CN114199952A - Ternary composite gas sensor and preparation method thereof - Google Patents
Ternary composite gas sensor and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
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- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 76
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- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims abstract description 20
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 19
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 238000000576 coating method Methods 0.000 claims abstract description 11
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- 239000007789 gas Substances 0.000 claims description 38
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- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 12
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- 239000010408 film Substances 0.000 claims 10
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 16
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
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- G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
- G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles
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Abstract
The invention belongs to the technical field of gas sensors and preparation thereof, and particularly relates to a ternary composite gas sensor and a preparation method thereof, wherein the preparation steps are as follows: dispersing hydroxylated multi-walled carbon nanotubes into a graphene oxide aqueous dispersion to prepare a graphene oxide/hydroxylated multi-walled carbon nanotube composite solution, reducing, washing and drying the composite solution to obtain a reductive graphene oxide/hydroxylated multi-walled carbon nanotube composite material, dispersing the composite material in deionized water, adding an aniline monomer, moving the composite material into an ice water bath, adding hydrochloric acid, dropwise adding an ammonium persulfate aqueous solution to initiate polymerization reaction to obtain a reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary complex, preparing the ternary composite material into a dispersion solution, coating the dispersion solution on the surface of an electrode substrate, and drying the ternary composite gas sensor to obtain a ternary composite gas sensor; the ternary composite gas sensor prepared by the invention has the characteristics of high sensitivity, good selectivity, good repeatability and the like in response to ammonia gas.
Description
Technical Field
The invention belongs to the technical field of gas sensors and preparation thereof, and particularly relates to a ternary composite gas sensor and a preparation method thereof.
Background
As an important organic gas sensitive device, the polyaniline gas sensor has the characteristics of simple film formation, low cost and the like, and has been widely regarded in recent years. The invention patent (application number 201310127805.8) discloses a polyaniline/carbon nano tube composite film gas sensor and a preparation method thereof, which comprises the following steps: ultrasonically dispersing carbon nanotubes in an aqueous solution of polystyrene sulfonic acid, sequentially adding an aniline monomer and an ammonium persulfate aqueous solution to initiate a polymerization reaction to obtain an aqueous dispersion polyaniline/carbon nanotube composite material aqueous solution after the reaction is finished, finally coating the composite material aqueous solution on an interdigital gold electrode, and drying to obtain the gas sensor. The gas sensor has better response to ammonia, but adjacent carbon tubes are easy to gather and entangle, which is not beneficial to further improving the gas-sensitive performance of the polyaniline by the carbon nanotubes. Therefore, it is necessary to develop a new method for improving the gas sensing performance of the polyaniline sensor.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite gas sensor which has high sensitivity, good selectivity to ammonia gas, room-temperature operation and a simple structure, and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
a preparation method of a ternary composite gas sensor comprises the following steps:
step 1: the preparation method comprises the following steps of (1) preparing a mixture of a hydroxylated multi-wall carbon nanotube and a graphene oxide aqueous dispersion according to a mass ratio of 1: (1-2) mixing, stirring, performing ultrasonic treatment and performing hydrothermal reduction to prepare a reducing graphene oxide/hydroxylated multi-walled carbon nanotube composite material;
step 2: sequentially adding aniline monomer, hydrochloric acid and ammonium persulfate aqueous solution into the reducing graphene oxide/hydroxylated multi-walled carbon nanotube composite material to initiate polymerization reaction, and preparing the reducing graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite material;
and step 3: growing a layer of silicon dioxide film on a silicon wafer by a thermal oxidation method, and depositing a layer of metal film on the surface of the silicon dioxide film by a vacuum coating method; processing the metal film by using a mask and a photoetching technology to form a first electrode and a second electrode to obtain an electrode substrate;
and 4, step 4: and preparing the sensor element attached with the reductive graphene oxide/hydroxylated multi-wall carbon nanotube/polyaniline ternary composite film.
By adopting the technical scheme, in the prior art, because strong van der Waals force exists between carbon tubes, adjacent carbon tubes are easy to aggregate and entangle, so that the adjacent carbon tubes are difficult to uniformly disperse in a polyaniline matrix in the polymerization reaction process of aniline monomers, and the further improvement of the polyaniline gas-sensitive performance of the carbon nanotubes is not facilitated.
Further, the response mechanism of gas sensors is typically based on charge transfer between the gas molecules and the sensitive material, due to sp2Due to the damage of the bonding network, the graphene oxide has poor conductivity, and therefore, after being compounded with polyaniline, the graphene oxide does not have performance advantages in the application of the sensor, so that in the technical scheme, the graphene oxide is further converted into reductive graphene oxide with good conductivity and then is compounded with polyaniline, a polyaniline-based composite material with better performance can be obtained, and the response sensitivity of the sensor to ammonia is further improved.
As a preferable mode, the step 1 specifically includes:
step 1.1: and (2) mixing the hydroxylated multi-wall carbon nanotube with the graphene oxide aqueous dispersion according to the mass ratio of 1: (1-2) mixing and stirring to obtain a dispersion solution with the concentration of 0.5-1 mg/ml, and performing ultrasonic treatment for 30-60 min to obtain a uniform and stable aqueous dispersion of graphene oxide/hydroxylated multi-walled carbon nanotubes;
step 1.2: and (3) putting the aqueous dispersion into a high-pressure reaction kettle, preventing the high-pressure reaction kettle from being placed in an environment at 160-220 ℃ for about 12-18 hours for hydrothermal reduction, and naturally cooling to room temperature after the reaction is finished to obtain the reducing graphene oxide/hydroxylated multi-walled carbon nanotube suspension.
Preferably, the original graphene oxide/hydroxylated multi-wall carbon nanotube suspension is further treated, and specifically, the suspension is washed for 3-5 times by deionized water and ethanol; drying at 60 ℃ under a vacuum condition to prepare reducing graphene oxide/hydroxylated multi-walled carbon nanotube composite powder; dispersing the reductive graphene oxide/hydroxylated multi-walled carbon nanotube composite powder into 10-100 ml of deionized water, and performing ultrasonic treatment for 30-60 min to obtain a treated reductive graphene oxide/hydroxylated multi-walled carbon nanotube suspension.
By adopting the preferred technical scheme, the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite powder is added into deionized water with controllable volume to be compounded with an aniline monomer, so that a fibrous polyaniline composite material with larger surface area can be prepared, the contact area of a ternary composite sensitive film and gas molecules is increased, and the gas-sensitive performance is improved.
As a preferable mode, the step 2 specifically includes:
step 2.1: adding an aniline monomer into the reductive graphene oxide/hydroxylated multi-walled carbon nanotube suspension to form a mixed solution;
step 2.2: transferring the mixed solution into an ice-water bath, carrying out continuous magnetic stirring, sequentially adding hydrochloric acid and an ammonium persulfate aqueous solution to initiate a polymerization reaction, and continuously carrying out continuous magnetic stirring until the polymerization reaction is finished to obtain a reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite solution;
step 2.3: and precipitating and filtering the ternary composite solution, rinsing and drying to obtain the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite powder.
Further preferably, the step 2.2 specifically comprises: and transferring the mixed solution into an ice-water bath, carrying out continuous magnetic stirring for 30-60 min, adding a hydrochloric acid solution with the concentration of 1-2 mol/L, continuing to carry out magnetic stirring for 30-60 min, then dropwise adding an ammonium persulfate aqueous solution with the concentration of 0.01-0.03mol/mL, and simultaneously keeping the continuous magnetic stirring until the polymerization reaction is completed to obtain the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite solution.
And (3) cleaning the electrode substrate obtained in the step 3 by using acetone, ethanol and deionized water respectively.
As a preferable mode, the step 4 specifically includes:
step 4.1: dispersing the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite material powder obtained in the step 2 into a mixed solution of deionized water and 1-3 mg/ml of ethanol, and performing ultrasonic treatment for 15-30 min to obtain a stable dispersion liquid;
step 4.2: and coating the obtained dispersion liquid on the surface of the electrode substrate, and drying in nitrogen for 6-24 hours to obtain the electrode substrate attached with the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite film.
More preferably, the sheet diameter of the graphene oxide is 20nm to 0.5 μm; the average diameter of the hydroxylated multi-wall carbon nano-tube is 10-100 nm, and the length of the hydroxylated multi-wall carbon nano-tube is 10 nm-1.2 mu m.
Further preferably, the thickness of the silicon dioxide film is 200-500 nm; the thickness of the metal film is 100-500 nm.
Further preferably, the vacuum coating method is an evaporation coating method or a sputter coating method.
Further preferably, the coating process is any one of a dropping coating method, a spin coating method, or a spray coating method.
A ternary composite gas sensor comprises a silicon substrate at the bottom of the sensor, a silicon dioxide film above the silicon substrate, a first electrode and a second electrode on the surface of the silicon dioxide film, and a reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite film attached between the first electrode and the second electrode and on the upper surface of the first electrode and the second electrode.
By adopting the technical scheme, the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite film is attached between the first electrode and the second electrode and on the upper surface of the first electrode and the second electrode, the response of polyaniline to ammonia gas is promoted by utilizing the complex synergistic effect between ternary composite materials, and the sensitivity of the sensor is improved.
As a preferable mode, the electrode pattern in the electrode substrate is in a comb-tooth shape in a staggered arrangement.
Further preferably, the distance between the adjacent first electrodes and the second electrodes is 10-80 μm, and the arrangement mode is favorable for improving the response sensitivity of the sensor.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
the ammonia-sensitive film of the ternary composite gas sensor consists of the reductive graphene oxide/hydroxylated multiwalled carbon nanotube/polyaniline ternary composite film, and the response of polyaniline to ammonia is promoted by utilizing the complex synergistic effect among ternary composite materials, so that the sensitivity of the sensor is improved; after the carbon nano tubes are dispersed by the graphene oxide aqueous solution, the carbon nano tubes can be more uniformly dispersed in the polyaniline matrix in the following in-situ polymerization process. Although graphene oxide has poor conductivity and is not beneficial to enhancing electron delocalization, the conductivity of the graphene oxide can be improved after the graphene oxide is reduced into reduced graphene oxide by a hydrothermal reduction method. In the process, reduced graphene oxide sheets converted from graphene oxide through hydrothermal reduction not only wrap the carbon nanotubes, but also are distributed among adjacent carbon nanotubes. Meanwhile, after the graphene oxide is reduced, most of oxygen-containing functional groups of the graphene oxide can be removed, and the conjugated structure and the conductivity are recovered. In the in-situ polymerization process, the polyaniline layer is polymerized not only on the carbon nanotubes, but also on a large number of reductive graphene oxide sheets with good conductivity. The existence of the reductive graphene oxide sheet enables the contact area between the gas molecules and the polyaniline layer to be remarkably increased, and the probability of pi electron delocalization is greatly enhanced, so that the charge transfer effect between the gas molecules and the ternary composite material is enhanced. Therefore, the ternary composite material has better gas-sensitive properties such as sensitivity, selectivity, repeatability and the like to a certain extent.
Drawings
The invention will now be described, by way of example, with reference to the accompanying drawings, in which:
FIG. 1 is a schematic side view of a ternary complex sensor according to the present invention.
FIG. 2 is a schematic top view of a ternary complex sensor according to the present invention.
FIG. 3 is a graph showing the response of the ternary complex sensor of the present invention to ammonia gas.
FIG. 4 is a graph of the results of the repetitive tests of the ternary composite sensor of the present invention.
FIG. 5 is a bar graph of the results of the selectivity test of the ternary complex sensor of the present invention.
Reference numerals
The preparation method comprises the following steps of 1-a silicon substrate, 2-a silicon dioxide film, 3-a first electrode, 4-a second electrode, 5-reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite film, 51-polyaniline, 52-reductive graphene oxide sheets and 53-hydroxylated multi-walled carbon nanotubes.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all the embodiments. The components of embodiments of the present application, generally described and illustrated in the figures herein, may be arranged and designed in a wide variety of different configurations. Thus, the following detailed description of the embodiments of the present application, presented in the accompanying drawings, is not intended to limit the scope of the claimed application, but is merely representative of selected embodiments of the application. All other embodiments, which can be derived by a person skilled in the art from the embodiments of the present application without making any creative effort, shall fall within the protection scope of the present application.
In the description of the embodiments of the present application, it should be noted that the terms "upper", "lower", "left", "right", "vertical", "horizontal", "inner", "outer", and the like indicate orientations or positional relationships based on the orientations or positional relationships shown in the drawings or orientations or positional relationships that the products of the present invention are usually placed in when used, and are only used for convenience of description and simplicity of description, but do not indicate or imply that the devices or elements that are referred to must have a specific orientation, be constructed and operated in a specific orientation, and thus, should not be construed as limiting the present application. Furthermore, the terms "first," "second," "third," and the like are used solely to distinguish one from another and are not to be construed as indicating or implying relative importance.
The present invention will be described in detail with reference to fig. 1 to 5.
It will be evident to those skilled in the art that the invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
The invention is further described below with reference to the accompanying drawings:
example 1
A preparation method of a ternary composite gas sensor comprises the following steps:
1) dispersing 5mg of hydroxylated multi-wall carbon nano-tubes into 20ml of brown graphene oxide aqueous dispersion (the concentration is 0.5mg/ml), and carrying out ultrasonic treatment for 30 minutes to achieve a uniform and stable state; transferring the obtained graphene oxide/hydroxylated multi-walled carbon nanotube aqueous dispersion into a sealed stainless steel high-pressure reaction kettle with a Teflon lining, preventing the reaction kettle from being placed in a heating box at 180 ℃ for about 18 hours for hydrothermal reduction, and standing and naturally cooling to room temperature after the reaction is finished; taking the obtained reductive graphene oxide/hydroxylated multi-walled carbon nanotube suspension out of the reaction kettle, and washing the suspension for 3-5 times by using deionized water and ethanol; finally, drying the mixture at the temperature of 60 ℃ under a vacuum condition to obtain reducing graphene oxide/hydroxylated multi-walled carbon nanotube composite powder;
2) dispersing 5mg of the reductive graphene oxide/hydroxylated multi-walled carbon nanotube composite powder obtained in the step 1) into 80ml of deionized water, and performing ultrasonic treatment for 30 minutes to obtain a reductive graphene oxide/hydroxylated multi-walled carbon nanotube suspension; adding 200 mu L of aniline monomer into the reductive graphene oxide/hydroxylated multi-walled carbon nanotube suspension to form a mixed solution, transferring the mixed solution into an ice water bath, carrying out continuous magnetic stirring for 30 minutes, adding 8.3ml (with the concentration of 1mol/L) of hydrochloric acid solution, adding into the mixed solution, and continuing to carry out magnetic stirring for 30 minutes; then, dropwise adding 20mL (0.02mol/mL) of ammonium persulfate aqueous solution, and simultaneously keeping continuous magnetic stirring until the polymerization reaction is completed to obtain a reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite solution; precipitating and filtering the ternary composite solution, then respectively rinsing with deionized water and ethanol for several times, and drying in a vacuum oven at 25 ℃ for 24 hours to finally obtain reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite material powder;
3) growing a layer of silicon dioxide film 2 on a silicon wafer by a thermal oxidation method, and depositing a layer of metal film on the surface of the silicon dioxide film 2 by a vacuum coating method; processing the metal film by using a mask and a photoetching technology to form a first electrode 3 and a second electrode 4 to obtain electrode substrates, and cleaning the electrode substrates respectively by using acetone, ethanol and deionized water for further use;
4) dispersing the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite material powder obtained in the step 2) into a mixed solution of deionized water and ethanol (1mg/ml), and performing ultrasonic treatment for 15 minutes to obtain a stable dispersion liquid; and (3) taking out 4 mu L of the obtained dispersion liquid, coating the dispersion liquid on the surface of the electrode substrate obtained in the step 3), and placing the electrode substrate in nitrogen for drying for 18 hours to obtain the electrode substrate attached with the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite film 5.
Example 2:
a preparation method of a ternary composite gas sensor comprises the following steps:
1) dispersing 15mg of hydroxylated multi-wall carbon nano-tubes into 30ml of brown graphene oxide aqueous dispersion (the concentration is 0.5mg/ml), and carrying out ultrasonic treatment for 60 minutes to achieve a uniform and stable state; transferring the obtained graphene oxide/hydroxylated multi-walled carbon nanotube aqueous dispersion into a sealed stainless steel high-pressure reaction kettle with a Teflon lining, preventing the reaction kettle from being placed in a heating box at 220 ℃ for about 12 hours for hydrothermal reduction, and standing and naturally cooling to room temperature after the reaction is finished; taking the obtained reductive graphene oxide/hydroxylated multi-walled carbon nanotube suspension out of the reaction kettle, and washing the suspension for 3-5 times by using deionized water and ethanol; finally, drying the mixture at the temperature of 60 ℃ under a vacuum condition to obtain reducing graphene oxide/hydroxylated multi-walled carbon nanotube composite powder;
2) dispersing 10mg of the reductive graphene oxide/hydroxylated multi-walled carbon nanotube composite powder obtained in the step 1) into 50ml of deionized water, and performing ultrasonic treatment for 30 minutes to obtain a reductive graphene oxide/hydroxylated multi-walled carbon nanotube suspension; adding 400 mu L of aniline monomer into the reductive graphene oxide/hydroxylated multi-walled carbon nanotube suspension to form a mixed solution, transferring the mixed solution into an ice water bath, carrying out continuous magnetic stirring for 60 minutes, adding 15ml (with the concentration of 2mol/L) of hydrochloric acid solution, adding into the mixed solution, and continuing to carry out magnetic stirring for 45 minutes; then, dropwise adding 50mL (0.03mol/mL) of ammonium persulfate aqueous solution, and simultaneously keeping continuous magnetic stirring until the polymerization reaction is completed to obtain a reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite solution; precipitating and filtering the ternary composite solution, then respectively rinsing with deionized water and ethanol for several times, and drying in a vacuum oven at 50 ℃ for 18 hours to finally obtain reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite material powder;
3) growing a layer of silicon dioxide film 2 on a silicon wafer by a thermal oxidation method, and depositing a layer of metal film on the surface of the silicon dioxide film 2 by a vacuum coating method; processing the metal film by using a mask and a photoetching technology to form a first electrode 3 and a second electrode 4 to obtain electrode substrates, and cleaning the electrode substrates respectively by using acetone, ethanol and deionized water for further use;
4) dispersing the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite material powder obtained in the step 2) into a mixed solution of deionized water and ethanol (1mg/ml), and performing ultrasonic treatment for 30 minutes to obtain a stable dispersion liquid; and (3) taking out 8 mu L of the obtained dispersion liquid, coating the dispersion liquid on the surface of the electrode substrate obtained in the step 3), and placing the electrode substrate in nitrogen for drying for 24 hours to obtain the electrode substrate attached with the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite film 5.
In the embodiment, the sheet diameter of the graphene oxide in the step 1) is 50-200 nm; the hydroxylated multi-walled carbon nanotube 53 has an average diameter of about 10 to 20nm and a length of 10 to 30 nm.
In the above embodiment, the thickness of the silicon dioxide insulating layer grown on the silicon substrate 1 in step 3) is 300 nm; the vacuum coating method in the step 3) is an evaporation coating method; the metal film deposited on the silicon dioxide film 2 by the vacuum coating method in the step 3) is gold, and the thickness is about 100 nm.
In the above embodiment, the coating process in step 4) is a dropping method.
Example 3:
a ternary composite gas sensor is disclosed, referring to fig. 1 and fig. 2, and comprises a silicon substrate 1 at the bottom of the sensor, a silicon dioxide film 2 above the silicon substrate 1, a first electrode 3 and a second electrode 4 on the surface of the silicon dioxide film 2, and a reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite film 5 attached between the first electrode 3 and the second electrode 4 and on the upper surface thereof.
Further, the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite film 5 is composed of reductive graphene oxide sheets 52, hydroxylated multi-walled carbon nanotubes 53 and polyaniline 51.
In a preferred embodiment, the electrode pattern in the electrode substrate has a shape of comb teeth arranged in a staggered manner.
Furthermore, the distance between the adjacent first electrodes 3 and the second electrodes 4 is 10 to 80 μm.
By testing the resistance response of the ternary composite gas sensor in the embodiment of the invention in the ammonia gas environments with different concentrations, the test result is shown in fig. 3, and the resistance response of the sensor is correspondingly increased along with the increase of the ammonia gas concentration.
The ternary complex gas sensor of the embodiment of the present invention was tested for repeatability and, as shown in fig. 4, exhibited good repeatability and faster response and recovery times.
The selectivity of the ternary composite gas sensor in the embodiment of the invention is tested, and as shown in fig. 5, the sensor shows high ammonia selectivity.
The above-mentioned embodiments are only used for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of a ternary composite gas sensor is characterized by comprising the following steps:
step 1: the preparation method comprises the following steps of (1) preparing a mixture of a hydroxylated multi-wall carbon nanotube and a graphene oxide aqueous dispersion according to a mass ratio of 1: (1-2) mixing, stirring, performing ultrasonic treatment and performing hydrothermal reduction to prepare a reducing graphene oxide/hydroxylated multi-walled carbon nanotube composite material;
step 2: sequentially adding aniline monomer, hydrochloric acid and ammonium persulfate aqueous solution into the reducing graphene oxide/hydroxylated multi-walled carbon nanotube composite material to initiate polymerization reaction, and preparing the reducing graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite material;
and step 3: growing a layer of silicon dioxide film on a silicon wafer by a thermal oxidation method, and depositing a layer of metal film on the surface of the silicon dioxide film by a vacuum coating method; processing the metal film by using a mask and a photoetching technology to form a first electrode and a second electrode to obtain an electrode substrate;
and 4, step 4: and preparing the sensor element attached with the reductive graphene oxide/hydroxylated multi-wall carbon nanotube/polyaniline ternary composite film.
2. The method for preparing a ternary composite gas sensor according to claim 1, wherein the step 1 specifically comprises:
step 1.1: and (2) mixing the hydroxylated multi-wall carbon nanotube with the graphene oxide aqueous dispersion according to the mass ratio of 1: (1-2) mixing and stirring to obtain a dispersion solution with the concentration of 0.5-1 mg/ml, and performing ultrasonic treatment for 30-60 min to obtain a uniform and stable aqueous dispersion of graphene oxide/hydroxylated multi-walled carbon nanotubes;
step 1.2: putting the aqueous dispersion into a high-pressure reaction kettle, preventing the high-pressure reaction kettle from being placed in an environment of 160-220 ℃ for about 12-18 hours for hydrothermal reduction, naturally cooling to room temperature after the reaction is finished, and washing for 3-5 times by using deionized water and ethanol; drying at 60 ℃ under a vacuum condition to prepare reducing graphene oxide/hydroxylated multi-walled carbon nanotube composite powder; dispersing the reductive graphene oxide/hydroxylated multi-walled carbon nanotube composite powder into 10-100 ml of deionized water, and performing ultrasonic treatment for 30-60 min to obtain a reductive graphene oxide/hydroxylated multi-walled carbon nanotube suspension.
3. The method for preparing a ternary composite gas sensor according to claim 2, wherein the step 2 specifically comprises:
step 2.1: adding an aniline monomer into the reductive graphene oxide/hydroxylated multi-walled carbon nanotube suspension to form a mixed solution;
step 2.2: transferring the mixed solution into an ice-water bath, carrying out continuous magnetic stirring, sequentially adding hydrochloric acid and an ammonium persulfate aqueous solution to initiate a polymerization reaction, and continuously carrying out continuous magnetic stirring until the polymerization reaction is finished to obtain a reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite solution;
step 2.3: and precipitating and filtering the ternary composite solution, rinsing and drying to obtain the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite powder.
4. The method for preparing a ternary composite gas sensor according to claim 3, wherein the step 2.2 specifically comprises: and transferring the mixed solution into an ice-water bath, carrying out continuous magnetic stirring for 30-60 min, adding a hydrochloric acid solution with the concentration of 1-2 mol/L, continuing to carry out magnetic stirring for 30-60 min, then dropwise adding an ammonium persulfate aqueous solution with the concentration of 0.01-0.03mol/mL, and simultaneously keeping the continuous magnetic stirring until the polymerization reaction is completed to obtain the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite solution.
5. The method for preparing a ternary composite gas sensor according to claim 4, wherein the step 4 specifically comprises:
step 4.1: dispersing the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite material powder obtained in the step 2 into a mixed solution of deionized water and 1-3 mg/ml of ethanol, and performing ultrasonic treatment for 15-30 min to obtain a stable dispersion liquid;
step 4.2: and coating the obtained dispersion liquid on the surface of the electrode substrate, and drying in nitrogen for 6-24 hours to obtain the electrode substrate attached with the reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite film.
6. The method for preparing a ternary composite gas sensor according to claim 5, wherein the thickness of the silica thin film is 200 to 500 nm; the thickness of the metal film is 100-500 nm.
7. The method for preparing a ternary composite gas sensor according to claim 1, wherein the sheet diameter of the reduced graphene oxide is 20nm to 0.5 μm; the average diameter of the hydroxylated multi-wall carbon nano-tube is 10-100 nm, and the length of the hydroxylated multi-wall carbon nano-tube is 10 nm-1.2 mu m.
8. The ternary composite gas sensor is characterized by comprising a silicon substrate (1) at the bottom of the sensor, a silicon dioxide film (2) above the silicon substrate (1), a first electrode (3) and a second electrode (4) on the surface of the silicon dioxide film (2), wherein a reductive graphene oxide/hydroxylated multi-walled carbon nanotube/polyaniline ternary composite film (5) is attached between the first electrode (3) and the second electrode (4) and on the upper surface of the first electrode and the second electrode.
9. The ternary composite gas sensor as claimed in claim 8, wherein the electrode pattern of the electrode substrate is in the shape of comb teeth arranged in a staggered manner.
10. The ternary composite gas sensor according to claim 9, wherein the distance between the adjacent first electrode (3) and the second electrode (4) is 10-80 μm.
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