperature of 25 ℃ and humidity of 35%, and simultaneously connecting the spinneret to a 20kV power supply to carry out electrostatic spinning to prepare nanofibers; depositing the spun fiber on an electrode of a quartz crystal microbalance, and receiving a click, wherein the distance between the shot and a spinning nozzle is 10cm; vacuum drying the electrode of the quartz crystal microbalance deposited with the fibers at room temperature for 2 hours, and then calcining in air at 500 ℃ for 3 hours; and injecting a 0.5 mu L air sample into the detection tank through the injector, placing the quartz crystal microbalance electrode in the detection tank, and finding that the reading of the quartz crystal microbalance is unchanged, which indicates that the nanofiber not doped with the metal oxide can not respond to the formaldehyde gas.
Comparative example 4
Stirring and dissolving 1g of cellulose acetate in 10g of mixed solvent of dichloromethane and acetone (the weight ratio is 2:1) in a stirring kettle at the room temperature of 25 ℃ at the rotating speed of 500rpm to obtain a cellulose acetate solution with the mass fraction of 10%; continuously adding 0.100g of copper acetate into the cellulose acetate solution at the room temperature of 25 ℃ to obtain an electrospinning raw material doped with metal ions; inputting the spinning solution to a spinneret at the flow rate of 0.8mL/h at the conditions of room temperature of 25 ℃ and humidity of 35%, and simultaneously connecting the spinneret to a 16kV power supply to carry out electrostatic spinning to prepare nanofibers; depositing the spun fiber on an electrode of a quartz crystal microbalance, and receiving a click, wherein the distance between the shot and a spinning nozzle is 10cm; vacuum drying the electrode of the quartz crystal microbalance deposited with the fibers for 2 hours at room temperature, and then calcining the electrode in air at 450 ℃ for 5 hours; when a 0.5 mu L air sample is injected into the detection tank through the syringe, the reading of the quartz crystal microbalance is not changed, which indicates that the nano-fiber not doped with the metal oxide can not respond to the formaldehyde gas.
Comparative example 5
Stirring and dissolving 1g of cellulose acetate in 10g of mixed solvent of dichloromethane and acetone (the weight ratio is 2:1) in a stirring kettle at the room temperature of 25 ℃ at the rotating speed of 500rpm to obtain a cellulose acetate solution with the mass fraction of 10%; continuously adding 0.100g of zinc acetate into the cellulose acetate solution at the room temperature of 25 ℃ to obtain an electrospinning raw material doped with metal ions; inputting the spinning solution to a spinneret at the flow rate of 0.8mL/h at the conditions of room temperature of 25 ℃ and humidity of 35%, and simultaneously connecting the spinneret to a 16kV power supply to carry out electrostatic spinning to prepare nanofibers; depositing the spun fiber on an electrode of a quartz crystal microbalance, and receiving a click, wherein the distance between the shot and a spinning nozzle is 10cm; vacuum drying the electrode of the quartz crystal microbalance deposited with the fibers for 2 hours at room temperature, and then calcining the electrode in air at 450 ℃ for 5 hours; when a 0.5 mu L air sample is injected into the detection tank through the syringe, the reading of the quartz crystal microbalance is not changed, which indicates that the nano-fiber not doped with the metal oxide can not respond to the formaldehyde gas.
Experimental example 1
For convenience of comparison, the data tabulation statistics for each example and each comparative example above are shown in table 1.
TABLE 1
From the data in table 1, it can be seen that:
in comparative examples 1 to 3, the formaldehyde concentration could not be read because no metal salt was added;
in comparative examples 4 to 5, the added monometallic salt, after calcination, failed to form heterojunction active sites capable of adsorbing and detecting formaldehyde, and failed to read formaldehyde concentration;
in inventive examples 1 to 5, the formaldehyde concentration can be read; and the lowest detection limit can reach 26ppb through experimental detection.
In addition, when an air sample containing volatile organic compounds such as ethanol, dichloromethane, acetone and dimethylformamide is introduced into the metal oxide nanofiber sensor obtained in the embodiment of the invention, the change of the indication value cannot be detected or only extremely weak response is obtained, which indicates that the selectivity of the sensor to formaldehyde gas is good. Meanwhile, in a formaldehyde gas detection experiment for three continuous weeks, the metal oxide nanofiber sensor shows a stable reading value, which shows that the sensor has long service life and strong stability. The sensitivity is high (the data is 1.2Hz/ppm, and the change of the concentration of trace formaldehyde can be detected);
in conclusion, the metal oxide nanofiber sensor disclosed by the invention is low in detection limit, high in sensitivity, good in selectivity, strong in stability and long in service life, and can realize real-time, rapid, accurate and long-term formaldehyde detection.
Finally, it should also be noted that the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus.
While preferred embodiments of the present invention have been described, additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including the preferred embodiment and all changes and modifications that fall within the scope of the invention.
It will be apparent to those skilled in the art that various changes and modifications may be made in the present invention without departing from the spirit and scope of the invention. Thus, if such modifications and variations of the present invention fall within the scope of the claims of the present invention and their equivalents, the present invention is also intended to include such modifications and variations.
Claims (8)
1. A method of making a metal oxide nanofiber sensor for detecting formaldehyde concentration, the method comprising:
dissolving a water-insoluble high molecular polymer in a solvent to obtain an electrospinning raw material;
adding metal salt into the electrospinning raw material to obtain the electrospinning raw material doped with metal ions; wherein the metal salt consists of a plurality of monometallic salts containing different metals; the metal salt is added into the electrospinning raw material at the concentration of 0.01-0.5 mol/L, and comprises two or more of titanium tetrachloride, ferric hydroxide, ferric nitrate, copper acetate, copper carbonate, copper sulfate, zinc acetate, zinc carbonate, zinc sulfate, copper nitrate, copper chloride, zinc nitrate, zinc dihydrogen phosphate, tin methane sulfonate, tin ethane sulfonate, tin propane sulfonate, tin 2-propane sulfonate, cerium trichloride, cerium sulfate, ferric chloride, ferric sulfate, aluminum nitrate, aluminum chloride and aluminum sulfate;
inputting the electrospinning raw material doped with the metal ions onto a spinneret and connecting the spinneret with a power supply to carry out electrostatic spinning to obtain fibers;
and depositing the fiber on an electrode of a quartz crystal microbalance, and then carrying out vacuum drying and calcining in an air atmosphere to obtain the metal oxide nanofiber sensor.
2. The method for preparing the metal oxide nanofiber sensor for detecting formaldehyde concentration as claimed in claim 1, wherein the mass fraction of the electrospinning raw material is 2-20%.
3. The method according to claim 1, wherein the water-insoluble polymer is one or more of nylon 6, polypropylene, chitin, dextran, fibrin, silk fibroin, polyurethane, polyethylene terephthalate, polyvinylidene fluoride, polystyrene, cellulose acetate, cellulose, chitosan, ethylene-vinyl alcohol copolymer, polymethyl methacrylate, polyisobutylene, polycarbonate, polyacrylonitrile, polycaprolactone, polyvinyl acetate, epoxy resin, polysiloxane, hyaluronic acid, and chondroitin sulfate;
the solvent is diethyl ether, dimethyl sulfoxide, benzene, chlorobenzene, acetonitrile, vinyl glycol, toluene, methylcyclohexane, N-dimethylformamide, ethanol, formic acid, xylene, cyclohexane, 2-methoxyethanol, 1,1,2-trichloroethylene, 1,2-dimethoxyethane, butyl acetate, isooctane, isopropyl ether, methyl isopropyl ketone, tributyl methyl ethyl ether, ethyl acetate, N-methylpyrrolidone, pentane, acetic acid, acetone, tetrahydrofuran and N, one or more of N-dimethylacetamide, 2-methyl-1-propanol, propyl acetate, 1,1-diethoxypropane, 1,1-dimethoxymethane, 2,2-dimethoxypropane, isopropyl acetate, methyl ethyl ketone, isopropyl benzene, methylene chloride, methanol, carbon tetrachloride, 1,2-dichloroethane, trichloroethane, 2-ethoxyethanol, sulfolane, pyrimidine, formamide, N-hexane, trichloroacetic acid, pyridine trifluoroacetate, 1,2-dichloroethylene, anisole, 1-propanol, 2-propanol, 1-butanol, 2-butanol, pentanol, ethyl formate, isobutyl acetate, methyl acetate, 3-methyl-1-butanol, methyl isobutyl ketone, methyltetrahydrofuran, and petroleum ether.
4. The method for preparing a metal oxide nanofiber sensor for detecting formaldehyde concentration as claimed in claim 1, wherein the electrospinning raw material is input into the spinneret and input at a flow rate of 0.5-3 mL/h at a room temperature of 25 ± 2 ℃ and a humidity range of 35-65%.
5. The method for preparing a metal oxide nanofiber sensor for detecting formaldehyde concentration as claimed in claim 1, wherein when the fiber is deposited on an electrode of a quartz crystal microbalance, the distance between the electrode and the spinneret is controlled to be 5-20 cm.
6. The method for preparing the metal oxide nanofiber sensor for detecting the concentration of formaldehyde as claimed in claim 1, wherein the time of vacuum drying is 1-3 h, the temperature of calcination is 200-800 ℃, and the time of calcination is 2-10 h.
7. A metal oxide nanofiber sensor for detecting formaldehyde concentration obtained according to the method of any one of claims 1 to 6.
8. A method for detecting formaldehyde using the metal oxide nanofiber sensor for detecting formaldehyde concentration as claimed in claim 7,
an air sample is injected into the test slot by a syringe,
placing the metal oxide nanofiber sensor of claim 7 in a detection tank, and reading the mass of formaldehyde in an air sample on the metal oxide nanofiber sensor by a quartz crystal microbalance;
and obtaining the concentration of the formaldehyde in the air according to the mass of the formaldehyde in the air sample.
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| WO2007114192A1 (en) * | 2006-03-29 | 2007-10-11 | Kitakyushu Foundation For The Advancement Of Industry, Science And Technology | Gas detector and process for manufacturing the same |
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