CN113214603B - Carbon nanotube epoxy resin composite material electrode, preparation method and application thereof - Google Patents
Carbon nanotube epoxy resin composite material electrode, preparation method and application thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/49—Systems involving the determination of the current at a single specific value, or small range of values, of applied voltage for producing selective measurement of one or more particular ionic species
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- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses a carbon nano tube epoxy resin composite material electrode, which comprises an electrode body, an electrode tube and an electrode lead; the electrode body is filled at one end of the electrode tube, and the bottom of the electrode body is round; the electrode lead is led out from the electrode body and is led out from the other end in the electrode tube; the electrode body comprises carbon nano tubes of a curing agent and epoxy resin, wherein the mass of the carbon nano tubes is 10-50% of the mass of the electrode body. The invention also discloses a preparation method of the carbon nano tube epoxy resin composite material electrode and application of the carbon nano tube epoxy resin composite material electrode in detection of chemical components in tobacco. The carbon nano tube epoxy resin composite material electrode has the advantages of high sensitivity, good reproducibility, strong pollution resistance and the like.
Description
Technical Field
The invention belongs to the technical field of tobacco chemistry, and particularly relates to a carbon nanotube epoxy resin composite material electrode, and a preparation method and application thereof.
Background
In 1991, carbon nanotubes were first discovered in Iijima, japan [1] It has a needle-like tubular structure of graphitic carbon, whose carbon atoms constitute coaxial cylinders of several to tens of layers. The carbon nano tube as a one-dimensional nano material has many abnormal mechanical, electrical and chemical properties due to the light weight and perfect connection of a hexagonal structure. With the research of carbon nanotubes and nanomaterials, the wide application prospect is continuously shown in recent years. The carbon nanotube is also named as Baseband tube, and is one-dimensional quantum material with nanometer level radial size and micron level axial size and basically sealed ends. Carbon nanotubes are coaxial circular tubes consisting of several to tens of layers of carbon atoms arranged in a hexagonal pattern, with a constant distance between layers, about 0.34nm, and a diameter of 2 to 20nm. The carbon hexagons can be divided into three types, namely a zigzag type, an armchair type and a spiral type, according to different orientations of the carbon hexagons in the axial direction. Carbon nanotubes can be classified into multi-walled carbon nanotubes or single-walled carbon nanotubes according to the number of layers. The carbon nano tube has excellent physical and chemical properties, so the carbon nano tube has good application prospect in the fields of electronics, biological medicine, aerospace, military, energy, lasers, medical treatment, sensors and the like [2,3] 。
Carbon nanotubes have extremely high electrical conductivity and electrocatalytic activity, which has the unique advantage of being prepared in electrochemical sensors, and have been successfully used as electrochemical response materials for enhancing some bioactive substances. The preparation method of the carbon nanotube-based electrode for electrochemical detection mainly comprises a surface modification method, an electrochemical polymerization surface modification method, a paraffin oil mixed filling method and the like, wherein the surface modification is the most commonly used method. The surface modification method is to disperse carbon nanotube powder in a solvent and then coat the solvent on the surface of the substrate electrode, but the carbon nanotube modification layer is easy to fall off in actual use, so that the electrode is poor in stability and short in service life. Mixed filling of paraffin oilThe filling method is that the carbon nano tube powder and the paraffin oil are mixed and then filled in the electrode tube; however, the electrode body is a paste-like, non-rigid material, and is deformed during use, and is a disposable electrode with high noise and poor signal reproducibility in electrochemical detection. The electrochemical polymerization surface modification method is to disperse the carbon nano tube in the conductive polymer monomer solution, and form a surface modification layer through electrochemical polymerization, so that the carbon nano tube is fixed on the surface of the electrode; however, the prepared electrode also has the problem that the carbon nanotube modification layer falls off, so that the stability and the service life of the electrode are influenced. In view of the disadvantages and problems of the original carbon nanotube electrode, the method of preparing the composite material electrode by compounding the polymer and the carbon nanotube is an important way for improving the stability and performance of the carbon nanotube electrode. Epoxy resin is an important thermosetting plastic and is widely used in a plurality of fields such as buildings, military, adhesives, coatings and the like [5] . At present, bisphenol A epoxy resin has the greatest yield and the widest use, and has the advantages of stable chemical property, organic solvent resistance, heat resistance, good electrical insulation, excellent mechanical and mechanical properties and the like.
The tobacco contains electrochemically active components such as phenols, flavones, alkaloids and amino acids, and the quality of tobacco can be examined by detecting the chemical components [6] . The electrochemical detection has the advantages of good selectivity and high sensitivity.
Reference documents
[1]Iijima,S.,Helical microtubules of graphitic carbon[J].Nature,1991,354(6348):56-58.
[2]Zhang,J.,Tahmasebid,A.,Omoriyekomwana,J.E.,Yu,J.L.,Microwave-assisted synthesis of biochar-carbon-nanotube-NiO composite as high-performance anode materials for lithium-ion batteries,Fuel Processing Technology,2021,213,106714.
[3]Rajabathar,J.R.,Periyasami,G.,Alanazi,A.M.,Govindasamy,M.,Arunachalam,P.,Review on carbon nanotube varieties for healthcare application:effect of preparation methods and mechanism insight,Processes,2020,1654.
[4]Zhang,F.L.,Zhang,L.,Yaseen,M.,Huang,K.A review on the self-healing ability of epoxy polymers,A review on the self-healing ability of epoxy polymers,Journal of Applied Polymer Science,2021,138,e50260.
[5]Giovanni,M.,Poh H.L.,Ambrosi A.,Zhao G.,Sofer Z.,Sanek F.,Khezri B.,Webster R.D.,Pumera M.,Nanoscale 2012,4,5002-5008.
[6]Soares,F.A.,Chiapetta,S.C.,Pacheco,W.F.,Development of an analytical method for the determination of N-nitrosamines in tobacco by GC-NCD after solid phase extraction,ANalytical Methods,2017,9,2284-2289.
Disclosure of Invention
The invention aims to provide a tobacco chemical component carbon nano tube epoxy resin composite material electrode which is high in detection sensitivity, high in mechanical strength and long in service life and a rapid preparation method thereof.
The technical scheme of the invention is as follows:
the invention discloses a carbon nano tube epoxy resin composite material electrode in a first aspect, which comprises an electrode body, an electrode tube and an electrode lead; the electrode body is filled at one end of the electrode tube, and the bottom of the electrode body is round; the electrode lead is led out from the electrode body and is led out from the other end in the electrode tube; the electrode body comprises carbon nano tubes of a curing agent and epoxy resin, wherein the mass of the carbon nano tubes is 10-50% of the mass of the electrode body.
Preferably, the electrode tube is made of an electrical insulation material, the electrode tube is one of a plastic tube, a ceramic tube, a quartz tube or a glass tube, and the inner diameter of the electrode tube is 25um-8mm; the electrode lead is fixed at the other end of the electrode tube by an adhesive, and the electrode tube at the end is sealed, wherein the adhesive is one of hot melt adhesive, epoxy resin, silicone adhesive or alpha-ethyl cyanoacrylate.
Preferably, the carbon nanotubes are single-walled carbon nanotubes or multi-walled carbon nanotubes treated with nitric acid.
The second aspect of the invention discloses a preparation method of the carbon nano tube epoxy resin composite material electrode, which comprises the following steps:
(1) Mixing carbon nano tube powder, epoxy resin prepolymer and curing agent according to a certain mass ratio to obtain a black viscous mixture with certain plasticity;
(2) Filling the mixture obtained in the step (1) into one end of an electrode tube, and then inserting an electrode lead into the mixture through the other end of the electrode tube;
(3) Curing the electrode tube obtained in the step (2) for a period of time at an infrared ray and a certain temperature;
(4) Polishing one end of the electrode tube solidified in the step (3) into a round shape; fixing the electrode lead at the other end of the electrode tube by using an adhesive, and sealing the electrode tube at the end; and obtaining the carbon nano tube epoxy resin composite material electrode.
Preferably, the step (1) of treating the carbon nanotubes with nitric acid comprises the following steps: dispersing carbon nano tubes in nitric acid, heating at 50-95 ℃ for 8-15 hours, cooling to room temperature, carrying out vacuum filtration, cleaning until the pH value of filtrate is higher than 5, and heating and drying the solid to obtain the carbon nano tubes treated by the nitric acid. The carbon nano tube is treated by nitric acid to remove metal impurities and oxidize the carbon nano tube, and meanwhile, carboxyl can be introduced to the surface of the carbon nano tube through nitric acid oxidation, so that the binding capacity of the carbon nano tube and epoxy resin can be improved, and the stability and the conductive capacity of an electrode are improved; the nitric acid used is concentrated nitric acid.
Preferably, the carbon nanotubes in step (1) are single-walled carbon nanotubes or multi-walled carbon nanotubes; the mass of the carbon nano tube is 10-50% of the mass of the carbon nano tube powder, the epoxy resin prepolymer and the curing agent.
Preferably, the electrode tube in the step (2) is made of an electrical insulation material, the electrode tube is one of a plastic tube, a ceramic tube, a quartz tube or a glass tube, and the inner diameter of the electrode tube is 25um-8mm; the adhesive in the step (4) is one of hot melt adhesive, epoxy resin, silicone adhesive or alpha-ethyl cyanoacrylate.
Preferably, the wavelength of the infrared ray in the step (3) is 1.40-11000um, the curing temperature is 80-120 ℃, and the curing time is 5-20min.
More preferably, the wavelength of the infrared ray in the step (3) is 3-100um, the curing temperature is 100 ℃, and the curing time is 10min.
The third aspect of the invention discloses application of the carbon nano tube epoxy resin composite material electrode in detection of chemical components in tobacco.
The invention has the beneficial effects that:
1. the invention utilizes the technical advantage of the polycondensation of the thermoplastic epoxy resin body to directly carry out infrared heating and in-situ polycondensation in the insulating material pipe body to prepare the rigid carbon nano tube epoxy resin composite material electrode. Because the electrode body of the carbon nano tube epoxy resin composite material formed by in-situ condensation in the novel electrode is rigid, the performance, the mechanical strength, the stability and the service life of the electrode are greatly improved, the electrode can be directly polished and updated, and the carbon nano tube material is prevented from falling off in the using process.
2. The carbon nanotubes in the carbon nanotube epoxy resin composite material electrode are uniformly dispersed in the epoxy resin to form a good composite conductive system, and the composite conductive system has the advantages of obvious electrocatalytic activity, high sensitivity, good detection reproducibility, strong pollution resistance and the like. The method can be used for electrochemical detection of microfluidic chip electrophoresis, flow injection analysis, liquid chromatography and the like, and can also be used for electrochemical analysis of voltammetry, amperometry, coulometry and the like. The method can be used for electrochemical detection of chemical components of tobacco such as phenols, flavonoids, alkaloids and the like, and can also be used in the fields of food and drug analysis, environmental monitoring, clinical diagnosis and the like. Has wide application prospect.
3. The preparation method of the carbon nano tube epoxy resin composite material electrode is simple and convenient in process, low in raw material cost and capable of being processed in batches. The invention adopts the mid-infrared and far-infrared heating curing with the wavelength of 1.40-11000um to prepare the carbon nano tube epoxy resin composite electrode, which is the first creation of the invention. The wavelength of the absorption spectrum of the organic matters including the polymer and the wavelength of the mid-far infrared rays are in the same range, and the mid-far infrared rays are absorbed very strongly, so that the mid-far infrared radiation is very suitable for a heat source for heating and curing the carbon nano tube epoxy resin composite material, the heating speed is high, the heating efficiency is high, the work can be started or stopped in a short time, and the intelligent control is easy to realize. The epoxy resin prepolymer containing the curing agent needs more than 24 hours for curing at room temperature, and the epoxy resin prepolymer is heated, condensed and cured by a common oven for more than 3 hours; the invention adopts middle infrared and far infrared light, and the epoxy resin prepolymer containing the curing agent and the mixed material of the epoxy resin prepolymer and the carbon nano tube can be completely cured within about 10 minutes at the temperature of about 100 ℃, so that the curing efficiency is obviously improved.
4. The carbon nano tube is treated by concentrated nitric acid before use to remove metal impurities and oxidize the carbon nano tube, and meanwhile, carboxyl can be introduced to the surface of the carbon nano tube through the oxidation of the concentrated nitric acid, so that the binding capacity of the carbon nano tube and epoxy resin can be improved, and the stability and the conductivity of an electrode are improved.
Drawings
Fig. 1 is a flow chart of the preparation of the carbon nanotube epoxy resin composite electrode of the present invention, wherein (D) is a finished product of the carbon nanotube epoxy resin composite electrode.
FIG. 2 is a schematic view of a metal box with air holes for infrared curing.
Fig. 3 shows a scanning electron micrograph (B) of a cross section of the carbon nanotube-epoxy composite electrode of example 1 and a scanning electron micrograph (a) of a multi-walled carbon nanotube used, both at 20000 times.
Fig. 4 is a raman spectrum of the carbon nanotube-epoxy composite electrode of example 1.
FIG. 5 is an electrophoresis chart of standard mixed solutions of nicotine, rutin, chlorogenic acid and quercetin with the concentration of 0.5mM respectively detected by infrared light heating and curing to prepare the carbon nanotube epoxy resin composite material electrode and a common heating and curing method to prepare the carbon nanotube epoxy resin composite material electrode, and the detection temperatures are all 100 ℃; wherein (A) is the detection result of preparing the carbon nano tube epoxy resin composite material electrode by a common heating and curing method; (B) The detection result of the carbon nano tube epoxy resin composite material electrode prepared by the infrared heating curing method is shown.
FIG. 6 is a capillary electrophoresis chart of the carbon nanotube epoxy resin composite electrode obtained in example 1 for detecting a methanol extract from tobacco leaves.
Fig. 7 shows the influence of different infrared irradiation times and temperatures on the response sensitivity of the prepared carbon nanotube-epoxy resin composite electrode to nicotine detection.
FIG. 8 is a voltammogram of a carbon nanotube epoxy composite electrode prepared by infrared heating and curing, and a carbon nanotube epoxy composite electrode prepared by a common heating and curing method, under 0.5mM rutin; temperature was 100 ℃, scanning speed: 100 mv/sec. Wherein (A) is a detection result of preparing the carbon nano tube epoxy resin composite material electrode by an infrared heating curing method; (B) The method is a detection result of preparing the carbon nano tube epoxy resin composite material electrode by a common heating and curing method.
The reference signs are: 1. an electrode tube; 2. an electrode lead; 3. a carbon nanotube epoxy resin prepolymer mixture; 4. a carbon nanotube epoxy resin composite electrode body; 5. a binder; 6. a metal box with air holes; 7. infrared light; 8. carbon nanotube epoxy resin composite material electrodes; 9. a thermocouple; 10. a fan; 11. and a temperature controller.
Detailed Description
The invention is further illustrated by the following examples and figures.
Example 1: preparation of carbon nano tube epoxy resin composite material electrode
2 g of commercial carbon nanotubes with a purity of more than 95% are dispersed in a flask containing 500 ml of concentrated nitric acid, the mixture is heated in a water bath at 60 ℃ for 12 hours, and the mixture in the flask is mechanically stirred at 120 rpm. And after the nitric acid oxidation heat treatment mixture is cooled to room temperature, carrying out vacuum filtration, carrying out suction filtration and cleaning by using a large amount of water through a water pump, and continuously detecting by using pH test paper until the pH value of the filtrate is higher than 5. Then, the solid was placed in a metal box with a gas-permeable hole of fig. 2, and dried at 110 ℃ for 20 minutes to obtain nitric acid oxidation-treated carbon nanotubes.
The preparation process of the carbon nano tube epoxy resin composite material electrode is shown in the attached figure 1. Mixing an E51 type epoxy resin prepolymer and a matched epoxy resin curing agent ethylenediamine according to a mass ratio of 10; weighing 0.5 g of the carbon nano tube powder treated by the nitric acid and 1 g of the epoxy resin prepolymer containing the curing agent, and fully stirring to obtain a black viscous mixture 3 with certain plasticity; inserting one end of a fused silica capillary tube 1 having an inner diameter of 320 μm, an outer diameter of 450 μm and a length of 5 cm into the black viscous mixture, and filling the black viscous mixture 3 into the capillary tube to a filling depth of about 4 mm; then a copper wire 2 of 10 cm length and 150 μm diameter is inserted into the fused silica capillary 1 through another opening until the copper wire 2 is inserted about 2 mm into the black viscous mixture 3 in the capillary 1, ensuring good contact; then, the carbon nanotube-containing epoxy resin was placed in a metal case 6 having an air hole as shown in FIG. 2, the distance between the electrode and the infrared ray bulb was 20 cm, and the condensation polymerization and curing of the carbon nanotube-containing epoxy resin were accelerated by infrared rays at 100 ℃ for 10 minutes.
Then, taking out the electrode, and polishing one end of the capillary tube filled with the carbon nanotube epoxy resin composite material electrode body 4 into a round shape by using abrasive paper; and then, after melting the hot melt adhesive 5, dripping the molten hot melt adhesive on the contact part of the copper wire lead 2 and the other opening end of the capillary 1 to fix the copper wire, and sealing the capillary at the end to obtain a finished product of the carbon nano tube epoxy resin composite material electrode. The adhesive 5 used may be one of a hot melt adhesive, an epoxy, a silicone adhesive, or a 502 adhesive (i.e., ethyl- α -cyanoacrylate), with the hot melt adhesive being most conveniently used.
Comparative example 1
The difference from example 1 is that the carbon nanotube epoxy resin is cured by oven heating at 100 ℃ for 6 hours to cure completely.
The residual carbon nanotube epoxy resin composite material for preparing the electrode is coated on a glass sheet and is placed in a metal box 6 with air holes shown in figure 2, the distance between the electrode and an infrared bulb is 20 cm, and the carbon nanotube epoxy resin composite material acts for 10 minutes at 100 ℃. And then used for test characterization of the material.
Fig. 3 is a scanning electron micrograph (B) of a cross section of the carbon nanotube-epoxy resin composite electrode obtained in example 1 and a scanning electron micrograph (a) of the multi-walled carbon nanotube used, both magnified 20000 times. As can be seen from the lower diagram (B) of fig. 3, the carbon nanotubes are dispersed in the epoxy resin bulk and form a good conductive network to give the material good conductivity; as can be seen from comparison with the scanning electron microscope photograph of the multi-walled carbon nanotube in the upper graph (a) of fig. 3, the carbon nanotube epoxy resin composite material has a significantly different morphology from the pure carbon nanotube, and the broken ends of a plurality of carbon nanotubes can be observed on the cross section of the composite material, and the exposed carbon nanotube electrode array plays a crucial role in response to the electrode and electrochemical catalysis. Because the epoxy resin carbon nano tubes are firmly bonded, the stability of the carbon nano tube conductive network is favorably maintained, and the repeatability and the stability of the electrode can be obviously improved.
Fig. 4 is a raman spectrum of the carbon nanotube-epoxy composite electrode of example 1. As can be seen from fig. 4, after the carbon nanotubes are composited with the epoxy resin, peaks D, G, and 2D of the carbon nanotubes in the composite can be observed, which indicates that the carbon nanotubes in the composite material have a complete structure; in addition, the 2D peak intensity of CNTs in the composite was higher than the D peak, indicating the occurrence of recombination.
Fig. 5 is an electrophoresis chart of standard mixed solutions of nicotine, rutin, chlorogenic acid and quercetin with concentrations of 0.5mM respectively detected by the carbon nanotube epoxy resin composite electrode prepared by infrared light heating and curing in example 1 and the carbon nanotube epoxy resin composite electrode prepared by the common heating and curing method in comparative example 1, and the detection temperatures are all 100 ℃; wherein (A) is the detection result of the carbon nanotube epoxy resin composite electrode prepared by the common heating curing method of comparative example 1; (B) The result of detecting the carbon nanotube-epoxy composite electrode prepared by the infrared light heating curing method of example 1 was obtained. As can be seen from FIG. 5, nicotine, rutin, chlorogenic acid and quercetin were completely separated within 8 minutes, and the peak shape was good. The response peak currents of the four substances on the electrode prepared by the infrared heating curing method in the example 1 are obviously higher than those of the electrode prepared by the common heating curing method in the comparative example 1, which shows that the infrared rays can improve the sensitivity of the composite material electrode; the infrared heating solidification improves the conductivity and the electrocatalytic activity of the carbon nano tube network in the composite material.
In order to explore and verify the application of the developed electrode in the analysis of tobacco reagent samples, the carbon nanotube epoxy resin composite material electrode obtained in the example 1 is also used for analyzing tobacco sample solutions. The preparation method of the tobacco sample solution comprises the following steps: weighing 2.5 g of mechanically pulverized tobacco powder, dispersing in 100 ml of methanol, extracting with an infrared auxiliary system for 5 minutes, filtering to obtain an extract, and storing for later use. Before analysis, 200 microliters of the extract is sucked into a glass weighing bottle, the diameter of the glass weighing bottle is 2 centimeters, the width of the glass weighing bottle is 2 centimeters, infrared solvent removal is carried out in the metal box 6 with the air vents, the solvent methanol can be volatilized within three minutes, then 1 milliliter of buffer solution is added for dilution, standing is carried out for 2 minutes, and then sample injection analysis is carried out. FIG. 6 is a capillary electrophoresis chart of the carbon nanotube epoxy resin composite electrode obtained in example 1 for detecting a methanol extract from tobacco leaves. The results of measurements on methanol extracts of the same tobacco were substantially the same for a plurality of times using different electrodes obtained by the preparation method of example 1. As can be seen from FIG. 6, tobacco contains a large amount of nicotine, rutin, chlorogenic acid, etc.; meanwhile, the carbon nano tube epoxy resin composite material electrode obtained by the preparation method of the embodiment 1 is used for analyzing the tobacco sample solution, and has high sensitivity, good detection reproducibility and strong anti-pollution capability. Because the methanol extract of the tobacco is complex in composition, other impurities do not influence the sensitivity and the reproducibility of detection.
The prepared carbon nano tube epoxy resin composite material electrode is used for detection under different infrared irradiation time and temperature, and the influence on the response sensitivity of nicotine is also investigated. Fig. 7 shows the influence of different infrared irradiation times and temperatures on the response sensitivity of the prepared carbon nanotube-epoxy resin composite electrode in nicotine detection. As can be seen from the upper graph (A) of FIG. 7, when the infrared temperature is 100 ℃, the infrared irradiation time is increased from 4 minutes to 10 minutes, the peak current of nicotine is increased from 43.4nA to 86.64nA, the irradiation time is continuously increased, the sensitivity increase is not large, and therefore, the far infrared irradiation curing time of the selective electrode is 10 minutes. In addition, temperature also has an effect on the peak current of nicotine, see fig. 7, lower panel (B), but increasing the curing temperature has little effect on the peak current of nicotine. The optimized infrared curing condition of the invention is that the infrared ray is irradiated for 10 minutes at 100 ℃, and the infrared ray with the wavelength of 3-100um is selected to have the best effect.
Example 2: carbon nanotube epoxy resin composite material electrode for voltammetry analysis of tobacco chemical components and preparation method thereof
Different from the electrode of the embodiment 1, the area of the working electrode used in various voltammetry methods such as linear voltammetry, cyclic voltammetry, stripping voltammetry, differential pulse voltammetry and the like of the chemical components of tobacco is larger, and the diameter of the generally used circular electrode is 1 to 6 mm, that is, the inner diameter of the electrode tube is required to be larger; meanwhile, a carbon nanotube epoxy resin composite material mixture which has higher viscosity and higher carbon nanotube content is used.
The procedure is as in example 1. The difference is that: weighing 1 g of the treated carbon nano tube powder and 1 g of epoxy resin prepolymer containing a curing agent, and fully stirring to obtain a black mixture with certain plasticity. Inserting one end of a hard glass tube with the outer diameter of 4 mm, the inner diameter of 2 mm and the length of 8 cm into the black mixture, filling the black mixture of the carbon nano tube epoxy resin prepolymer into the hard glass tube to the filling depth of about 6 mm, then inserting a copper wire with the length of 15 cm and the diameter of 0.3 mm into the hard glass tube through another opening until the copper wire is inserted into the black mixture of the carbon nano tube epoxy resin prepolymer in the hard glass tube by about 3 mm to ensure good contact, then placing the hard glass tube in a metal box with air vents shown in figure 2, and keeping the temperature at 100 ℃ for 10 minutes; then taking out and polishing one end of the hard glass tube filled with the mixture by using sand paper to form a circle; and after being melted, the hot melt adhesive is dripped at the contact part of the copper wire and the opening end of the hard glass tube to fix the copper wire and seal the hard glass tube, thus obtaining the finished product of the carbon nanotube epoxy resin composite material electrode for the voltammetry analysis of the chemical components of the tobacco.
Comparative example 2: the difference from example 2 is that the carbon nanotube epoxy resin composite electrode is prepared by a common heating and curing method.
FIG. 8 is a voltammogram at 0.5mM rutin for the electrode prepared in example 2 and the electrode prepared in comparative example 2, both at 100 ℃ and at 100 mV/s. Wherein FIG. 8 (A) is the result of detection of the electrode of example 2; and (B) is the detection result of the electrode of comparative example 2. Rutin is a common flavonoid substance in tobacco, and as can be seen from fig. 8, the oxidation peak current of rutin on the electrode prepared in example 2 is twice that of rutin on the electrode prepared in comparative example 2. It is demonstrated that infrared can improve the conductivity and electrocatalytic activity of carbon nanotube networks in the composite material.
The foregoing shows and describes the general principles, essential features, and advantages of the invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The carbon nanotube epoxy resin composite material electrode is characterized by comprising an electrode body, an electrode tube and an electrode lead; the electrode body is filled at one end of the electrode tube, and the bottom of the electrode body is round; the electrode lead is led out from the electrode body and is led out from the other end in the electrode tube; the electrode body is obtained by condensation polymerization of carbon nanotubes containing a curing agent and epoxy resin, wherein the mass of the carbon nanotubes is 10-50% of the mass of the electrode body.
2. The carbon nanotube epoxy composite electrode according to claim 1, wherein the electrode tube is made of an electrically insulating material, the electrode tube is one of a plastic tube, a ceramic tube, a quartz tube or a glass tube, and the inner diameter of the electrode tube is 25um to 8mm; the electrode lead is fixed at the other end of the electrode tube by using an adhesive, and the electrode tube at the end is sealed, wherein the adhesive is one of hot melt adhesive, epoxy resin, silicone adhesive or alpha-ethyl cyanoacrylate.
3. The carbon nanotube epoxy composite electrode of claim 1, wherein the carbon nanotubes are single-walled carbon nanotubes or multi-walled carbon nanotubes treated with nitric acid.
4. The method for preparing the carbon nanotube epoxy composite electrode according to any one of claims 1 to 3, comprising the steps of:
(1) Mixing the carbon nano tube, the epoxy resin and the curing agent according to a certain mass ratio to obtain a black viscous mixture with certain plasticity;
(2) Filling the mixture obtained in the step (1) into one end of an electrode tube, and then inserting an electrode lead into the mixture through the other end of the electrode tube;
(3) Curing the electrode tube obtained in the step (2) for a period of time at an infrared ray and a certain temperature;
(4) Polishing one end of the electrode tube solidified in the step (3) into a round shape; fixing the electrode lead at the other end of the electrode tube by using an adhesive, and sealing the end electrode tube; and obtaining the carbon nano tube epoxy resin composite material electrode.
5. The method according to claim 4, wherein the step of treating the carbon nanotubes with nitric acid in step (1) is as follows: dispersing carbon nano tubes in nitric acid, heating at 50-95 ℃ for 8-15 hours, cooling to room temperature, carrying out vacuum filtration, cleaning until the pH value of filtrate is higher than 5, and heating and drying the solid to obtain the carbon nano tubes treated by the nitric acid.
6. The method according to claim 4, wherein the carbon nanotubes of step (1) are single-walled carbon nanotubes or multi-walled carbon nanotubes; the mass of the carbon nano tube is 10-50% of the mass of the carbon nano tube, the epoxy resin and the curing agent.
7. The preparation method according to claim 4, wherein the electrode tube in the step (2) is made of an electrically insulating material, the electrode tube is one of a plastic tube, a ceramic tube, a quartz tube or a glass tube, and the inner diameter of the electrode tube is 25um-8mm; the adhesive in the step (4) is one of hot melt adhesive, epoxy resin, silicone adhesive or alpha-ethyl cyanoacrylate.
8. The method according to claim 4, wherein the infrared ray of step (3) has a wavelength of 1.40-11000um, a curing temperature of 80-120 ℃, and a curing time of 5-20min.
9. The method according to claim 8, wherein the infrared ray of step (3) has a wavelength of 3 to 100um, a curing temperature of 100 ℃ and a curing time of 10min.
10. Use of the carbon nanotube epoxy composite electrode according to any one of claims 1 to 3 for the detection of chemical components in tobacco.
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| CN100569851C (en) * | 2007-04-29 | 2009-12-16 | 南昌大学 | A kind of preparation method of carbon nano tube/epoxy resin matrix material |
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