CN105092646B - A kind of graphene/metal oxide is combined film gas transducer and preparation method thereof - Google Patents
A kind of graphene/metal oxide is combined film gas transducer and preparation method thereof Download PDFInfo
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Abstract
Film gas transducer and preparation method thereof is combined the invention discloses a kind of graphene/metal oxide, belong to microelectromechanical systems gas sensor technical field, its object is to propose a kind of sensor, by reducing the chemical potential barrier of gas molecule electro transfer when graphene film is responded to gas using metal oxide nanoparticles as catalysis medium, so as to strengthen the gas sensitization characteristic of single graphene film.The present invention is based on the excellent gas sensitization characteristic of grapheme material, one layer of nano level metal oxide particle of preferential deposition in interdigital electrode, redeposited graphene film layer, the graphene/metal oxide laminated film with gas sensitization enhancement effect is obtained by heating technique.The present invention is applied to gas sensor, realizes and gas with various high sensitivity and high selectivity are detected.
Description
Technical field
The invention belongs to gas sensor and composite nano materials technical field, it is related to a kind of graphene/metal oxide
Compound film gas transducer, more particularly to a kind of be made based on graphene, metal oxide composite Nano sensitive material
Gas sensor with support and catalytic effect.
Background technology
Received more and more attention with the raising of people's health consciousness, the problem of room air pollution.In recent years, with
Production and life style is more modernized, increasing work, entertainment and sports are all carried out indoors, such people
It is average to there are 80% even more times to spend indoors daily.Therefore, the relation of IAQ and health just seems
It is closer.
Contaminants of chemical origin is the main matter of indoor pollution, its generally comprise formaldehyde, carbon monoxide, benzene homologues, ammonia,
Radon and its daughter and suspended particulate etc..And the concentration of the pollutant is often relatively low, this brings difficulty to detection.For chemistry
The detection of contact scar thing, the detection method of present main flow has：Gas chromatography, electrochemical process, infra-red sepectrometry, phenol reagent light splitting
Several conventional detection methods such as photometry.Although these detection methods can detect the dusty gas of trace level,
In detection process exist need sampling, instrumentation complexity, analysis time length, it is expensive, power consumption it is larger the shortcomings of.And gas
Sensor is as a kind of fast and effectively analysis means, and with can measure in real time, small volume, response is fast, price is low, power consumption is few etc.
Air pollutants in environment can be supervised by advantage in real time with gas sensor for the remote sensing monitoring system of core devices
Control, management.In consideration of it, urgently a kind of sensitivity of research and development it is higher, selectivity preferably, stability preferably, response speed compared with
Fast gas sensor.
The main cause of restriction gas sensor development has at present：The sensitivity of gas sensor is relatively low, selectivity is poor,
The factor such as power consumption is big, preparation technology is complicated, price is high, and the sensitive material that all of these factors taken together is all used with gas sensor
It is relevant with the structure of gas sensor.It can be said that the structure of sensitive material and sensor is new gas sensor or even new
The basis of gas sensor technology and key.
Graphene has been subjected to the ardent of all trades and professions researcher and pursued as a kind of new material.Its huge ratio table
Area, high electrical conductivity, extremely low intrinsic noise and the change extremely characteristic such as sensitivity of giving and accepting electronics, make it be led in sensor
Domain obtains extensive concern.However, research shows：Because single grapheme material has the intrinsic absorption weaker to gas molecule
Power and indiscriminate response characterization of adsorption, make it in sensitivity and the aspect of selectivity two by fatefulue restriction.Therefore, it is existing
It is to be combined grapheme material and other functional materials to improve single grapheme material in the widespread consensus of industry
Gas sensitization characteristic.
It is thin that application for a patent for invention such as Application No. 201410166226.9 discloses a kind of graphene-based tri compound
Film gas transducer and preparation method thereof, it is made up of tri compound film and substrate, and tri compound film is by graphene, metal
Or metal oxide nanoparticles, conducting polymer are composited, this application takes full advantage of the height of graphene and nano particle
Specific surface area, excellent electricity and physicochemical characteristics, and the special air-sensitive response characteristic of conducting polymer, tri compound make
Formation gain complementary mechanisms between different materials are obtained, the gas sensitization characteristic and stability of system is enhanced；In combination with order
Good self-assembly process, available for preparing highly sensitive room temperature probe gas sensor.
However, because there is graphene thermal polycondensation effect, i.e. graphene thermal polycondensation will be produced in thermal histories, it is single
One graphene-based film does not have the support for supporting node in thermal histories and produces contraction or even occur film division, so that
Reduce the sensitivity to gas, cause the sensitivity of gas sensor relatively low.
The content of the invention
The goal of the invention of the present invention is：There is provided a kind of graphite in higher sensitivity for the problem of existing for prior art
Alkene/metal oxide is combined film gas transducer and preparation method thereof.
To achieve these goals, the technical solution adopted by the present invention is：
A kind of graphene/metal oxide is combined film gas transducer, including Sensitive Apparatus, and the Sensitive Apparatus is provided with
Have between nanosize metal oxide particle film, the metal oxide particle of the nanosize metal oxide particle film
Hole；The nanosize metal oxide particle film is provided with oxidation graphene film, the redox graphene
Film is reductive amination graphene oxide film, hydroxylating oxidation graphene film, carboxylated redox graphene
One or more in film, fluorination oxidation graphene film and thin base oxidation graphene film；In oxygen reduction
On the contact interface of graphite alkene film and nanosize metal oxide particle film, the functional group of oxidation graphene film
It is bonded with the metal oxide particle of nanosize metal oxide particle film.
As the preferred scheme of the present invention, the Sensitive Apparatus is interdigital electrode, and the interdigital electrode is gold electrode or aluminium
Electrode, the interdigital spacing of the interdigital electrode is 20 μm -50 μm, and the interdigital width of the interdigital electrode is 20 μm -50 μm, institute
The thickness of electrode for stating interdigital electrode is 20nm-500nm.
It is used as the preferred scheme of the present invention, the metal oxide nano particles of the nanosize metal oxide particle film
Including nano granular of zinc oxide, Nano granules of stannic oxide, nano oxidized tungsten particle, nano titania particle, nano indium oxide
One or more in grain, nano manganese oxide particle and nano nickel oxide particles.
It is used as the preferred scheme of the present invention, the metal oxide nano particles of the nanosize metal oxide particle film
Particle diameter be less than 150nm.
A kind of graphene/metal oxide is combined the preparation method of film gas transducer, comprises the following steps：
Step 1: cleaning interdigital electrode；
Step 2: graphene oxide solution, nanosize metal oxide particle dispersion are prepared, and the graphene oxide
Solution is that graphene oxide is amination graphene oxide, hydroxylating graphene oxide, carboxylated graphene oxide, fluorinated
Graphene, the one or more dredged in base graphene oxide；
Step 3: preparing nanosize metal oxide particle film, nanosize metal oxide particle dispersion is passed through
Spin coating, gas blowout or drop coating process deposits are to forming nanosize metal oxide particle film in interdigital electrode；
Step 4: preparing graphene oxide film, graphene oxide solution is sunk by spin coating, gas blowout or drop coating technique
Accumulate onto interdigital electrode, and graphene oxide film is formed on nanosize metal oxide particle film；
Step 5: having nanosize metal oxide particle film and graphite oxide to deposition under the atmosphere of nitrogen or argon gas
The interdigital electrode of alkene film is heated, and graphene oxide film is heated and is reduced into oxidation graphene film.
As the preferred scheme of the present invention, in step one, during cleaning interdigital electrode, successively using acetone, ethanol, deionization
Water carries out ultrasonic cleaning 9min-12min to interdigital electrode.
As the preferred scheme of the present invention, the concentration of the nanosize metal oxide particle dispersion in step 2 is
The particle diameter of nanosize metal oxide particle is less than 150nm in 0.01%-5%, the nanosize metal oxide particle dispersion,
The boiling point of the nanosize metal oxide particle dispersion is 100 °C, the nanosize metal oxide particle dispersion
Density is 0.1mg/ml-5mg/ml.
As the preferred scheme of the present invention, in step 5, deposition there are into nanosize metal oxide particle film and oxidation
The interdigital electrode of graphene film is put into nitrogen atmosphere stove or argon gas atmosphere stove, and the flow of nitrogen or argon gas is 100mL/
Min-500mL/min, heats 1min-5h in the environment of heating-up temperature is 100 DEG C -1500 DEG C, and graphene oxide film is heated
It is reduced into oxidation graphene film.
In summary, by adopting the above-described technical solution, the beneficial effects of the invention are as follows：
In the present invention, nanosize metal oxide particle film, reduction have been sequentially depositing from the bottom up on Sensitive Apparatus
Nanosize metal oxide particle film on graphene oxide film, Sensitive Apparatus passes through gas blowout nanosize metal oxide
Grain dispersion liquid deposition is formed, thus has between the metal oxide particle of nanosize metal oxide particle film a hole,
It is easy to sensitive gas to be measured to enter oxidation graphene film bottom by the space, increases sensitive gas to be measured and stone
The contact area of black alkene, the characteristics of giving full play to the two-sided effect of graphene upper and lower surface improves the spirit of gas sensor
Sensitivity；Due to being provided with oxidation graphene film, nanosize metal oxide on nanosize metal oxide particle film
The granularity of metal oxide particle on particle film reaches nanoscale, thus nanosize metal oxide particle film surface will
With the oxygen effect in air and form oxonium ion chemisorbed layer, and according to the semiconductor ability of metal oxide is different and shape
Into different chemically active oxonium ions（O-2、O-、O2 -Deng）, and the dense of different chemically active oxonium ions can be changed by heating
Degree, these oxonium ions will reduce the chemical potential barrier of gas molecule electron transfer as catalysis medium, be treated so as to strengthen graphene
The sensitive response of sensitive gas is surveyed, the sensitivity of gas sensor is improved；In addition, oxidation graphene film is by amination
Graphene oxide, hydroxylating graphene oxide, carboxylated graphene oxide, Fluorinated graphene oxide and thin base graphene oxide
In it is one or more it is heated reduction form, thus on oxidation graphene film have corresponding structure of functional groups, this
Graphene grid and nanosize metal oxide particle film that a little structure of functional groups will promote in oxidation graphene film
On nano level metal oxide particle produce bonding action, so as to promote the speed of electron transfer, strengthen and accelerate gas
Response of the sensor to sensitive gas to be measured, improves sensitivity and the detection efficiency of gas sensor；In addition, reduction-oxidation graphite
Nanosize metal oxide particle film is additionally provided with below alkene film, due to the thermal polycondensation effect of graphene, thus in heating
During oxidation graphene film, the metal oxide particle in nanosize metal oxide particle film can be used as reduction-oxidation
The strong point of graphene grid in graphene film, it is to avoid graphene film shrinks or even occurred film division in thermal histories
And reduce sensitivity of the gas sensor to sensitive gas to be measured.
Brief description of the drawings
Fig. 1 is the structural representation of the gas sensor of the present invention；
Fig. 2 is that Fig. 1 existsThe partial enlarged drawing at place；
Fig. 3 is that laminated film responds schematic diagram with single graphene gas；
Fig. 4 is rGO/TiO2With response test figures of the single rGO to 0.1-0.5ppm formaldehyde；
Fig. 5 is rGO/TiO2With single rGO to the repeated response test figure of 0.5ppm formaldehyde；
Fig. 6 is rGO/TiO2With selective response side views of the single rGO to 1ppm variety classes gases；
Fig. 7 is rGO/TiO2, and TiO2/rGO（Graphene is in lower floor, and titanium dioxide is on upper strata）Laminated film with it is single
Response test figures of the rGO to 0.5ppm and 1pmm formaldehyde；
Wherein, reference is：1-Sensitive Apparatus, 2-nanosize metal oxide particle film, 3-oxygen reduction fossil
Black alkene film, 21-hole.
Embodiment
Below in conjunction with the accompanying drawings, the present invention is described in detail.
In order to make the purpose , technical scheme and advantage of the present invention be clearer, it is right below in conjunction with drawings and Examples
The present invention is further elaborated.It should be appreciated that specific embodiment described herein is only to explain the present invention, not
For limiting the present invention.
Embodiment 1
A kind of graphene/metal oxide is combined film gas transducer, and the gas sensor includes Sensitive Apparatus, and this is quick
Inductor component is interdigital electrode.The interdigital electrode is gold electrode or aluminium electrode, and the interdigital spacing of the interdigital electrode is 20 μm of -50 μ
M, the interdigital width of interdigital electrode is 20 μm -50 μm, and the thickness of electrode of interdigital electrode is 20 μm -500 μm.In the present embodiment, fork
Refer to electrode and select gold electrode, and the interdigital spacing of interdigital electrode is 25 μm, the interdigital width of interdigital electrode is 26 μm, interdigital electrode
Thickness of electrode be 50 nm.
Nanosize metal oxide particle film is provided with the Sensitive Apparatus, nanosize metal oxide particle film
Metal oxide nano particles include nano granular of zinc oxide, Nano granules of stannic oxide, nano oxidized tungsten particle, nano-titanium oxide
One or more in particle, nano indium oxide particle, nano manganese oxide particle and nano nickel oxide particles, wherein nano oxidized
Zinc particle reaches nano level zinc oxide for the particle diameter of particle, and Nano granules of stannic oxide reaches nano level oxygen for the particle diameter of particle
Change tin, nano oxidized tungsten particle reaches nano level tungsten oxide for the particle diameter of particle, and nano titania particle is the particle diameter of particle
Nano level titanium oxide is reached, nano indium oxide particle reaches nano level indium oxide, nano manganese oxide for the particle diameter of particle
Grain reaches nano level manganese oxide for the particle diameter of particle, and nano nickel oxide particles reach nano level oxidation for the particle diameter of particle
Nickel.The nanosize metal oxide particle film is deposited by concentration for 0.01%-5% nanosize metal oxide particle dispersion
Form, thus have between the metal oxide particle of nanosize metal oxide particle film hole, and the nanometer grade gold
The particle diameter for belonging to metal oxide particle in oxide particle dispersion liquid is less than 150nm.In the present embodiment, nanosize metal oxide
The metal oxide nano particles of particle film are selected golden in nano granular of zinc oxide, nanosize metal oxide particle dispersion
The particle diameter for belonging to oxide particle is 80nm.
The nanosize metal oxide particle film is provided with oxidation graphene film, and the redox graphene is thin
Film is formed by the heated reduction of the graphene oxide film being deposited on nanosize metal oxide particle film.The oxygen reduction
Graphite alkene film is reductive amination graphene oxide film, hydroxylating oxidation graphene film, carboxylated oxygen reduction
One or more in graphite alkene film, fluorination oxidation graphene film and thin base oxidation graphene film,
Wherein reductive amination graphene oxide film refers to by the heated film for reducing and depositing of amination graphene oxide,
Hydroxylating oxidation graphene film refers to by the heated film for reducing and depositing of hydroxylating graphene oxide, carboxyl
Change oxidation graphene film to refer to by the heated film for reducing and depositing of carboxylated graphene oxide, fluorination reduction
Graphene oxide film refers to, by the heated film for reducing and depositing of Fluorinated graphene oxide, dredge base oxygen reduction fossil
Black alkene film refers to by dredging the heated film for reducing and depositing of base graphene oxide.In the present embodiment, reduction-oxidation
Graphene film select reductive amination graphene oxide film, i.e., by amination graphene oxide it is heated reduction and deposit and
Into film.
Because oxidation graphene film is the graphite oxide by being deposited on nanosize metal oxide particle film
The heated reduction of alkene film is formed, thus during graphene oxide film heating reduction, oxidation graphene film
Functional group be bonded with the coating metal oxide particle of nanosize metal oxide particle film, so as to promote electron transfer
Speed, strengthens and accelerates response of the gas sensor to sensitive gas to be measured, and the sensitivity and detection for improving gas sensor are imitated
Rate.
Embodiment 2
A kind of graphene/metal oxide is combined film gas transducer, and the gas sensor includes Sensitive Apparatus, and this is quick
Inductor component is interdigital electrode.The interdigital electrode is gold electrode or aluminium electrode, and the interdigital spacing of the interdigital electrode is 20 μm of -50 μ
M, the interdigital width of interdigital electrode is 20 μm -50 μm, and the thickness of electrode of interdigital electrode is 20 μm -500 μm.In the present embodiment, fork
Refer to electrode and select aluminium electrode, the interdigital spacing of interdigital electrode is 35 μm, and the interdigital width of interdigital electrode is 36 μm, interdigital electrode
Thickness of electrode is 210nm.
Nanosize metal oxide particle film is provided with the Sensitive Apparatus, nanosize metal oxide particle film
Metal oxide nano particles include nano granular of zinc oxide, Nano granules of stannic oxide, nano oxidized tungsten particle, nano-titanium oxide
One or more in particle, nano indium oxide particle, nano manganese oxide particle and nano nickel oxide particles, wherein nano oxidized
Zinc particle reaches nano level zinc oxide for the particle diameter of particle, and Nano granules of stannic oxide reaches nano level oxygen for the particle diameter of particle
Change tin, nano oxidized tungsten particle reaches nano level tungsten oxide for the particle diameter of particle, and nano titania particle is the particle diameter of particle
Nano level titanium oxide is reached, nano indium oxide particle reaches nano level indium oxide, nano manganese oxide for the particle diameter of particle
Grain reaches nano level manganese oxide for the particle diameter of particle, and nano nickel oxide particles reach nano level oxidation for the particle diameter of particle
Nickel.The nanosize metal oxide particle film is deposited by concentration for 0.01%-5% nanosize metal oxide particle dispersion
Form, thus have between the metal oxide particle of nanosize metal oxide particle film hole, and the nanometer grade gold
The particle diameter for belonging to metal oxide particle in oxide particle dispersion liquid is less than 150nm.In the present embodiment, nanosize metal oxide
The metal oxide nano particles of particle film are selected golden in Nano granules of stannic oxide, nanosize metal oxide particle dispersion
The particle diameter for belonging to oxide particle is 100nm.
The nanosize metal oxide particle film is provided with oxidation graphene film, and the redox graphene is thin
Film is formed by the heated reduction of the graphene oxide film being deposited on nanosize metal oxide particle film.The oxygen reduction
Graphite alkene film is reductive amination graphene oxide film, hydroxylating oxidation graphene film, carboxylated oxygen reduction
One or more in graphite alkene film, fluorination oxidation graphene film and thin base oxidation graphene film,
Wherein reductive amination graphene oxide film refers to by the heated film for reducing and depositing of amination graphene oxide,
Hydroxylating oxidation graphene film refers to by the heated film for reducing and depositing of hydroxylating graphene oxide, carboxyl
Change oxidation graphene film to refer to by the heated film for reducing and depositing of carboxylated graphene oxide, fluorination reduction
Graphene oxide film refers to, by the heated film for reducing and depositing of Fluorinated graphene oxide, dredge base oxygen reduction fossil
Black alkene film refers to by dredging the heated film for reducing and depositing of base graphene oxide.In the present embodiment, reduction-oxidation
Graphene film select hydroxylating oxidation graphene film, i.e., by hydroxylating graphene oxide it is heated reduction and deposit and
Into film.
Because oxidation graphene film is the graphite oxide by being deposited on nanosize metal oxide particle film
The heated reduction of alkene film is formed, thus during graphene oxide film heating reduction, oxidation graphene film
Functional group be bonded with the coating metal oxide particle of nanosize metal oxide particle film, so as to promote electron transfer
Speed, strengthens and accelerates response of the gas sensor to sensitive gas to be measured, and the sensitivity and detection for improving gas sensor are imitated
Rate.
Embodiment 3
A kind of graphene/metal oxide is combined film gas transducer, and the gas sensor includes Sensitive Apparatus, and this is quick
Inductor component is interdigital electrode.The interdigital electrode is gold electrode or aluminium electrode, and the interdigital spacing of the interdigital electrode is 20 μm of -50 μ
M, the interdigital width of interdigital electrode is 20 μm -50 μm, and the thickness of electrode of interdigital electrode is 20 μm -500 μm.In the present embodiment, fork
Refer to electrode and select aluminium electrode, the interdigital spacing of interdigital electrode is 45 μm, and the interdigital width of interdigital electrode is 46 μm, interdigital electrode
Thickness of electrode is 430nm.
Nanosize metal oxide particle film is provided with the Sensitive Apparatus, nanosize metal oxide particle film
Metal oxide nano particles include nano granular of zinc oxide, Nano granules of stannic oxide, nano oxidized tungsten particle, nano-titanium oxide
One or more in particle, nano indium oxide particle, nano manganese oxide particle and nano nickel oxide particles, wherein nano oxidized
Zinc particle reaches nano level zinc oxide for the particle diameter of particle, and Nano granules of stannic oxide reaches nano level oxygen for the particle diameter of particle
Change tin, nano oxidized tungsten particle reaches nano level tungsten oxide for the particle diameter of particle, and nano titania particle is the particle diameter of particle
Nano level titanium oxide is reached, nano indium oxide particle reaches nano level indium oxide, nano manganese oxide for the particle diameter of particle
Grain reaches nano level manganese oxide for the particle diameter of particle, and nano nickel oxide particles reach nano level oxidation for the particle diameter of particle
Nickel.The nanosize metal oxide particle film is deposited by concentration for 0.01%-5% nanosize metal oxide particle dispersion
Form, thus have between the metal oxide particle of nanosize metal oxide particle film hole, and the nanometer grade gold
The particle diameter for belonging to metal oxide particle in oxide particle dispersion liquid is less than 150nm.In the present embodiment, nanosize metal oxide
The metal oxide nano particles of particle film select nano indium oxide particle, nano manganese oxide particle, nano level metal oxidation
The particle diameter of metal oxide particle is 130nm in composition granule dispersion liquid.
The nanosize metal oxide particle film is provided with oxidation graphene film, and the redox graphene is thin
Film is formed by the heated reduction of the graphene oxide film being deposited on nanosize metal oxide particle film.The oxygen reduction
Graphite alkene film is reductive amination graphene oxide film, hydroxylating oxidation graphene film, carboxylated oxygen reduction
One or more in graphite alkene film, fluorination oxidation graphene film and thin base oxidation graphene film,
Wherein reductive amination graphene oxide film refers to by the heated film for reducing and depositing of amination graphene oxide,
Hydroxylating oxidation graphene film refers to by the heated film for reducing and depositing of hydroxylating graphene oxide, carboxyl
Change oxidation graphene film to refer to by the heated film for reducing and depositing of carboxylated graphene oxide, fluorination reduction
Graphene oxide film refers to, by the heated film for reducing and depositing of Fluorinated graphene oxide, dredge base oxygen reduction fossil
Black alkene film refers to by dredging the heated film for reducing and depositing of base graphene oxide.In the present embodiment, reduction-oxidation
Graphene film is aoxidized from carboxylated oxidation graphene film, fluorination oxidation graphene film by carboxylated
The heated film for reducing and depositing of mixture of graphene and Fluorinated graphene oxide.
Because oxidation graphene film is the graphite oxide by being deposited on nanosize metal oxide particle film
The heated reduction of alkene film is formed, thus during graphene oxide film heating reduction, oxidation graphene film
Functional group be bonded with the coating metal oxide particle of nanosize metal oxide particle film, so as to promote electron transfer
Speed, strengthens and accelerates response of the gas sensor to sensitive gas to be measured, and the sensitivity and detection for improving gas sensor are imitated
Rate.
Embodiment 4
A kind of graphene/metal oxide is combined the preparation method of film gas transducer, comprises the following steps：
Step 1: cleaning interdigital electrode；
When cleaning interdigital electrode, interdigital electrode is cleaned by ultrasonic using acetone, ethanol, deionized water successively
10min。
Step 2: preparing graphene oxide solution, nanosize metal oxide particle dispersion；
When preparing graphene oxide solution, 2g powdered graphite is added in 250mL beakers, then under the conditions of cold bath
1g sodium nitrate, the 46mL concentrated sulfuric acids are added into beaker successively and is sufficiently stirred for, then add into beaker 6g potassium permanganate and
92mL water simultaneously stirs 15min, the hydrogen peroxide that the concentration for finally continuing to add 80mL into beaker is 3%, and is made through centrifugal filtration
Graphene oxide solution.Graphene oxide in the step is amination graphene oxide, hydroxylating graphene oxide, carboxylated
In graphene oxide, Fluorinated graphene oxide, the one or more dredged in base graphene oxide, the present embodiment, graphite oxide
Alkene is amination graphene oxide.
, can be using conventional scattered liquid and preparation method thereof when preparing nanosize metal oxide particle dispersion, but need
The concentration of nanosize metal oxide particle dispersion is 0.01%-5%, is received in the nanosize metal oxide particle dispersion
The particle diameter of meter level metal oxide particle is less than 150nm, and the boiling point of the nanosize metal oxide particle dispersion is 100 °
C, the density of the nanosize metal oxide particle dispersion is 0.1mg/ml-5mg/ml.Wherein, nanosize metal oxide
Metal oxide particle in particle dispersion is nano granular of zinc oxide, Nano granules of stannic oxide, nano oxidized tungsten particle, received
One or more in rice titan oxide particles, nano indium oxide particle, nano manganese oxide particle and nano nickel oxide particles, this reality
It is nano titania particle to apply the metal oxide particle in example in nanosize metal oxide particle dispersion.
Step 3: preparing nanosize metal oxide particle film, nanosize metal oxide particle dispersion is passed through
Spin coating, gas blowout or drop coating process deposits are to forming nanosize metal oxide particle film in interdigital electrode.In the present embodiment,
1mL nano size Titania particles dispersion liquid is deposited on interdigital electrode surface by gas blowout method.
Step 4: preparing graphene oxide film, graphene oxide solution liquid is passed through into spin coating, gas blowout or drop coating technique
Deposit in interdigital electrode, and graphene oxide film is formed on nanosize metal oxide particle film.In the present embodiment,
1mL graphene oxide solution liquid is deposited on interdigital electrode surface by gas blowout method.
Step 5: having nanosize metal oxide particle film and graphite oxide to deposition under the atmosphere of nitrogen or argon gas
The interdigital electrode of alkene film is heated, and graphene oxide film is heated and is reduced into oxidation graphene film.I.e.
By deposit have nanosize metal oxide particle film and graphene oxide film interdigital electrode be put into nitrogen atmosphere stove or
In argon gas atmosphere stove, the flow of nitrogen or argon gas is 200mL/min, heats 2h in the environment of heating-up temperature is 220 DEG C, aoxidizes
Graphene film is heat reduced to oxidation graphene film.
Embodiment 5
A kind of graphene/metal oxide is combined the preparation method of film gas transducer, comprises the following steps：
Step 1: cleaning interdigital electrode；
When cleaning interdigital electrode, interdigital electrode is cleaned by ultrasonic using acetone, ethanol, deionized water successively
11min。
Step 2: preparing graphene oxide solution, nanosize metal oxide particle dispersion；
When preparing graphene oxide solution, 4g powdered graphite is added in 250mL beakers, then under the conditions of cold bath
2g sodium nitrate, the 42mL concentrated sulfuric acids are added into beaker successively and is sufficiently stirred for, then add into beaker 7g potassium permanganate and
96mL water simultaneously stirs 17min, the hydrogen peroxide that the concentration for finally continuing to add 65mL into beaker is 3%, and is made through centrifugal filtration
Graphene oxide solution.Graphene oxide in the step is amination graphene oxide, hydroxylating graphene oxide, carboxylated
In graphene oxide, Fluorinated graphene oxide, the one or more dredged in base graphene oxide, the present embodiment, graphite oxide
Alkene is amination graphene oxide.
, can be using conventional scattered liquid and preparation method thereof when preparing nanosize metal oxide particle dispersion, but need
The concentration of nanosize metal oxide particle dispersion is 0.01%-5%, is received in the nanosize metal oxide particle dispersion
The particle diameter of meter level metal oxide particle is less than 150nm, and the boiling point of the nanosize metal oxide particle dispersion is 100 °
C, the density of the nanosize metal oxide particle dispersion is 0.1mg/ml-5mg/ml.Wherein, nanosize metal oxide
Metal oxide particle in particle dispersion is nano granular of zinc oxide, Nano granules of stannic oxide, nano oxidized tungsten particle, received
One or more in rice titan oxide particles, nano indium oxide particle, nano manganese oxide particle and nano nickel oxide particles, this reality
It is nano indium oxide particle to apply the metal oxide particle in example in nanosize metal oxide particle dispersion.
Step 3: preparing nanosize metal oxide particle film, nanosize metal oxide particle dispersion is passed through
Spin coating, gas blowout or drop coating process deposits are to forming nanosize metal oxide particle film in interdigital electrode.In the present embodiment,
1mL nanoscale indium particle dispersion is deposited on interdigital electrode surface by gas blowout method.
Step 4: preparing graphene oxide film, graphene oxide solution liquid is passed through into spin coating, gas blowout or drop coating technique
Deposit in interdigital electrode, and graphene oxide film is formed on nanosize metal oxide particle film.In the present embodiment,
1mL graphene oxide solution liquid is deposited on interdigital electrode surface by gas blowout method.
Step 5: having nanosize metal oxide particle film and graphite oxide to deposition under the atmosphere of nitrogen or argon gas
The interdigital electrode of alkene film is heated, and graphene oxide film is heated and is reduced into oxidation graphene film.I.e.
By deposit have nanosize metal oxide particle film and graphene oxide film interdigital electrode be put into nitrogen atmosphere stove or
In argon gas atmosphere stove, the flow of nitrogen or argon gas is 390mL/min, and 4.2h, oxygen are heated in the environment of heating-up temperature is 800 DEG C
Graphite alkene film is heat reduced to oxidation graphene film.
Embodiment 6
Gas sensor prepared by the method to embodiment 4 carries out performance test, and compound sensor is inserted into air-sensitive test
In chamber, the formaldehyde gas under 500ml/min total gas couettes under room temperature detection various concentrations, and with being obtained under same sample preparation method
The single graphene film sensor obtained carries out performance comparison.
The method provided by the application, as shown in 3 figures, the Nano titanium dioxide particle film of bottom is not only graphite
Alkene provides the effect of catalysis medium, and the effect of support is also provided for graphene so that formaldehyde molecule is not only made in graphenic surface
With can also be by entering oxidation graphene film basal surface between porous titanium dioxide nano-particle and carrying out electronics
Transfer, reaches the effect of enhancing oxidation graphene film PARA FORMALDEHYDE PRILLS(91,95) gas response.As shown in Figures 4 and 5, compared to single graphite
Alkene thin film gas sensor, graphene/metal oxide be combined film gas transducer respectively 0.1-0.5ppm various concentrations with
And in 0.5ppm formaldehyde reperformance tests, have bigger response and faster response recovery time, with bigger sensitivity.
It can be obtained by Fig. 6, compared to single graphene film gas sensor, graphene/metal oxide is combined film gas transducer to first
Aldehyde has more excellent selective response.In order to verify Nano titanium dioxide particle film to graphene supporting role, using same
The preparation method of sample is prepared for TiO2/rGO（Graphene is in lower floor, and titanium dioxide is on upper strata）Laminated film sensor.Such as Fig. 7 institutes
Show, TiO2/ rGO has certain response gain compared to single stone rGO, and this is due to TiO2Catalysis humidification caused by；But
rGO/ TiO2There is bigger response than the former two under the conditions of same test, this is due to that formaldehyde gas molecule can enter stone
Black alkene bottom is responded.Therefore the supporting role of titanium dioxide is also proven.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
Any modifications, equivalent substitutions and improvements made within refreshing and principle etc., should be included in the scope of the protection.
Claims (8)
1. a kind of graphene/metal oxide is combined film gas transducer, including Sensitive Apparatus（1）, it is characterised in that：It is described quick
Inductor component（1）It is provided with nanosize metal oxide particle film（2）, the nanosize metal oxide particle film（2）'s
There is hole between metal oxide particle（21）；The nanosize metal oxide particle film（2）It is provided with reduction-oxidation
Graphene film（3）, the oxidation graphene film（3）For reductive amination graphene oxide film（3）, hydroxylating also
Former graphene oxide film（3）, carboxylated oxidation graphene film（3）, fluorination oxidation graphene film（3）With dredge
Base oxidation graphene film（3）In one or more；In oxidation graphene film（3）With nano level metal oxygen
Compound particle film（2）Contact interface on, oxidation graphene film（3）Functional group and nanosize metal oxide
Grain film（2）Metal oxide particle bonding.
2. a kind of graphene/metal oxide as claimed in claim 1 is combined film gas transducer, it is characterised in that：It is described
Sensitive Apparatus（1）For interdigital electrode, the interdigital electrode is gold electrode or aluminium electrode, and the interdigital spacing of the interdigital electrode is 20
μm -50 μm, the interdigital width of the interdigital electrode is 20 μm -50 μm, and the thickness of electrode of the interdigital electrode is 20nm-
500nm。
3. a kind of graphene/metal oxide as claimed in claim 1 is combined film gas transducer, it is characterised in that：It is described
Nanosize metal oxide particle film（2）Metal oxide nano particles include nano granular of zinc oxide, nano tin dioxide
Particle, nano oxidized tungsten particle, nano titania particle, nano indium oxide particle, nano manganese oxide particle and nano-nickel oxide
One or more in particle.
4. a kind of graphene/metal oxide as claimed in claim 3 is combined film gas transducer, it is characterised in that：It is described
Nanosize metal oxide particle film（2）Metal oxide nano particles particle diameter be less than 150nm.
5. a kind of graphene/metal oxide is combined the preparation method of film gas transducer, it is characterised in that including following step
Suddenly：
Step 1: cleaning interdigital electrode；
Step 2: graphene oxide solution, nanosize metal oxide particle dispersion are prepared, and the graphene oxide solution
It is amination graphene oxide, hydroxylating graphene oxide, carboxylated graphene oxide, fluorinated graphite for graphene oxide
Alkene, the one or more dredged in base graphene oxide；
Step 3: preparing nanosize metal oxide particle film（2）, nanosize metal oxide particle dispersion is passed through into rotation
Apply, form nanosize metal oxide particle film in gas blowout or drop coating process deposits to interdigital electrode（2）；
Step 4: preparing graphene oxide film, graphene oxide solution is arrived by spin coating, gas blowout or drop coating process deposits
In interdigital electrode, and in nanosize metal oxide particle film（2）Upper formation graphene oxide film；
Step 5: having nanosize metal oxide particle film to deposition under the atmosphere of nitrogen or argon gas（2）And graphite oxide
The interdigital electrode of alkene film is heated, and graphene oxide film is heated and is reduced into oxidation graphene film（3）.
6. a kind of graphene/metal oxide as claimed in claim 5 is combined the preparation method of film gas transducer, its feature
It is, in step one, during cleaning interdigital electrode, interdigital electrode is cleaned by ultrasonic using acetone, ethanol, deionized water successively
9min-12min。
7. a kind of graphene/metal oxide as claimed in claim 5 is combined the preparation method of film gas transducer, its feature
It is, the concentration of the nanosize metal oxide particle dispersion in step 2 is 0.01%-5%, the nano level metal oxidation
The particle diameter of nanosize metal oxide particle is less than 150nm, the nanosize metal oxide particle point in composition granule dispersion liquid
The boiling point of dispersion liquid is 100 °C, and the density of the nanosize metal oxide particle dispersion is 0.1mg/ml-5mg/ml.
8. a kind of graphene/metal oxide as claimed in claim 5 is combined the preparation method of film gas transducer, its feature
It is that in step 5, deposition is had into nanosize metal oxide particle film（2）Put with the interdigital electrode of graphene oxide film
Enter in nitrogen atmosphere stove or argon gas atmosphere stove, the flow of nitrogen or argon gas is 100mL/min-500mL/min, in heating-up temperature
To heat 1min-5h in the environment of 100 DEG C -1500 DEG C, graphene oxide film is heat reduced to oxidation graphene film
（3）.
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Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US8932671B2 (en) * | 2010-12-01 | 2015-01-13 | The University Of Houston System | Polymer nanocomposite precursors with carbon nanotubes and/or graphene and related thin films and patterning |
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| CN102636522A (en) * | 2012-03-29 | 2012-08-15 | 浙江大学 | Graphene/ stannic oxide nanometer compounding resistance type film gas sensor and manufacturing method thereof |
| CN103009730B (en) * | 2012-12-14 | 2015-10-14 | 电子科技大学 | A kind of method and composite nano film thereof manufacturing composite nano film |
| CN103412001A (en) * | 2013-08-02 | 2013-11-27 | 电子科技大学 | Method for manufacturing gas sensitive nano-film |
| CN103862751A (en) * | 2014-02-24 | 2014-06-18 | 电子科技大学 | Method for preparing composite nano film |
| CN104181209A (en) * | 2014-08-14 | 2014-12-03 | 电子科技大学 | Nitrogen dioxide gas sensor and preparation method thereof |
| CN104569052B (en) * | 2014-12-17 | 2017-02-22 | 东南大学 | Method for preparing graphene oxide sensor |
| CN104634824A (en) * | 2015-01-28 | 2015-05-20 | 天津大学 | Preparation method of gas-sensitive sensor with porous-silicon-based tungsten-oxide nano-rod composite structure |
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