CN109932400B - Composite membrane and preparation method and application thereof - Google Patents
Composite membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a composite membrane and a preparation method and application thereof, wherein the method comprises the following steps: mixing the fullerol with a silane coupling agent and then dehydrating to obtain fullerene modified by the silane coupling agent; preparing an alkaline solution of fullerene modified by a silane coupling agent; depositing an alkaline solution of the silane coupling agent modified fullerene on the substrate to form a first thin film; and depositing the metal oxide nanoparticle solution on the first film to form a second film, and combining amino or sulfhydryl on the surface of fullerene on the surface of the first film with surface metal elements in metal oxide nanoparticles on the surface of the second film at the combined interface of the first film and the second film to prepare the composite film. The invention not only can reduce the preparation cost of the gas sensor, but also can further improve the selection performance of the gas sensor.
Description
Technical Field
The invention relates to the technical field of gas-sensitive sensing devices, in particular to a composite film and a preparation method and application thereof.
Background
Semiconductor sensors (semiconductor sensors) utilize various physical, chemical, and biological properties of semiconductor materials to make sensors. Most of the semiconductor materials used are silicon and compounds of elements of groups III-V and II-VI. Semiconductor sensors are various in types, and have various sensory functions similar to human eyes, ears, noses, tongues, skins and the like by utilizing the characteristics of nearly one hundred physical effects and materials. For the gas sensor, the metal oxide nano material is mainly used for preparation, and the metal oxide nano material has the characteristics of large specific surface area, excellent electrical property and sensitivity to surface adsorption, so that the application of the semiconductor metal oxide to the gas of the gas sensor is expected to obtain a sensing device with high response speed, high sensitivity and good selectivity.
Although certain achievements have been made in the current metal oxide-based gas sensors, further improvements and improvements in sensitivity and selectivity are still needed. Reducing the size of the nanoparticles and increasing the specific surface area of the material are key to improving the sensitivity and selectivity of the sensor. In the prior art, in order to increase the specific surface area, the electrical conductivity and the surface adsorption sensitivity of the nano material, graphene and nano particles are compounded to improve the selection performance of the sensor. However, the graphene and nanoparticle composite also has some disadvantages, such as the loose combination between the graphene and the nanoparticle affects the conductivity between the nanoparticle film and the graphene, and the high cost of the vapor deposition technology is needed when the graphene layer is prepared.
Accordingly, the prior art is yet to be improved and developed.
Disclosure of Invention
In view of the above disadvantages of the prior art, an object of the present invention is to provide a composite film, a method for preparing the same, and an application of the composite film, which are intended to solve the problems that the existing graphene and nanoparticles are not tightly bonded, which affects the conductivity between the nanoparticle film and the graphene, and that the cost is high due to the need of using a vapor deposition technique when preparing the graphene layer.
The technical scheme of the invention is as follows:
a method of making a composite membrane, comprising the steps of:
providing fullerol, mixing the fullerol with a silane coupling agent, and dehydrating to obtain fullerene modified by the silane coupling agent, wherein the general formula of the silane coupling agent is YSiX3Wherein X is alkoxy, Y is a non-hydrolyzable group, and the end of the carbon chain in Y contains an amino substituent or a mercapto substituent;
providing a metal oxide nanoparticle solution;
providing a substrate, and depositing an alkaline solution of the fullerene modified by the silane coupling agent on the substrate to form a first thin film;
and depositing the metal oxide nanoparticle solution on the first film to form a second film, and combining amino or sulfhydryl on the surface of fullerene on the surface of the first film with surface metal elements in metal oxide nanoparticles on the surface of the second film at the combined interface of the first film and the second film to prepare the composite film.
The preparation method of the composite membrane, wherein the general formula of the fullerol is Cm(OH)nWherein m is more than or equal to 28 and less than or equal to 104, n is more than or equal to 16 and less than or equal to 60, n<m。
The preparation method of the composite membrane comprises the step of selecting the silane coupling agent from NH2(CH2)3Si（OCH3）3、NH2(CH2)3Si（OC2H5）3、NH2(CH2)2NH(CH2)3Si（OCH3）3、NH2(CH2)2NH(CH2)3Si（OC2H5）3And SH (CH)2)3Si（OC2H5）3One kind of (1).
The preparation method of the composite film comprises the following steps of mixing the fullerol and the silane coupling agent and then dehydrating, wherein the molar ratio of the fullerol to the silane coupling agent is 1 mmol: (15-20 mmol), and mixing the fullerol with the silane coupling agent.
The preparation method of the composite membrane comprises the step of adding silane coupling agent modified fullerene into alkaline solution of silane coupling agent modified fullerene, wherein the concentration of the silane coupling agent modified fullerene is 20-40 mg/mL.
In the preparation method of the composite film, in the metal oxide nanoparticle solution, the particle size of the metal oxide nanoparticles is 1-100 nm.
The preparation method of the composite film comprises the following steps of depositing an alkaline solution of fullerene modified by the silane coupling agent on the substrate to form a first film: and depositing an alkaline solution of the fullerene modified by the silane coupling agent on the substrate by a solution method in an atmospheric environment, and annealing for 30-60min at 40-60 ℃ to form a first film on the substrate.
The method for preparing the composite film, wherein the step of depositing the metal oxide nanoparticle solution on the first thin film to form a second thin film, and bonding an amino group or a thiol group on the surface of the fullerene on the surface of the first thin film to a surface metal element on the metal oxide nanoparticle on the surface of the second thin film at the bonding interface between the first thin film and the second thin film comprises: depositing the metal oxide nanoparticle solution on the surface of the first film, annealing for 30-60min at 60-90 ℃, and laminating the first film and the second film to form a second film.
A composite film comprises a first film, wherein the material of the first film comprises fullerene modified by silane coupling agent, and the general formula of the silane coupling agent is YSiX3Wherein X is alkoxy, Y is a non-hydrolyzable group, and the end of the carbon chain in Y contains an amino substituent or a mercapto substituent;
the second film is formed on one surface of the first film in a laminated mode, and the material of the second film is metal oxide nano particles;
at the bonding interface of the first and second thin films, an amino group or a mercapto group in the silane coupling agent in the fullerene located on the surface of the first thin film is bonded to a surface metal element in the metal oxide nanoparticle located on the surface of the second thin film.
Use of a composite film according to the invention as a gas-sensitive layer in a gas sensor.
Has the advantages that: compared with the prior art, the invention has the following advantages: firstly, the preparation cost can be reduced, and the specific surface area of the composite membrane can be further increased, so that the selection performance of the gas sensor is further improved; secondly, the electric conductivity of the composite film can be further enhanced, and the photoresponse rate can be improved; and thirdly, the silane coupling agent not only can effectively enable the fullerol and the metal nanoparticles to be closely associated to improve the density of the composite membrane, but also can improve the charge conductivity between the metal oxide nanoparticles and the fullerol.
Drawings
Fig. 1 is a schematic structural diagram of a gas sensor according to an embodiment of the present invention.
Detailed Description
The invention provides a composite membrane and a preparation method and application thereof, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a composite membrane, which comprises the following steps:
providing fullerol, mixing the fullerol with a silane coupling agent, and dehydrating to obtain fullerene modified by the silane coupling agent, wherein the general formula of the silane coupling agent is YSiX3Wherein X is alkoxy, Y is a non-hydrolyzable group, and the end of the carbon chain in Y contains an amino substituent or a mercapto substituent;
preparing an alkaline solution of fullerene modified by a silane coupling agent;
providing a metal oxide nanoparticle solution;
providing a substrate, and depositing an alkaline solution of the fullerene modified by the silane coupling agent on the substrate to form a first thin film;
and depositing the metal oxide nanoparticle solution on the first film to form a second film, and combining amino or sulfhydryl on the surface of fullerene on the surface of the first film with surface metal elements in metal oxide nanoparticles on the surface of the second film at the combined interface of the first film and the second film to prepare the composite film.
In the prior art, the graphene and the metal oxide nanoparticles are not tightly bonded, so that the conductivity between the graphene and the metal oxide nanoparticles is affected, and a vapor deposition technology is required to be used for preparing the graphene layer, so that the cost is high. In order to solve the problems in the prior art, the invention mainly improves the following steps: the composite membrane is prepared by utilizing the characteristics of the fullerol, the silane coupling agent and the metal oxide nano particles. The method specifically comprises the following steps: firstly, carrying out surface modification on fullerol by using a silane coupling agent to obtain fullerene modified by the silane coupling agent, then depositing the fullerene modified by the silane coupling agent to obtain a first film, and finally depositing metal oxide nano particles on the first film to obtain a second film, wherein at the joint interface of the first film and the second film, amino or sulfhydryl on the surface of the fullerene on the surface of the first film is combined with surface metal elements in the metal oxide nano particles on the surface of the second film to form the composite film. The prepared composite film is used as a gas-sensitive layer in a gas-sensitive sensing device. Compared with the prior art, the invention has the following advantages: firstly, the preparation cost can be reduced, and the specific surface area of the composite membrane can be further increased, so that the selection performance of the gas sensor is further improved; secondly, the electric conductivity of the composite film can be further enhanced, and the photoresponse rate can be improved; and thirdly, the silane coupling agent not only can effectively enable the fullerol and the metal nanoparticles to be closely associated to improve the density of the composite membrane, but also can improve the charge conductivity between the metal oxide nanoparticles and the fullerol.
The fullerene has excellent electrical conductivity and larger specific surface area than graphene, so that the conductivity of the gas-sensitive layer can be further improved by utilizing the fullerene and the metal oxide nanoparticles. In addition, when the fullerene and the metal oxide nanoparticles are used for preparing the gas-sensitive layer together, the preparation of the fullerene solid film does not need to adopt a vapor deposition technology, thereby reducing the preparation cost.
The silane coupling agent not only has the function of a molecular bridge and can connect fullerene and metal oxide nanoparticles to realize the cross-linking between the fullerene and the metal oxide nanoparticles and generate ohmic contact, but also can play an anti-aging role to prolong the service life of the device, and simultaneously, the silane coupling agent is connected with the fullerene and the metal oxide nanoparticles to realize the uniform and close connection between the fullerene and the metal oxide nanoparticles and increase the contact area between the fullerene and the metal oxide nanoparticles.
After the metal oxide nanoparticles are combined with the fullerene, the adsorption and desorption rate of the metal oxide nanoparticles to other can be increased, and the conductivity of the metal oxide nanoparticles can be improved.
Fullerol is a derivative of fullerene, and is obtained by chemically introducing hydroxyl groups into fullerene carbons. The number of the introduced hydroxyl groups will be different due to different synthesis methods and different reaction conditions. In one embodiment of the present invention, the fullerene alcohol is obtained by alcoholizing fullerene by a conventional catalytic base method. The general formula of the fullerol is Cm(OH)nWherein m is more than or equal to 28 and less than or equal to 104, n is more than or equal to 16 and less than or equal to 60, and n<And m is selected. For example, C can be prepared by conventional catalytic alkaline process28，C60，C70，C76，C78，C82，C84，C88，C90，C96，C100Or C104And carrying out alcoholization on the fullerene. In order to achieve better solubility of the fullerol, the number of hydroxyl groups (-OH) is generally in the range (50%)<n/m<70%) the most preferred fullerol according to formula is C60(OH)36。
The silane coupling agent may be of a wide variety and in one embodiment may be used in the classical formula YSiX3Wherein X is a hydrolyzable group, preferably X is an alkoxy group, Y is a non-hydrolyzable group, and Y must contain an amino group (-NH)2) Or a mercapto group (-SH). The amino and the sulfhydryl can be well bonded with metal elements on the surface of metal oxide nanoparticles, and the hydrolytic group X is used for carrying out dehydration reaction with the hydroxyl of the fullerene alcohol, so that the surface modification of the fullerene is realized, and the fullerene material modified by the silane coupling agent is obtained. The fullerene has excellent conductivity, and the modified fullerene inherits the good conductivity of the fullerene because the hydroxyl on the surface of the fullerene alcohol is modified by the silane coupling agent to form-Si-O group which shows electronegativity and has little influence on the good conductivity (electron donor) of the fullerene.
Preferably, the silane coupling agent is selected from gamma-aminopropyl trimethoxy siliconAlkane (molecular formula is NH)2(CH2)3Si（OCH3）3KH-540 for short), and gamma-aminopropyltriethoxysilane (molecular formula NH)2(CH2)3Si（OC2H5）3KH-550 for short), N- (beta-aminoethyl) -gamma-aminopropyltriethoxysilane (NH in molecular formula)2(CH2)2NH(CH2)3Si（OC2H5）3KH-791) and N- (beta-aminoethyl) -gamma-aminopropyl trimethoxysilane (NH)2(CH2)2NH(CH2)3Si（OCH3）3Abbreviated as KH-792) and gamma-mercaptopropyltriethoxysilane (molecular formula SH (CH)2)3Si（OC2H5）3Abbreviated as KH-580), and the like. Still further preferably, the silane coupling agent is selected from KH-540 or KH-580.
With fullerol as C60(OH)36For example, the silane coupling agent is used for the reaction of fullerol C60(OH)36The procedure for performing the surface modification was as follows:
YSiX3 +3H2O
YSi(OH)3+3HX
12YSi(OH)3+ C60(OH)36 
(YSiO3)12C60 + 36H2O
in a preferred embodiment, in the step of mixing the fullerol with the silane coupling agent and then dehydrating, the ratio of the molar ratio of the fullerol to the silane coupling agent is 1 mmol: (15-20 mmol), and mixing the fullerol with the silane coupling agent. This is because the amount of the fullerene alcohol is too large, the modification is insufficient, and too small and excessive silane coupling agents are entangled with each other to affect the subsequent use.
In a preferred embodiment, in the alkaline solution of fullerene modified by silane coupling agent, the concentration of fullerene modified by silane coupling agent is 20-40 mg/mL. Preferably, the solvent in the alkaline solution of the fullerene modified by the silane coupling agent is selected from one or more of ethanol, methanol, cyclohexane and bicyclohexane.
In a preferred embodiment, in the metal oxide nanoparticle solution, the metal oxide nanoparticles have a particle size of 1 to 100nm, because the effective contact area between the metal oxide nanoparticles having an excessively large particle size and the fullerene alcohol is reduced, thereby affecting the charge conduction between the interfaces.
In a preferred embodiment, the concentration of the metal oxide nanoparticles in the metal oxide nanoparticle solution is 15 to 60 mg/mL. Preferably, the solvent in the metal oxide nanoparticle solution is selected from one or more of ethanol, methanol, cyclohexane and bicyclohexane. Preferably, the metal oxide nanoparticles are selected from Fe2O8Nanoparticles, TiO2The nanoparticles, CoO nanoparticles, MgO nanoparticles, or the like are not limited thereto. The preparation of the metal oxide nanoparticles of the present invention is prior art and will not be described herein.
In a preferred embodiment, providing a substrate, depositing an alkaline solution of the silane coupling agent modified fullerene on the substrate, and forming a first thin film comprises: and depositing an alkaline solution of the fullerene modified by the silane coupling agent on the substrate by a solution method (such as a printing or printing method) in an atmospheric environment, and annealing at 40-60 ℃ for 30-60min to form a first thin film on the substrate.
In a preferred embodiment, the step of depositing the metal oxide nanoparticle solution on the first thin film to form a second thin film, and bonding the surface amino group or thiol group in the fullerene on the surface of the first thin film to the surface metal element in the metal oxide nanoparticle on the surface of the second thin film at the bonding interface between the first thin film and the second thin film specifically comprises: depositing the metal oxide nanoparticle solution on the surface of the first film by a solution method (such as a printing or printing method), and performing heat treatment at 60-90 ℃ for 30-60min to form a second film on the first film in a laminated manner.
(YSiO) of the surface of the first film3)12C60The chemical reaction formula of the metal oxide nanoparticles combined with the surface of the second film is as follows: (with Y being NH)2(CH2)3M is an example of a metal element in the metal oxide nanoparticles
（NH2(CH2)3SiO3)12C60+12M+12OH- 
（MNH(CH2)3SiO3)12C60 +12H2O
Preferably, the above reaction process is carried out under alkaline conditions. More preferably, the required alkaline condition is adjusted by an alkaline substance such as NaOH or tetramethylammonium hydroxide.
In a preferred embodiment, the thickness of the first thin film is 2 to 10nm, and an excessively thick film may cause charge migration between fullerene structures in the first thin film due to electronegativity, and an excessively thin film may not effectively contact metal oxide nanoparticles in the second thin film.
In a preferred embodiment, the thickness of the second thin film is 10 to 40 nm.
The invention also provides a composite film, which comprises a first film, wherein the material of the first film comprises fullerene modified by silane coupling agent, and the general formula of the silane coupling agent is YSiX3Wherein X is a hydrolyzable group, Y is a non-hydrolyzable group, and the terminal of the carbon chain in Y contains an amino substituent or a mercapto substituent;
the second film is formed on one surface of the first film in a laminated mode, and the material of the second film comprises metal oxide nano particles;
at the bonding interface of the first film and the second film, the surface amino group or thiol group in the fullerene on the surface of the first film is bonded to the surface metal element in the metal oxide nanoparticle on the surface of the second film.
The composite membrane of the invention has the following advantages: firstly, the preparation cost can be reduced, and the specific surface area of the composite membrane can be further increased, so that the selection performance of the gas sensor is further improved; secondly, the electric conductivity of the composite film can be further enhanced, and the photoresponse rate can be improved; and thirdly, the silane coupling agent not only can effectively enable the fullerol and the metal nanoparticles to be closely associated to improve the density of the composite membrane, but also can improve the charge conductivity between the metal oxide nanoparticles and the fullerol.
The invention also provides application of the composite film, wherein the composite film is used as a gas-sensitive layer in a gas sensor. The composite film is used as a gas-sensitive layer, so that the performance of the gas-sensitive sensor can be effectively improved, and the preparation cost is reduced. The gas sensor is used for detecting liquefied petroleum gas, alcohol, air-fuel ratio control or tail gas of combustion furnace gas and the like.
The present invention will be described in detail below with reference to examples.
This example was to use titanium dioxide nanoparticles, C60The preparation of the composite membrane by taking gamma-aminopropyl trimethoxy silane (KH-540) as a main raw material is described in detail.
1. Fullerol C60(OH)36The preparation method comprises the following steps:
1) then, 10mL (20mmol/mL) of NaOH solution was added to the flask, and 0.5mL (10%) of tetrabutylammonium hydroxide TBAH solution was added dropwise. 12mL of a solution containing 20mg of C was added dropwise with vigorous stirring60Then 1mL (30%) of H was added dropwise2O2Continuously stirring the solution for reaction for 2 hours;
2) and standing, wherein the reaction mixture is divided into two layers, the upper layer is a colorless organic phase, and the lower layer is a brownish black aqueous phase. Separating, filtering to remove water phase insoluble substances to obtain a brownish black solution;
3) adding methanol, separating out precipitate (earthy yellow), and centrifuging to remove methanol; dissolving the precipitate with water, adding methanol to precipitate, repeating the above steps for 3 times until NaOH and TBAH are completely removed. Vacuum drying the obtained precipitate at room temperature, dissolving in water, standing, and hydrolyzing for 24 hr. Adding methanol to precipitate, centrifuging to remove methanol, washing precipitate with methanol for 2 times, and vacuum drying the obtained solid at room temperature to obtain brown black product, i.e. fullerol C60(OH)36。
2. The preparation method of the fullerene modified by the silane coupling agent comprises the following steps:
1) 0.02mmol of the prepared fullerol C is taken60(OH)36Dispersing 0.3mmol of gamma-aminopropyl trimethoxy silane (KH-540) in 5mL of ethanol solution, and stirring at room temperature for 40min for full reaction;
2) adding a precipitant to the solution, and centrifuging at high speed to obtain fullerene (i.e., (NH) modified with silane coupling agent2(CH2)3SiO3)12C60) (NH) of the obtained2(CH2)3SiO3)12C60Drying under vacuum at room temperature.
3. The preparation method of the titanium dioxide nano-particles comprises the following steps:
taking 2mol of titanium tetrachloride (TiCl)4) And 10mL of benzyl alcohol were put in a 25mL three-necked flask, and heated and stirred at 85 ℃ for 3 hours in an atmospheric environment to obtain titanium dioxide (TiO) having a particle size of about 5nm in a non-hydrolytic process2). The titanium dioxide nanoparticles were precipitated by centrifugation using ethanol and ethyl acetate, and then dispersed in a mixed methanol and chloroform solution. The resulting titanium dioxide (TiO)2) The outer surface of the nanoparticles is covered with Cl atoms, where the Cl atoms account for about 12% of the Ti atoms of the outer surface of the titanium dioxide nanoparticles.
4. The preparation method of the composite membrane comprises the following steps:
1) dispersing 60mg of the prepared fullerene modified by the silane coupling agent into 2mL of ethanol solution for later use;
2) 80mg of the prepared titanium dioxide nanoparticles are dispersed in 2mL of ethanol solution, and tetramethylammonium hydroxide is dropwise added into the solution to adjust the pH value of the solution to 9 for later use;
3) sequentially preparing a fullerol solid film modified by a silane coupling agent (KH-540) and a titanium dioxide solid film from the raw materials prepared in the steps 1) and 2) in a printing mode, and annealing for 40min at 60 ℃ under the same post-treatment condition to obtain the composite film.
5. The preparation method of the gas sensor comprises the following steps:
as shown in fig. 1, a conductive coating layer 2, a gas-sensitive layer 3 and an electrode 4 are sequentially prepared on a transparent substrate 1 from bottom to top; the gas-sensitive layer 3 comprises a fullerene solid film 31 modified by a silane coupling agent and formed on the conductive coating layer 2 and a titanium dioxide solid film 32 formed on the fullerene alcohol solid film 31, and is prepared by adopting the preparation process.
In summary, the invention provides a composite film, a preparation method and an application thereof. The composite membrane of the invention has the following advantages: firstly, the preparation cost can be reduced, and the specific surface area of the composite membrane can be further increased, so that the selection performance of the gas sensor is further improved; secondly, the electric conductivity of the composite film can be further enhanced, and the photoresponse rate can be improved; and thirdly, the silane coupling agent not only can effectively enable the fullerol and the metal nanoparticles to be closely associated to improve the density of the composite membrane, but also can improve the charge conductivity between the metal oxide nanoparticles and the fullerol.
It is to be understood that the invention is not limited to the examples described above, but that modifications and variations may be effected thereto by those of ordinary skill in the art in light of the foregoing description, and that all such modifications and variations are intended to be within the scope of the invention as defined by the appended claims.
Claims (14)
1. A method of preparing a composite film for use as a gas-sensitive layer in a gas sensor, comprising the steps of:
providing fullerol, mixing the fullerol with a silane coupling agent, and dehydrating to obtain fullerene modified by the silane coupling agent, wherein the general formula of the silane coupling agent is YSiX3Wherein X is alkoxy, Y is a non-hydrolyzable group, and the end of the carbon chain in Y contains an amino substituent or a mercapto substituent;
providing a metal oxide nanoparticle solution;
providing a substrate, and depositing an alkaline solution of the fullerene modified by the silane coupling agent on the substrate to form a first thin film;
depositing the metal oxide nanoparticle solution on the first film to form a second film, and combining amino or sulfhydryl on the surface of fullerene on the surface of the first film with surface metal elements in metal oxide nanoparticles on the surface of the second film at the combined interface of the first film and the second film to prepare the composite film;
the metal oxide nanoparticle solution is a semiconductor metal oxide nanoparticle solution.
2. The method of claim 1, wherein the fullerol compound has the formula Cm(OH)nWherein m is more than or equal to 28 and less than or equal to 104, n is more than or equal to 16 and less than or equal to 60, n<m。
3. The method of claim 2, wherein the fullerol is C60(OH)36。
4. A method of making a composite membrane according to claim 1, wherein said silane coupling agent is selected from NH2(CH2)3Si(OCH3)3、NH2(CH2)3Si(OC2H5)3、NH2(CH2)2NH(CH2)3Si(OCH3)3、NH2(CH2)2NH(CH2)3Si(OC2H5)3And SH (CH)2)3Si(OC2H5)3One kind of (1).
5. The method of claim 1, wherein the metal oxide nanoparticles in the metal oxide nanoparticle solution are selected from Fe2O3Nanoparticles, TiO2Nanoparticles, CoO nanoparticles, or MgO nanoparticles.
6. The method for producing a composite film according to claim 1, wherein in the step of mixing and dehydrating the fullerol with the silane coupling agent, the molar ratio of the fullerol to the silane coupling agent is 1 mmol: (15-20 mmol), and mixing the fullerol with the silane coupling agent.
7. The method for producing a composite film according to claim 1, wherein the concentration of the silane coupling agent-modified fullerene in the alkaline solution of the silane coupling agent-modified fullerene is 20 to 40 mg/mL.
8. The method for preparing the composite film according to claim 1, wherein in the metal oxide nanoparticle solution, the particle size of the metal oxide nanoparticles is 1 to 100 nm.
9. The method of claim 1, wherein depositing the silane coupling agent modified fullerene in an alkaline solution on the substrate to form a first thin film comprises: and depositing an alkaline solution of fullerene modified by the silane coupling agent on the substrate, and annealing for 30-60min at 40-60 ℃ to form a first film on the substrate.
10. The method of claim 1, wherein the step of depositing the metal oxide nanoparticle solution on the first thin film to form a second thin film, and bonding an amino group or a thiol group on the surface of the fullerene on the surface of the first thin film to a surface metal element on the metal oxide nanoparticle on the surface of the second thin film at the bonding interface between the first thin film and the second thin film comprises: depositing the metal oxide nanoparticle solution on the surface of the first film, annealing for 30-60min at 60-90 ℃, and laminating the first film and the second film to form a second film.
11. The composite film used as a gas-sensitive layer in a gas-sensitive sensor is characterized by comprising a first film, wherein the material of the first film comprises fullerene modified by a silane coupling agent, and the general formula of the silane coupling agent is YSiX3Wherein X is alkoxy, Y is a non-hydrolyzable group, and the end of the carbon chain in Y contains an amino substituent or a mercapto substituent;
the second film is formed on one surface of the first film in a laminated mode, and the material of the second film comprises metal oxide nano particles;
at the combination interface of the first film and the second film, the amino or the sulfhydryl on the surface of the fullerene on the surface of the first film is combined with the surface metal element in the metal oxide nano-particles on the surface of the second film;
the metal oxide nanoparticles are semiconducting metal oxide nanoparticles.
12. The composite film of claim 11, wherein the metal oxide nanoparticles are selected from Fe2O3Nanoparticles, TiO2Nanoparticles, CoO nanoparticles, or MgO nanoparticles.
13. The composite film according to claim 11, wherein the first thin film has a thickness of 2 to 10 nm.
14. The composite film according to claim 11, wherein the first thin film has a thickness of 10 to 40 nm.
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