CN106442642B - A kind of preparation method of zinc oxide/graphene composite material, resistor-type gas sensor - Google Patents
A kind of preparation method of zinc oxide/graphene composite material, resistor-type gas sensor Download PDFInfo
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- CN106442642B CN106442642B CN201610765892.3A CN201610765892A CN106442642B CN 106442642 B CN106442642 B CN 106442642B CN 201610765892 A CN201610765892 A CN 201610765892A CN 106442642 B CN106442642 B CN 106442642B
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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 kind of preparation methods of zinc oxide/graphene composite material, resistor-type gas sensor, preparation method step includes hydro-thermal process, compound working procedure, calcining process, preparation method of the present invention makes Zinc oxide nanoparticle uniform load in the surface and cellular structure of three-dimensional grapheme, by washing, it is dry to obtain zinc oxide/graphene composite material, the material is applied to resistor-type gas sensor, has that selectivity is good, high sensitivity, stablizes, the excellent properties such as response quickly.
Description
Technical field
The present invention relates to a kind of technical field of inorganic nanometer material, in particular to a kind of zinc oxide/graphene composite material
Preparation method, resistor-type gas sensor.
Background technique
Gas sensor is a kind of detection gas device, can will be divided gas componant, volume using physics and chemical effect
Number is converted into electric signal according to certain rules, is required with meeting processing, display, record and control of information for obtaining etc., so as to
It is the core of gas detecting system to be detected, be monitored, analyzed and alarmed.In recent years, gas sensor is answered extensively
For producing, living etc., fields are monitored some toxic or imflammable gas.Resistance-type gas sensor utilizes material table
Face adsorption and desorption gas molecule can cause the variation of conductivity semiconductor to carry out detection gas.It has high sensitivity, operation side
Just, the advantages that small in size, low in cost, response time and recovery time are short, it is most widely used.Three constructed for sensor
Graphene composite material is tieed up, there is high perforative pore structure, specific surface area, light weight and excellent electric conductivity, be conducive to sense
It is come into full contact between the detection layers and detected gas of device, to increase the sensitivity and stability of sensor.
Three-dimensional grapheme is a kind of carbon material that structure is special, have extremely-low density, surface area big, high thermal conductivity, high temperature resistant,
The advantages that corrosion-resistant, ductility, flexibility are good makes it have huge application potential in sensor field.With porous knot
The three-dimensional grapheme of structure can reduce the reunion of graphene sheet layer, provide it is bigger using surface area, higher mechanical strength,
Faster proton and electron transmission and more reactivity sites.Nanocomposite due to its excellent comprehensive performance and
Designability, it has also become one of nano materials research hot spot.Graphene inorganic nanocomposite not only maintain graphene and
The respective property of inorganic nano material, and since the synergistic effect between them can also greatly reinforce their inherent characteristic,
Make its catalysis, sensing, energy storage and in terms of obtain important application.
Zinc oxide is a kind of multifunctional semiconductor material of broad-band gap, the uniqueness with optics, electricity, catalysis etc.
Can, have wide practical use, can be used for the fields such as sensor, solar battery, lithium battery, catalysis.Zinc oxide material has
The advantages that preparation cost is low, chemical stability and thermal stability are good, abundant and controllable surface texture is studied in gas sensor
In be concerned.Zinc oxide/graphene composite material building soft sensor research at present is not very much, to have wide
Application prospect.Since Zinc oxide nanoparticle is easy to reunite, to reduce the air-sensitive performance of sensitive material.Chinese invention patent CN
104764779A discloses a kind of zinc oxide and spongy graphene composite nano materials for gas sensor, which uses
Chemical vapor deposition method prepares spongy graphene on foam metal, and then compound upper nano zine oxide, this method consume again
Can be big, it is unfavorable for industrialized production.Liu Xin et al. (Sensors and Actuators B, 2015,211,220-226) is adopted
Zinc oxide and three-dimensional porous graphene oxide composite material, three-dimensional surface of graphene oxide and body phase are prepared with one step hydro thermal method
It is larger to load Zinc oxide particles partial size, and homogeneity is poor, to influence gas sensor test performance.In conclusion big at present
More graphene composite materials are the admixtures of graphene and zinc oxide, and zinc oxide is unevenly distributed with inside on the surface of graphene
Even, in gas molecule absorption and desorption process, gas molecule is difficult to be adsorbed on zinc oxide and graphene boundary layer, so as to cause
Electron transport ability decline, the final air-sensitive performance for influencing sensor.
Summary of the invention
In view of the shortcomings of the prior art, technical problem to be solved by the invention is to provide a kind of zinc oxide/graphite
The preparation method of alkene composite material, resistor-type gas sensor.Three-dimensional reduction is prepared using cheap raw material in the present invention
Graphene oxide obtains zinc oxide/graphene composite material by hydro-thermal, compound, washing, dry and roasting.The present invention is directed to
Extensive use of the zinc oxide as the technical problems and graphene composite material such as the sensitivity of sensing material and selectivity is improved, is mentioned
A kind of composite material and preparation method thereof of high, the easy expanding production of simple process, yield is supplied.
The technical solution adopted by the present invention is that:
A kind of preparation method of zinc oxide/graphene composite material, step include:
A, hydro-thermal process: graphite oxide is dispersed in water the obtained graphene oxide solution of ultrasound, sulphur is added into solution
Mixed liquor is uniformly made in acid, re-ultrasonic dispersion, then by mixed liquor be transferred in reaction kettle at 160~260 DEG C reaction 18~
30 hours, washing being taken out, obtains three-dimensional column redox graphene, reaction condition reacts 20 preferably at 190~220 DEG C~
24 hours；
Graphite oxide is by improving the synthesis of Hummers method, specific steps are as follows: weigh 5.0g graphite respectively in the step A
With 3.75g NaNO3It is put into the beaker of 1L, mechanical strong stirring, is slowly added to the concentrated sulfuric acid of 150mL, stir 0.5 hour, then
It is slowly added to the KMnO of 20g4, add within 0.5 hour, after continuing stirring 20 hours, reactant viscosity increases, and stops stirring, obtains
The purplish red color substance of starchiness.After placing 5 days, it is respectively added slowly to 500mL deionized water and 30mL H2O2, solution colour becomes at this time
For obvious glassy yellow, after solution sufficiently reacts, centrifugation, washing obtain graphite oxide.
The concentration of graphene oxide is 0.75~1.5g/L, preferably 1.0~1.25g/L in mixed liquor in the step A；
The concentration of sulfuric acid is 0.8~1.7mol/L, preferably 1.2~1.4mol/L in mixed liquor in the step A.
B, compound working procedure: zinc salt is dissolved in deionized water, and precipitating reagent is added, and soak is made in stirring, then will be three-dimensional
Column redox graphene is put into above-mentioned solution, is impregnated at 3~40 DEG C immersion 1 at 1 day or more, preferably 10~30 DEG C~
3 days；Finally solution and three-dimensional column redox graphene are transferred in hydrothermal reaction kettle, at 80~160 DEG C react 2~
It 12 hours, is reacted 4~6 hours preferably at 100~120 DEG C, after product is washed and dry, obtains zinc oxide and graphene is multiple
Condensation material, that is, zinc oxide/graphene composite material.
Zinc salt is selected from one or more of zinc nitrate, zinc acetate, zinc chloride and zinc sulfate, the zinc in the step B
Concentration of the salt in soak is 0.1~0.8mol/L, preferably 0.15~0.40mol/L；
Precipitating reagent is selected from one of ammonium hydroxide, hexa, urea in the step B, and precipitating reagent is in soak
When ammonium hydroxide, concentration of the ammonium hydroxide in soak is 1.0~8.0mol/L, preferably 2.0~5.0mol/L；Precipitating reagent is in soak
When hexa, hexa 0.1~1.5mol/L of concentration in soak, preferably 0.2~1.0mol/L；Leaching
When precipitating reagent is urea in bubble liquid, concentration of the urea in soak is 1.0~6.0mol/L, preferably 2.5~4.0mol/L；It is heavy
The preferred ammonium hydroxide of shallow lake agent；
The concentration of three-dimensional column redox graphene in the solution is 0.1~4.0mg/mL in the step B, preferably
0.6~1.2mg/mL；
It is dry to be dried in vacuo in the step B, 30~80 DEG C of vacuum drying temperature, drying time 4~24 hours, preferably
It is 8~16 hours dry at 40~70 DEG C.
C, calcining process: predecessor obtained in compound working procedure is roasted 0.5~6 hour at 250~550 DEG C, from
It is so cooled to room temperature, zinc oxide/graphene nanocomposite material is made；It is preferred that being roasted 1~3 hour at 300~500 DEG C；
Described roasting is whole to be carried out in air atmosphere, cooled to room temperature after roasting；
A kind of resistor-type gas sensor, including that sensitive layer made of zinc oxide/graphene composite material is made.
The present invention be directed to conventional semiconductors resistor-type gas sensors to be studied using limitation, is designed a kind of new
Method synthesis have larger active area zinc oxide/graphene composite material, this be conducive to provide more adsorption sites and
Active site, to improve gas sensing performance.The present invention synthesizes three-dimensional column redox graphene using hydro-thermal method, by it
It is immersed in the aqueous solution of zinc salt, by high temperature hydro-thermal, so that table of the Zinc oxide nanoparticle uniform load in three-dimensional grapheme
In face and cellular structure, dry to obtain zinc oxide/graphene composite material by washing, which is applied to resistor-type gas
Sensor, has that selectivity is good, high sensitivity, stablizes, the excellent properties such as response 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 cellular structure.
Compared with the prior art, the present invention has the following advantages:
(1) zinc oxide/graphene composite material obtained by, zinc oxide uniform load are tied on three-dimensional grapheme surface and duct
In structure, increase object gas adsorption surface area；
(2) zinc oxide obtained by/graphene composite material performance is stablized, and the cellular structure of high temperature resistant, three-dimensional grapheme adds
Fast generation electron transfer rate, increases the electric conductivity of material, so that air-sensitive tests signal stabilization；
(3) zinc oxide/graphene composite material large specific surface area obtained by, under test gas are sufficiently adsorbed in the interior of material
Outer surface, three-dimensional cavernous structure provide multiple electronic channel, to realize to the quick sensitive detection of object gas；
(4) zinc oxide/graphene composite material obtained by be used for resistor-type gas sensor, have higher sensitivity and compared with
Good selectivity；
(5) synthesis step is simple, and the instrument and equipment used to experiment requires low, and raw material sources are extensive, and cost is relatively low, can be into
Row batch production.
Detailed description of the invention
Fig. 1 is zinc oxide/graphene composite material SEM figure prepared by embodiment 1；
Fig. 2 is zinc oxide/graphene composite material SEM figure prepared by embodiment 2；
Fig. 3 is zinc oxide/graphene composite material SEM figure prepared by embodiment 3；
Fig. 4 is zinc oxide/graphene composite material XRD diagram prepared by embodiment 3；
Fig. 5 is zinc oxide/graphene composite material SEM figure prepared by embodiment 4；
Fig. 6 is zinc oxide/graphene composite material SEM figure prepared by embodiment 5；
Fig. 7 is zinc oxide/graphene composite material gas sensor of the preparation of embodiment 5 in the case where operating temperature is 240 DEG C,
Response to 7 kinds of organic steams (100ppm).
Specific embodiment
Embodiment 1
The preparation of graphite oxide: 5.0g graphite and 3.75g NaNO are weighed respectively3It is put into the beaker of 1L, mechanical strength is stirred
It mixes, is slowly added to the concentrated sulfuric acid of 150mL, stir 0.5 hour, be slow added into the KMnO of 20g4, add within 0.5 hour, continue to stir
After mixing 20 hours, reactant viscosity increases, and stops stirring, obtains the purplish red color substance of starchiness.After placing 5 days, slowly add respectively
Enter 500mL deionized water and 30mL H2O2, solution colour becomes obvious glassy yellow at this time, after solution sufficiently reacts, from
The heart, washing, obtain graphite oxide.
Hydro-thermal process: 90mg graphite oxide is dissolved in 80mL deionized water, and the 6mL concentrated sulfuric acid (ρ=1.84g/ is added
cm3), ultrasonic disperse 3 hours, solution is moved into vial, then by its mean transferred into 5 hydrothermal reaction kettles,
It reacts 30 hours, washs in 160 DEG C of baking ovens, collection obtains 18mg three-dimensional column redox graphene.
Compound working procedure: 1.5g zinc nitrate is dissolved in 14mL deionized water, and 6mL 15mol/L concentrated ammonia liquor, magnetic force is added
Stirring a period of time, solution is formed, 18mg three-dimensional column redox graphene is added in above-mentioned solution, 3 DEG C are impregnated 3
Solution and three-dimensional column redox graphene, are then transferred in reaction kettle by it, react 12 hours for 80 DEG C in an oven, will
Product washing, 80 DEG C are dried in vacuo 4 hours, collect product.
Calcining process: take product in air in 250 DEG C constant temperature calcining 6 hours, cooled to room temperature is aoxidized
Zinc/graphene composite material.
Embodiment 2
The preparation method is the same as that of Example 1 for graphite oxide.
Hydro-thermal process: 70mg graphite oxide is dissolved in 80mL deionized water, and the 6mL concentrated sulfuric acid (ρ=1.84g/ is added
cm3), ultrasonic disperse 3 hours, solution is moved into vial, then by its mean transferred into 5 hydrothermal reaction kettles,
It reacts 26 hours, washs in 200 DEG C of baking ovens, collection obtains 14mg three-dimensional column redox graphene.
Compound working procedure: 3.0g zinc sulfate is dissolved in 14mL deionized water, and 6mL15mol/L concentrated ammonia liquor is added, and magnetic force stirs
A period of time is mixed, solution is formed, 14mg three-dimensional column redox graphene is added in above-mentioned solution, 15 DEG C are impregnated 4 days,
Then solution and three-dimensional grapheme are transferred in reaction kettle, reacts 6 hours for 100 DEG C in an oven, product is washed, 30 DEG C true
Sky is 24 hours dry, collects product.
Calcining process: take product in air in 300 DEG C constant temperature calcining 5 hours, cooled to room temperature is aoxidized
Zinc/graphene composite material.
Embodiment 3
The preparation method is the same as that of Example 1 for graphite oxide.
Hydro-thermal process: 60mg graphite oxide is dissolved in 80mL deionized water, and the 6mL concentrated sulfuric acid (ρ=1.84g/ is added
cm3), ultrasonic disperse 3 hours, solution is moved into vial, then by its mean transferred into 5 hydrothermal reaction kettles,
It reacts 20 hours, washs in 200 DEG C of baking ovens, collection obtains 12mg three-dimensional column redox graphene.
Compound working procedure: 1.3g zinc acetate is dissolved in 20mL deionized water, and 0.2g hexamethylene tetramine, magnetic force is added
Stirring a period of time, solution is formed, 12mg three-dimensional column redox graphene is added in above-mentioned solution, 35 DEG C are impregnated 1
Solution and three-dimensional column redox graphene, are then transferred in reaction kettle by it, react 8 hours for 120 DEG C in an oven, will
Product washing, 70 DEG C are dried in vacuo 8 hours, collect product.
Calcining process: take product in air in 400 DEG C constant temperature calcining 3 hours, cooled to room temperature is aoxidized
Zinc/graphene composite material.
Embodiment 4
The preparation method is the same as that of Example 1 for graphite oxide.
Hydro-thermal process: 120mg graphite oxide is dissolved in 80mL deionized water, and the 6mL concentrated sulfuric acid (ρ=1.84g/ is added
cm3), ultrasonic disperse 3 hours, solution is moved into vial, then by its mean transferred into 5 hydrothermal reaction kettles,
It reacts 18 hours, washs in 260 DEG C of baking ovens, collection obtains 24mg three-dimensional column redox graphene.
Compound working procedure: 1.7g zinc acetate is dissolved in 14mL deionized water, and 6mL15mol/L concentrated ammonia liquor is added, and magnetic force stirs
A period of time is mixed, solution is formed, 24mg three-dimensional column redox graphene is added in above-mentioned solution, 40 DEG C are impregnated 2 days,
Then solution and three-dimensional column redox graphene are transferred in reaction kettle, reacts 4 hours for 140 DEG C, will produce in an oven
Object washing, 50 DEG C are dried in vacuo 5 hours, collect product.
Calcining process: take product in air in 450 DEG C constant temperature calcining 2 hours, cooled to room temperature is aoxidized
Zinc/graphene composite material.
Embodiment 5
The preparation method is the same as that of Example 1 for graphite oxide.
Hydro-thermal process: 100mg graphite oxide is dissolved in 80mL deionized water, and the 6mL concentrated sulfuric acid (ρ=1.84g/ is added
cm3), ultrasonic disperse 3 hours, solution is moved into vial, then by its mean transferred into 5 hydrothermal reaction kettles,
It reacts 18 hours, washs in 220 DEG C of baking ovens, collection obtains 20mg three-dimensional column redox graphene.
Compound working procedure: 1.3g zinc chloride is dissolved in 20mL deionized water, 1.2g urea is added, at one section of magnetic agitation
Between, solution is formed, 20mg three-dimensional column redox graphene is added in above-mentioned solution, is impregnated 3 days in 30 DEG C of water-baths,
Then solution and three-dimensional column redox graphene are transferred in reaction kettle, reacts 2 hours for 160 DEG C, will produce in an oven
Object washing, 60 DEG C are dried in vacuo 4 hours, collect product.
Calcining process: take product in air in 550 DEG C constant temperature calcining 0.5 hour, cooled to room temperature is aoxidized
Zinc/graphene composite material.
5 gained final product zinc oxide of embodiment/graphene nanocomposite material is sized mixing with ethyl alcohol, has been applied to a pair
The outer surface of the aluminium oxide tubular substrate of Au electrode, it is then 2 hours dry at 60 DEG C, then calcined 2 hours at 300 DEG C.Finally,
One small Ni-Cr alloy coil is inserted into this pipe as heater, provides operating temperature for gas sensor.It is passed to improve
Sensor is placed in (240 DEG C) of operating temperature and is kept for 48 hours by the long-time stability of sensor.When test, formaldehyde etc. is tested into gas
Body injection test box mixes with air, and carries out in ART-2000A (Beijing Art Technology Development Co., Ltd.) test macro
Detection.In the test macro, sensor can calculate the sensitivity that gas responds with following formula: S=Ra/Rg=Vgas·
(5000mV-Vair)/Vair·(5000mV-Vgas), VairAnd VgasIt is output electricity of the sensor in air and test gas respectively
Pressure.Response time and recovery time refer to after sample introduction or abstraction test gas after sensor output reach needed for the 90% of stationary value
Time.At 240 DEG C of operating temperature, sensor is as shown in Figure 7 to the sensitive response of 7 kinds of organic steams (100ppm).By Fig. 7
As it can be seen that sensor, which is 240 DEG C in operating temperature, has good sensitive response to gases such as 100ppm ethyl alcohol and methanol.
Claims (17)
1. a kind of preparation method of zinc oxide/graphene composite material, step include:
A, hydro-thermal process: being dispersed in water the obtained graphene oxide solution of ultrasound for graphite oxide, sulfuric acid be added into solution, then
Mixed liquor is uniformly made in ultrasonic disperse, and it is small that mixed liquor is then transferred in reaction kettle the reaction 18~30 at 160~260 DEG C
When, washing is taken out, three-dimensional column redox graphene is obtained；
B, compound working procedure: zinc salt is dissolved in deionized water, and precipitating reagent is added, and soak is made, then by three-dimensional column in stirring
Redox graphene is put into above-mentioned solution, is impregnated 1 day or more at 3~40 DEG C；Finally solution and three-dimensional column are restored
Graphene oxide is transferred in hydrothermal reaction kettle, is reacted 2~12 hours at 80~160 DEG C, after product is washed and dry, is obtained
To zinc oxide and graphene composite material, that is, zinc oxide/graphene composite material；
C, calcining process: predecessor obtained in compound working procedure is roasted 0.5~6 hour at 250~550 DEG C, naturally cold
But to room temperature, zinc oxide/graphene composite material is made.
2. preparation method as described in claim 1, it is characterised in that: the reaction of mixed liquor in a kettle in the step A
Condition is to react 20~24 hours at 190~220 DEG C；Three-dimensional column redox graphene is in soak in the step B
Middle soaking conditions are to impregnate 1~3 day at 10~30 DEG C, and solution and three-dimensional column redox graphene are in hydrothermal reaction kettle
Reaction condition is to react 4~6 hours at 100~120 DEG C.
3. preparation method as described in claim 1, it is characterised in that: in the step A in mixed liquor graphene oxide it is dense
Degree is 0.75~1.5g/L.
4. preparation method as claimed in claim 3, it is characterised in that: in the step A in mixed liquor graphene oxide it is dense
Degree is 1.0~1.25g/L.
5. preparation method as described in claim 1, it is characterised in that: the concentration of sulfuric acid is 0.8 in mixed liquor in the step A
~1.7mol/L.
6. preparation method as claimed in claim 5, it is characterised in that: the concentration of sulfuric acid is 1.2 in mixed liquor in the step A
~1.4mol/L.
7. preparation method as described in claim 1, it is characterised in that: in the step B zinc salt be selected from zinc nitrate, zinc acetate,
One or more of zinc chloride and zinc sulfate, the concentration of the zinc salt in the solution are 0.1~0.8mol/L.
8. preparation method as claimed in claim 7, it is characterised in that: the concentration of the zinc salt in the solution be 0.15~
0.40mol/L。
9. preparation method as described in claim 1, it is characterised in that: precipitating reagent is selected from ammonium hydroxide, hexa-methylene in the step B
One of tetramine, urea, when precipitating reagent is ammonium hydroxide in soak, concentration of the ammonium hydroxide in soak is 1.0~8.0mol/L；
When precipitating reagent is hexa in soak, concentration 0.1~1.5mol/L of the hexa in soak；It impregnates
When precipitating reagent is urea in liquid, concentration of the urea in soak is 1.0~6.0mol/L.
10. preparation method as claimed in claim 9, it is characterised in that: when precipitating reagent is ammonium hydroxide in soak, ammonium hydroxide is impregnating
Concentration in liquid is 2.0~5.0mol/L；When precipitating reagent is hexa in soak, hexa is in soak
In concentration be 0.2~1.0mol/L；In soak precipitating reagent be urea when, concentration of the urea in soak be 2.5~
4.0mol/L。
11. preparation method as described in claim 1, it is characterised in that: three-dimensional column redox graphene in the step B
Concentration in the solution is 0.1~4.0mg/mL.
12. preparation method as claimed in claim 11, it is characterised in that: three-dimensional column reduction-oxidation graphite in the step B
The concentration of alkene in the solution is 0.6~1.2mg/mL.
13. preparation method as described in claim 1, it is characterised in that: dry to be dried in vacuo in the step B, vacuum is dry
30~80 DEG C of dry temperature, drying time 4~24 hours.
14. preparation method as claimed in claim 13, it is characterised in that: dry to be dried in vacuo in the step B, vacuum is dry
40~70 DEG C of dry temperature, drying time 8~16 hours.
15. preparation method as described in claim 1, it is characterised in that: the temperature roasted in the step C is 300~500
℃。
16. preparation method as described in claim 1, it is characterised in that: calcining time is 1~3 hour in the step C.
17. a kind of resistor-type gas sensor, as including the preparation method as described in any one of claim 1-16 claim
The zinc oxide of preparation/graphene composite material sensitive layer is made.
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