CN106442642A - Preparation method of zinc oxide/graphene composite material and resistance type gas sensor - Google Patents
Preparation method of zinc oxide/graphene composite material and resistance type gas sensor Download PDFInfo
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- CN106442642A CN106442642A CN201610765892.3A CN201610765892A CN106442642A CN 106442642 A CN106442642 A CN 106442642A CN 201610765892 A CN201610765892 A CN 201610765892A CN 106442642 A CN106442642 A CN 106442642A
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
- G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
- G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/02—Oxides; Hydroxides
Abstract
The invention discloses a preparation method of a zinc oxide/graphene composite material and a resistance type gas sensor. The preparation method comprises the following steps: a hydrothermal procedure, a compounding procedure and a roasting procedure. According to the preparation method disclosed by the invention, zinc oxide nanoparticles are uniformly loaded on the surface and a pore channel structure of three-dimensional graphene, and are washed and dried to obtain the zinc oxide/graphene composite material. The material is applied to the resistance type gas sensor and has excellent performances including good selectivity, high sensitivity, good stability, rapid response and the like.
Description
Technical field
The present invention relates to a kind of technical field of inorganic nanometer material, particularly to a kind of zinc oxide/graphene composite material
Preparation method, resistor-type gas sensor.
Background technology
Gas sensor is a kind of detection gas device, physics and chemical effect can will be utilized gas componant, volume integral
Number is converted into the signal of telecommunication according to certain rules, with requirements such as the process of the information of satisfied acquisition, display, record and controls, thus can
It to carry out detecting, monitor, analyze and reporting to the police, is the core of gas detecting system.In recent years, gas sensor extensively should
For producing, the field such as life is poisonous to some or imflammable gas is monitored.Resistance-type gas sensor utilizes material list
Face adsorption and desorption gas molecule can cause the change of conductivity semiconductor to detect gas.It has highly sensitive, operation side
Just, volume is little, with low cost, response time and the advantage such as recovery time is short, is most widely used.Three constructing for sensor
Dimension graphene composite material, has pore structure, specific surface area height, light weight and the excellent electric conductivity running through, is conducive to sensing
It is fully contacted between the detection layers of device and detected gas, thus increase sensitivity and the stability of sensor.
Three-dimensional grapheme is the special material with carbon element of a kind of structure, have extremely-low density, surface area heat conduction big, high, high temperature resistant,
The advantages such as corrosion-resistant, ductility, pliability are good so that it is have huge application potential in sensor field.There is porous knot
The three-dimensional grapheme of structure can reduce the reunion of graphene sheet layer, provide bigger available surface area, higher mechanical strength,
Faster proton and electron transmission and more reactivity site.Nano composite material due to its excellent combination property and
Designability, it has also become one of nano materials research focus.Graphene inorganic nanocomposite not only maintain Graphene and
The respective character of inorganic nano material, and owing to the synergy between them can also be greatly reinforced their inherent characteristic,
It is made to obtain important application at aspects such as catalysis, sensing, energy storage and conversions.
The multifunctional semiconductor material of a kind of broad-band gap of zinc oxide, has the uniqueness of the aspects such as optics, electricity, catalysis
Performance, has wide practical use, and can be used for the fields such as sensor, solar cell, lithium battery, catalysis.Zinc oxide material has
Have that preparation cost is low, chemical stability and the advantage such as Heat stability is good, abundant and controlled surface texture, grind at gas sensor
Receive much concern in studying carefully.The research that current zinc oxide/graphene composite material builds soft sensor is not a lot, has wide
Application prospect.Owing to Zinc oxide nanoparticle is easily reunited, thus reduce the air-sensitive performance of sensitive material.Chinese invention patent
CN104764779A discloses a kind of zinc oxide with spongy graphene composite nano materials for gas sensor, and this patent is adopted
Prepare spongy graphene with chemical gaseous phase depositing process on foam metal, be then combined upper nano zine oxide, the method again
Power consumption is big, is unfavorable for industrialized production.Liu Xin et al. (Sensors and Actuators B, 2015,211,220-226)
One step hydro thermal method is used to prepare zinc oxide and three-dimensional porous graphene oxide composite material, three-dimensional surface of graphene oxide and body
Phase load Zinc oxide particles particle diameter is relatively big, and homogeneity difference, thus affects gas sensor test performance.In sum, at present
Most graphene composite material is the admixture of Graphene and zinc oxide, and zinc oxide is at graphenic surface and internal skewness
Even, in gas molecule absorption and desorption process, gas molecule is difficult to adsorb at zinc oxide and Graphene boundary layer, thus causes
Electron transport ability declines, and finally affects the air-sensitive performance of sensor.
Content of the invention
The deficiency existing in view of prior art, the technical problem to be solved is to provide a kind of zinc oxide/graphite
The preparation method of alkene composite, resistor-type gas sensor.The present invention utilizes cheap raw material to prepare three-dimensional reduction
Graphene oxide, by hydro-thermal, compound, washing, is dried and roasting, obtains zinc oxide/graphene composite material.The present invention is directed to
Improve the extensive application as the sensitivity of sensing material and technical barrier and the graphene composite material such as selectively for the zinc oxide, carry
Supply that a kind of technique is simple, productivity is high, the composite material and preparation method thereof of easy expanding production.
The technical solution used in the present invention is：
The preparation method of a kind of zinc oxide/graphene composite material, step includes：
A, hydro-thermal operation：Graphite oxide is dispersed in water ultrasonic prepared graphene oxide solution, in solution, adds sulphur
Acid, then ultrasonic disperse uniformly prepares mixed liquor, then mixed liquor is transferred in reactor at 160～260 DEG C to react 18～
30 hours, taking out washing, obtain three-dimensional column redox graphene, reaction condition preferably reacts 20 at 190～220 DEG C～
24 hours；
In described step A, graphite oxide is by improving the synthesis of Hummers method, concretely comprises the following steps：Weigh 5.0g graphite respectively
With 3.75g NaNO3Put in the beaker of 1L, machinery strong stirring, it is slowly added to the concentrated sulfuric acid of 150mL, stir 0.5 hour, then
It is slowly added to the KMnO of 20g4, within 0.5 hour, add, after continuing stirring 20 hours, reactant viscosity increases, and stops stirring, obtains
Starchiness aubergine material.It after placing 5 days, is respectively added slowly to 500mL deionized water and 30mL H2O2, now solution colour becomes
For obvious glassy yellow, after solution fully reacts, centrifuge, wash, obtain graphite oxide.
In described step A, in mixed liquor, the concentration of graphene oxide is 0.75～1.5g/L, preferably 1.0～1.25g/L；
In described step A, in mixed liquor, the concentration of sulfuric acid is 0.8～1.7mol/L, preferably 1.2～1.4mol/L.
B, compound working procedure：Zinc salt is dissolved in deionized water, adds precipitating reagent, stirring, prepare soak, then by three-dimensional
Column redox graphene puts in above-mentioned solution, soaks more than 1 day at 3～40 DEG C, soak 1 at preferably 10～30 DEG C～
3 days；It finally is transferred to solution and three-dimensional column redox graphene in hydrothermal reaction kettle, at 80～160 DEG C, react 2～
12 hours, preferably react 4～6 hours at 100～120 DEG C, after product is scrubbed and dry, obtain zinc oxide multiple with Graphene
Condensation material i.e. zinc oxide/graphene composite material.
One or more in zinc nitrate, zinc acetate, zinc chloride and zinc sulfate of zinc salt, described zinc in described step B
Concentration in soak for the salt is 0.1～0.8mol/L, preferably 0.15～0.40mol/L；
One in ammoniacal liquor, hexa, urea for the precipitating reagent in described step B, in soak, precipitating reagent is
During ammoniacal liquor, concentration in soak for the ammoniacal liquor is 1.0～8.0mol/L, preferably 2.0～5.0mol/L；In soak, precipitating reagent is
During hexa, concentration 0.1～1.5mol/L in soak for the hexa, preferably 0.2～1.0mol/L；Leaching
When in bubble liquid, precipitating reagent is urea, concentration in soak for the urea is 1.0～6.0mol/L, preferably 2.5～4.0mol/L；Heavy
The preferred ammoniacal liquor of shallow lake agent；
In described step B, three-dimensional column redox graphene concentration in the solution is 0.1～4.0mg/mL, preferably
0.6～1.2mg/mL；
Described step B is dried for being vacuum dried, vacuum drying temperature 30～80 DEG C, 4～24 hours drying times, preferably
It is dried 8～16 hours at 40～70 DEG C.
C, calcining process：By predecessor obtained in compound working procedure at 250～550 DEG C roasting 0.5～6 hour, from
It is so cooled to room temperature, prepare tin ash/graphene nanocomposite material；Preferably roasting 1～3 hour at 300～500 DEG C；
Described roasting whole process is carried out in air atmosphere, and roasting naturally cools to room temperature after terminating；
A kind of resistor-type gas sensor, by including that the sensitive layer that zinc oxide/graphene composite material is made is made.
The application limitation that the present invention be directed to conventional semiconductors resistor-type gas sensor is studied, and designs a kind of new
Method synthesis has the zinc oxide/graphene composite material long-pending compared with large active surface, this be conducive to provide more adsorption site and
Avtive spot, thus improve gas sensing performance.The present invention utilizes the three-dimensional column redox graphene of water heat transfer, by it
It is immersed in the aqueous solution of zinc salt, through high temperature hydro-thermal so that Zinc oxide nanoparticle uniform load is at the table of three-dimensional grapheme
In face and pore passage structure, through washing, being dried and obtaining zinc oxide/graphene composite material, this materials application is in resistor-type gas
Sensor, have selectively good, highly sensitive, stablize, respond the excellent properties such as quickly.
Main innovation point of the present invention is that three-dimensional redox graphene, as template, is aoxidized by hydro-thermal method growth in situ
Zinc nanoparticles, Zinc oxide nanoparticle uniform load is in three-dimensional grapheme surface and pore passage structure.
The present invention compared with prior art has the following advantages：
(1) zinc oxide/graphene composite material obtained by, zinc oxide uniform load is tied on three-dimensional grapheme surface and duct
In structure, increase object gas adsorption surface area；
(2) zinc oxide obtained by/graphene composite material stable performance, high temperature resistant, the pore passage structure of three-dimensional grapheme adds
Fast generation electron transfer rate, increases the electric conductivity of material so that air-sensitive tests signal stabilization；
(3) specific surface area of zinc oxide/graphene composite material obtained by is big, and gas to be measured is fully adsorbed in the interior of material
Outer surface, three-dimensional cavernous structure provides multiple electronic passage, thus realizes the detection of the quick sensitivity to object gas；
(4) zinc oxide/graphene composite material obtained by is used for resistor-type gas sensor, has higher sensitivity and relatively
Good selectivity；
(5) synthesis step is simple, requires low to the instrument and equipment that experiment is used, and raw material sources are extensive, and cost is relatively low, can enter
Row batch production.
The present patent application is by Anhui Normal University's Students' Innovation foundation drill program funded projects.
Brief description
Fig. 1 is the SEM figure of the zinc oxide/graphene composite material of embodiment 1 preparation；
Fig. 2 is the SEM figure of the zinc oxide/graphene composite material of embodiment 2 preparation；
Fig. 3 is the SEM figure of the zinc oxide/graphene composite material of embodiment 3 preparation；
Fig. 4 is the XRD of the zinc oxide/graphene composite material of embodiment 3 preparation；
Fig. 5 is the SEM figure of the zinc oxide/graphene composite material of embodiment 4 preparation；
Fig. 6 is the SEM figure of the zinc oxide/graphene composite material of embodiment 5 preparation；
Fig. 7 be embodiment 5 preparation zinc oxide/graphene composite material gas sensor be at 240 DEG C in operating temperature,
Response to 7 kinds of organic steams (100ppm).
Detailed description of the invention
Embodiment 1
The preparation of graphite oxide：Weigh 5.0g graphite and 3.75g NaNO respectively3Putting in the beaker of 1L, machinery strength is stirred
Mix, be slowly added to the concentrated sulfuric acid of 150mL, stir 0.5 hour, be slow added into the KMnO of 20g4, within 0.5 hour, add, continue to stir
After mixing 20 hours, reactant viscosity increases, and stops stirring, obtains starchiness aubergine material.After placing 5 days, slowly add respectively
Enter 500mL deionized water and 30mLH2O2, now solution colour becomes obvious glassy yellow, after solution fully reacts, from
The heart, washing, obtain graphite oxide.
Hydro-thermal operation：90mg graphite oxide is dissolved in 80mL deionized water, adds the 6mL concentrated sulfuric acid (ρ=1.84g/
cm3), ultrasonic disperse 3 hours, move into solution in vial, be then averaged and transfer in 5 hydrothermal reaction kettles,
160 DEG C of baking ovens react 30 hours, washing, collect and obtain the three-dimensional column redox graphene of 18mg.
Compound working procedure：1.5g zinc nitrate is dissolved in 14mL deionized water, adds 6mL 15mol/L concentrated ammonia liquor, magnetic force
Stirring a period of time, forming solution, joining in above-mentioned solution by three-dimensional for 18mg column redox graphene, 3 DEG C are soaked 3
My god, it is transferred to solution and three-dimensional column redox graphene in reactor subsequently, 80 DEG C are reacted 12 hours in an oven, will
Product washs, and 80 DEG C are vacuum dried 4 hours, collect product.
Calcining process：Take product in atmosphere in 250 DEG C of constant temperature calcinings 6 hours, naturally cool to room temperature, aoxidized
Zinc/graphene composite material.
Embodiment 2
The preparation method of graphite oxide is with embodiment 1.
Hydro-thermal operation：70mg graphite oxide is dissolved in 80mL deionized water, adds the 6mL concentrated sulfuric acid (ρ=1.84g/
cm3), ultrasonic disperse 3 hours, move into solution in vial, be then averaged and transfer in 5 hydrothermal reaction kettles,
200 DEG C of baking ovens react 26 hours, washing, collect and obtain the three-dimensional column redox graphene of 14mg.
Compound working procedure：Being dissolved in 3.0g zinc sulfate in 14mL deionized water, adding 6mL15mol/L concentrated ammonia liquor, magnetic force stirs
Mixing a period of time, forming solution, join in above-mentioned solution by three-dimensional for 14mg column redox graphene, 15 DEG C are soaked 4 days,
Being transferred to solution and three-dimensional grapheme in reactor subsequently, 100 DEG C are reacted 6 hours in an oven, wash product, and 30 DEG C true
Empty dry 24 hours, collect product.
Calcining process：Take product in atmosphere in 300 DEG C of constant temperature calcinings 5 hours, naturally cool to room temperature, aoxidized
Zinc/graphene composite material.
Embodiment 3
The preparation method of graphite oxide is with embodiment 1.
Hydro-thermal operation：60mg graphite oxide is dissolved in 80mL deionized water, adds the 6mL concentrated sulfuric acid (ρ=1.84g/
cm3), ultrasonic disperse 3 hours, move into solution in vial, be then averaged and transfer in 5 hydrothermal reaction kettles,
200 DEG C of baking ovens react 20 hours, washing, collect and obtain the three-dimensional column redox graphene of 12mg.
Compound working procedure：1.3g zinc acetate is dissolved in 20mL deionized water, adds 0.2g hexamethylene tetramine, magnetic force
Stirring a period of time, forming solution, joining in above-mentioned solution by three-dimensional for 12mg column redox graphene, 35 DEG C are soaked 1
My god, it is transferred to solution and three-dimensional column redox graphene in reactor subsequently, 120 DEG C are reacted 8 hours in an oven, will
Product washs, and 70 DEG C are vacuum dried 8 hours, collect product.
Calcining process：Take product in atmosphere in 400 DEG C of constant temperature calcinings 3 hours, naturally cool to room temperature, aoxidized
Zinc/graphene composite material.
Embodiment 4
The preparation method of graphite oxide is with embodiment 1.
Hydro-thermal operation：120mg graphite oxide is dissolved in 80mL deionized water, adds the 6mL concentrated sulfuric acid (ρ=1.84g/
cm3), ultrasonic disperse 3 hours, move into solution in vial, be then averaged and transfer in 5 hydrothermal reaction kettles,
260 DEG C of baking ovens react 18 hours, washing, collect and obtain the three-dimensional column redox graphene of 24mg.
Compound working procedure：Being dissolved in 1.7g zinc acetate in 14mL deionized water, adding 6mL15mol/L concentrated ammonia liquor, magnetic force stirs
Mixing a period of time, forming solution, join in above-mentioned solution by three-dimensional for 24mg column redox graphene, 40 DEG C are soaked 2 days,
Being transferred to solution and three-dimensional column redox graphene in reactor subsequently, 140 DEG C are reacted 4 hours in an oven, will produce
Thing washs, and 50 DEG C are vacuum dried 5 hours, collect product.
Calcining process：Take product in atmosphere in 450 DEG C of constant temperature calcinings 2 hours, naturally cool to room temperature, aoxidized
Zinc/graphene composite material.
Embodiment 5
The preparation method of graphite oxide is with embodiment 1.
Hydro-thermal operation：100mg graphite oxide is dissolved in 80mL deionized water, adds the 6mL concentrated sulfuric acid (ρ=1.84g/
cm3), ultrasonic disperse 3 hours, move into solution in vial, be then averaged and transfer in 5 hydrothermal reaction kettles,
220 DEG C of baking ovens react 18 hours, washing, collect and obtain the three-dimensional column redox graphene of 20mg.
Compound working procedure：1.3g zinc chloride is dissolved in 20mL deionized water, adds 1.2g urea, during magnetic agitation one section
Between, form solution, three-dimensional for 20mg column redox graphene joined in above-mentioned solution, soaks 3 days in 30 DEG C of water-baths,
Being transferred to solution and three-dimensional column redox graphene in reactor subsequently, 160 DEG C are reacted 2 hours in an oven, will produce
Thing washs, and 60 DEG C are vacuum dried 4 hours, collect product.
Calcining process：Take product in atmosphere in 550 DEG C of constant temperature calcinings 0.5 hour, naturally cool to room temperature, aoxidized
Zinc/graphene composite material.
Embodiment 5 gained end product zinc oxide/graphene nanocomposite material ethanol is sized mixing, has spread upon a pair
The outer surface of the aluminum oxide tubular substrate of Au electrode, then 60 DEG C of dryings 2 hours, then calcines 2 hours at 300 DEG C.Finally,
One little Ni-Cr alloy coil is inserted in this pipe as heater, provide operating temperature for gas sensor.Pass for improving
Sensor is placed in operating temperature (240 DEG C) and keeps 48 hours by the long-time stability of sensor.During test, by test gas such as formaldehyde
Body injects test box and mixes with air, carries out in ART-2000A (Beijing Art Technology Development Co., Ltd.) test system
Detection.In this test system, the sensitivity that gas is responded by sensor can be calculated by formula below：S=Ra/Rg=Vgas·
(5000mV-Vair)/Vair·(5000mV-Vgas), VairAnd VgasIt is output electricity in air and test gas for the sensor respectively
Pressure.After response time and recovery time refer to sample introduction or extract test gas after sensor output reach stationary value 90% needed for
Time.At operating temperature 240 DEG C, the sensitive of 7 kinds of organic steams (100ppm) is responded as shown in Figure 7 by sensor.By Fig. 7
Visible, sensor is 240 DEG C in operating temperature and has good sensitive response to gases such as 100ppm ethanol and methyl alcohol.
Claims (10)
1. a preparation method for zinc oxide/graphene composite material, step includes：
A, hydro-thermal operation：Graphite oxide is dispersed in water ultrasonic prepared graphene oxide solution, in solution, adds sulfuric acid, then
Ultrasonic disperse uniformly prepares mixed liquor, then mixed liquor is transferred in reactor react 18～30 at 160～260 DEG C little
When, taking out washing, obtain three-dimensional column redox graphene, it is little that reaction condition preferably reacts 20～24 at 190～220 DEG C
When；
B, compound working procedure：Zinc salt is dissolved in deionized water, adds precipitating reagent, stirring, prepare soak, then by three-dimensional column
Redox graphene puts in above-mentioned solution, soaks more than 1 day at 3～40 DEG C, soaks 1～3 day at preferably 10～30 DEG C；
It is finally transferred to solution and three-dimensional column redox graphene in hydrothermal reaction kettle, at 80～160 DEG C, react 2～12 little
When, preferably react 4～6 hours at 100～120 DEG C, after product is scrubbed and dry, obtain zinc oxide and Graphene composite wood
Material i.e. zinc oxide/graphene composite material.
C, calcining process：By predecessor obtained in compound working procedure at 250～550 DEG C roasting 0.5～6 hour, naturally cold
But to room temperature, zinc oxide/graphene composite material is prepared；Preferably roasting 1～3 hour at 300～500 DEG C.
2. preparation method as claimed in claim 1, it is characterised in that：Graphene oxide dense in mixed liquor in described step A
Degree is 0.75～1.5g/L, preferably 1.0～1.25g/L.
3. preparation method as claimed in claim 1, it is characterised in that：In described step A, in mixed liquor, the concentration of sulfuric acid is 0.8
～1.7mol/L, preferably 1.2～1.4mol/L.
4. preparation method as claimed in claim 1, it is characterised in that：In described step B zinc salt selected from zinc nitrate, zinc acetate,
One or more in zinc chloride and zinc sulfate, described zinc salt concentration in the solution is 0.1～0.8mol/L, preferably 0.15～
0.40mol/L.
5. preparation method as claimed in claim 1, it is characterised in that：In described step B, precipitating reagent is selected from ammoniacal liquor, hexa-methylene
One in tetramine, urea, when in soak, precipitating reagent is ammoniacal liquor, concentration in soak for the ammoniacal liquor is 1.0～8.0mol/L,
Preferably 2.0～5.0mol/L；When in soak, precipitating reagent is hexa, concentration in soak for the hexa
0.1～1.5mol/L, preferably 0.2～1.0mol/L；When in soak, precipitating reagent is urea, concentration in soak for the urea is
1.0～6.0mol/L, preferably 2.5～4.0mol/L；The preferred ammoniacal liquor of precipitating reagent.
6. preparation method as claimed in claim 1, it is characterised in that：In described step B, three-dimensional redox graphene is molten
Concentration in liquid is 0.1～4.0mg/mL, preferably 0.6～1.2mg/mL.
7. preparation method as claimed in claim 1, it is characterised in that：Described step B is dried for vacuum drying, vacuum drying
Temperature 30～80 DEG C, 4～24 hours drying times, is preferably dried 8～16 hours at 40～70 DEG C.
8. preparation method as claimed in claim 1, it is characterised in that：In described step C, the temperature of roasting is 300～500 DEG C.
9. preparation method as claimed in claim 1, it is characterised in that：In described step C, roasting time is 1～3 hour.
10. a resistor-type gas sensor, by including that zinc oxide/graphene composite material sensitive layer is made.
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