CN109399616A - A kind of graphene organic material and its application in gas sensor - Google Patents
A kind of graphene organic material and its application in gas sensor Download PDFInfo
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Abstract
The present invention provides a kind of graphene organic material and its application in gas sensor, is related to grapheme material field, and preparation method is previously prepared zinc oxide/graphene complex；By above-mentioned zinc oxide/graphene complex under argon gas protection, terephthalonitrile and nano tin dioxide mixing, after ball milling 30-50min, mixture is transferred in ceramic crucible, 400-450 DEG C of heating reaction 40-50h obtains black solid in Muffle furnace under argon gas protection, it is ground into after black powder to be added in dilute hydrochloric acid and is stored at room temperature 20-25h after stir process 5-10h, after suction filtration, it is washed three times with water and tetrahydrofuran respectively, it filters in vacuum drying oven, it is dried in vacuo at 80-95 DEG C, the graphene organic material can be obtained, graphene organic material of the present invention has big theoretical specific surface area, and the gas load ability of unit volume is strong, covalent bond can be formed with gas molecule, it is captured, the original part for being suitable as gas sensor uses.
Description
Technical field
The present invention relates to grapheme material fields, and in particular to a kind of graphene organic material and its in gas sensor
Application.
Background technique
Gas sensor can be used for detecting flammable, the equipment of inflammable and toxic gas and/or the consumption of oxygen this seed type
Device be also widely used for industry or fire extinguishing.A variety of materials such as inorganic semiconductor, conjugated polymer and carbon nanomaterial have been visited
Rope is into manufacture gas sensor.
Among these, the gas sensor based on graphene causes strong concern recently.As gas sensor
Sensing material, the excellent properties of graphene have kind unique and attractive.
Firstly, graphene has big theoretical specific surface area, all atoms of single-layer graphene film are considered table
The molecule of face atom and their energy adsorbed gases, provides the maximum sensing region of per unit volume.Secondly, between graphene film
Interaction and absorption may be because of faint Van der Waals forces, with powerful covalent bond.The disturbance of all these interactions is by stone
The electronic system of black alkene, the system can pass through convenient electronic method with easily MONI-tored.Third, the charge of graphene
It is zero to show significant high carrier mobility at room temperature close to its dirac point and graphene that carrier, which has rest mass,
So that graphene is than silver-colored conductive and to have in substance at room temperature be minimum resistivity.
In addition, graphene has intrinsic low electrical noise, since the lattice of its high-quality is together with its two-dimensional structure, so that
It being capable of the more charge fluctuations of the one-dimensional correspondence of shielding ratio.As a result, a small amount of additional electronics can cause the conductance of graphite
Rate changes significantly.The resistance of the graphene film of gas absorption caused by one very small variation even has decreased to point
Sub- level is detectable.Moreover, graphene film, it can also be used to four-point equipment is manufactured, effectively to eliminate contact resistance
It influences.The graphene of chemical conversion can also be synthesized in large-scale advantage of lower cost.In fact, grapheme material is extensive
For detecting toxic and explosive gas.
The mechanism of action of graphene gas sensor is that its conductivity changes after graphene adsorbed target gas, is passed through
Determine the variation relation between conductivity variations and object table gas concentration, so that it may by measure graphene conductivity variations from
And measure the concentration of object gas.It belongs to a kind of resistance sensor, and the detection by grapheme material gas is mainly base
In its conductance of absorption variation in sensing substance.Gaseous sorbate has different the Nomenclature Composition and Structure of Complexes from graphene in different moulds
Formula interacts.The absorption of inertia closed pore does not induce graphene to detect local distortion's state as water, they influence the conductance of graphene
By shaking up the electronics in graphene film or between piece graphene and its substrate.On the other hand, open cells adsorbate is for example
NO2, alkali metal and halogen have chemically active；They, which can serve as this, facilitates electronics or hole to graphite and changes its electronics
Concentration is temporary dopant.The ion of these molecule combination graphenes, but hybridize with graphene band weak.Another adsorbate is
Covalent bond absorption, including H and OH free radical, it can form covalent bond and graphene.
Graphene is substantially a p-n junction semiconductor.When it is exposed to various gases, the response direction of conductance can
It can be different.The absorption of the gas molecule of electron-withdrawing group such as NO2 enhances the doped level of graphene, and increases its electricity
It leads.On the other hand, electron molecule such as NH3 solves the graphene of stoste, and reduces its conductivity.
Various graphene composite materials are also used as sensing material, to improve the gas sensor based on graphene
Performance.Wherein, graphene/polymer composites usually have porous microstructure, to accelerate the gas in sensing layer to expand
It dissipates.In this case, two kinds of components of complex with adsorption gas molecule, can promote the conductance variation of sensing layer.Your gold
Belong to the nano particle of Pt and Pd such as and is fixed on graphene film with the reaction of catalyzed gas, in order to improve sensing signal.Absorption
Oxygen or hydrone on the surface of graphene and its composite material can also interact with sensor molecules, and to sensing response
Contribution.In particular, for graphite/metal oxide composite, the absorption of oxygen is sometimes to pass for realizing detection reaction
Important.The oxygen molecule absorbed is captured may to be converted into ionic species from the electronics of metal oxide.Introduce the gas of detection
After body type, the electron concentration on the surface of metal oxide changes, because of the phase between gas and the oxonium ion being adsorbed
Interaction, and the conductance of sensing layer is caused to change.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of graphene organic material and its in gas sensor
Using.
(2) technical solution
In order to achieve the above object, the present invention is achieved by the following technical programs:
A kind of graphene organic material, preparation method are as follows:
(1) it is added to graphite oxide is dilute in ethylene glycol, ultrasonic vibration processing makes it be completely dispersed and remove, and dries after filtering out
It is dry stand-by, then zinc acetate and sodium hydroxide are dissolved in ethylene glycol solution, magnetic agitation is to after being completely dissolved, by above-mentioned oxidation stone
The dilute addition 400-500r/min mechanical mixture 20-40min of ink, mixed material is transferred in autoclave, at 150-160 DEG C
Heating reaction 25-30h, the product of generation is centrifuged, and acetone elutes after ethanol rinse, 60-70 DEG C of oven drying 5-10h,
Obtain zinc oxide/graphene complex；
(2) above-mentioned zinc oxide/graphene complex, terephthalonitrile and nano tin dioxide are mixed under argon gas protection, ball milling
After 30-50min, mixture is transferred in ceramic crucible, 40- is reacted in 400-450 DEG C of heating in Muffle furnace under argon gas protection
50h obtains black solid, is ground into after black powder to be added in dilute hydrochloric acid and is stored at room temperature 20-25h after stir process 5-10h,
After suction filtration, is washed three times with water and tetrahydrofuran respectively, filter in vacuum drying oven, be dried in vacuo at 80-95 DEG C, institute can be obtained
State graphene organic material.
Preferably, the graphite oxide is dilute is prepared using Hummers method.
Preferably, the Hummers method prepares graphite oxide dilute specific step is as follows:
Graphite powder and sodium nitrate is added under ice-water bath into the concentrated sulfuric acid, then potassium permanganate is added by several times, controls reaction temperature
≤ 20 DEG C, be stirred to react 2-5h, be warming up to 35-40 DEG C, continue stir 30-40min, be slow added into appropriate hydrogen peroxide and go from
Sub- water, is filtered while hot, and deionized water is washed until sulfate radical-free is detected in filtrate, 70-80 DEG C of filter cake drying.
Preferably, the mass ratio of graphite powder and sodium nitrate is 10-20:1-3.
Preferably, the mass ratio of zinc oxide/graphene complex, terephthalonitrile and nano tin dioxide three is 1:3-4:
1.1-1.2。
Preferably, the mass concentration of dilute hydrochloric acid is 5-8%.
Preferably, the temperature of dilute hydrochloric acid stir process is 40-55 DEG C.
Application of the above-mentioned graphene organic material in gas sensor.
Preferably, the gas sensor can be used to detect CO, CO2, H2, NO, NO2, CH4.
(3) beneficial effect
The present invention provides a kind of graphene organic material and its application in gas sensor, have below beneficial to effect
Fruit:
Graphene organic material contains triazine based structures in the present invention, and which imparts its excellent thermal stability and acidproof
Zinc oxide is supported in graphene by alkali, corrosion resistance using hydro-thermal method, has both improved the conductivity of graphene, and it
Gas sensor can be improved to gas sensing the behavior of the architecture that is mixed to form, nano tin dioxide is a kind of outstanding
Transparent conductive material but also there is superior cycle performance, its addition can be formed microcosmic in graphene organic material
Storage organization provides the attachment point of gas molecule, improves sensitivity and service life of the gas sensor to detection, stone of the present invention
Black alkene organic material has big theoretical specific surface area, and the gas load ability of unit volume is strong, can be with gas point
Son forms covalent bond, is captured, and the original part for being suitable as gas sensor uses.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention,
Technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is the present invention one
Divide embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making
Every other embodiment obtained, shall fall within the protection scope of the present invention under the premise of creative work.
Embodiment 1:
A kind of graphene organic material, preparation method are as follows:
(1) it is added to graphite oxide is dilute in ethylene glycol, ultrasonic vibration processing makes it be completely dispersed and remove, and dries after filtering out
It is dry stand-by, then zinc acetate and sodium hydroxide are dissolved in ethylene glycol solution, magnetic agitation is to after being completely dissolved, by above-mentioned oxidation stone
The dilute addition 500r/min mechanical mixture 25min of ink, mixed material are transferred in autoclave, and reaction is heated at 155 DEG C
The product of generation is centrifuged by 26h, and acetone elutes after ethanol rinse, and 60 DEG C of oven drying 8h obtain zinc oxide/graphene
Compound；
(2) above-mentioned zinc oxide/graphene complex, terephthalonitrile and nano tin dioxide are mixed under argon gas protection, oxidation
The mass ratio of zinc/graphene complex, terephthalonitrile and nano tin dioxide three is 1:3:1.1, after ball milling 40min, will be mixed
Object is transferred in ceramic crucible, and 420 DEG C of heating reaction 45h obtain black solid in Muffle furnace under argon gas protection, is ground into black
It is stored at room temperature for 24 hours after 50 DEG C of stir process 5h in the last dilute hydrochloric acid for being added to mass concentration and being 5% of toner, after suction filtration, respectively
It is washed three times with water and tetrahydrofuran, filters in vacuum drying oven, be dried in vacuo at 85 DEG C, the organic material of the graphene can be obtained
Material.
Graphite oxide is dilute to be prepared using Hummers method, the specific steps are as follows:
It is added graphite powder and sodium nitrate under ice-water bath into the concentrated sulfuric acid, the mass ratio of graphite powder and sodium nitrate is 10:1, then
Potassium permanganate is added by several times, controls reaction temperature≤20 DEG C, is stirred to react 4h, is warming up to 36 DEG C, continues to stir 35min, then delay
Slowly appropriate hydrogen peroxide and deionized water is added, filters while hot, deionized water is washed until sulfate radical-free is detected to be in filtrate
Only, 80 DEG C of filter cake drying.
Application of the above-mentioned graphene organic material in gas sensor, the gas sensor can be used to detect CO,
CO2、H2、NO、NO2、CH4。
Embodiment 2:
A kind of graphene organic material, preparation method are as follows:
(1) it is added to graphite oxide is dilute in ethylene glycol, ultrasonic vibration processing makes it be completely dispersed and remove, and dries after filtering out
It is dry stand-by, then zinc acetate and sodium hydroxide are dissolved in ethylene glycol solution, magnetic agitation is to after being completely dissolved, by above-mentioned oxidation stone
The dilute addition 400r/min mechanical mixture 20min of ink, mixed material are transferred in autoclave, and reaction is heated at 150 DEG C
The product of generation is centrifuged by 25h, and acetone elutes after ethanol rinse, and 60 DEG C of oven drying 5h obtain zinc oxide/graphene
Compound；
(2) above-mentioned zinc oxide/graphene complex, terephthalonitrile and nano tin dioxide are mixed under argon gas protection, oxidation
The mass ratio of zinc/graphene complex, terephthalonitrile and nano tin dioxide three is 1:3:1.1, after ball milling 30min, will be mixed
Object is transferred in ceramic crucible, and 400 DEG C of heating reaction 40h obtain black solid in Muffle furnace under argon gas protection, is ground into black
Toner is last to be added in the dilute hydrochloric acid that mass concentration is 5% and is stored at room temperature 20h after 40 DEG C of stir process 5h, after suction filtration, respectively
It is washed three times with water and tetrahydrofuran, filters in vacuum drying oven, be dried in vacuo at 80 DEG C, the organic material of the graphene can be obtained
Material.
Graphite oxide is dilute to be prepared using Hummers method, the specific steps are as follows:
It is added graphite powder and sodium nitrate under ice-water bath into the concentrated sulfuric acid, the mass ratio of graphite powder and sodium nitrate is 10:1, then
Potassium permanganate is added by several times, controls reaction temperature≤20 DEG C, is stirred to react 2h, is warming up to 35 DEG C, continues to stir 30min, then delay
Slowly appropriate hydrogen peroxide and deionized water is added, filters while hot, deionized water is washed until sulfate radical-free is detected to be in filtrate
Only, 70 DEG C of filter cake drying.
Application of the above-mentioned graphene organic material in gas sensor, the gas sensor can be used to detect CO,
CO2、H2、NO、NO2、CH4。
Embodiment 3:
A kind of graphene organic material, preparation method are as follows:
(1) it is added to graphite oxide is dilute in ethylene glycol, ultrasonic vibration processing makes it be completely dispersed and remove, and dries after filtering out
It is dry stand-by, then zinc acetate and sodium hydroxide are dissolved in ethylene glycol solution, magnetic agitation is to after being completely dissolved, by above-mentioned oxidation stone
The dilute addition 500r/min mechanical mixture 40min of ink, mixed material are transferred in autoclave, and reaction is heated at 160 DEG C
The product of generation is centrifuged by 30h, and acetone elutes after ethanol rinse, and 70 DEG C of oven drying 10h obtain zinc oxide/graphene
Compound；
(2) above-mentioned zinc oxide/graphene complex, terephthalonitrile and nano tin dioxide are mixed under argon gas protection, oxidation
The mass ratio of zinc/graphene complex, terephthalonitrile and nano tin dioxide three is 1:4:1.2, after ball milling 50min, will be mixed
Object is transferred in ceramic crucible, and 450 DEG C of heating reaction 50h obtain black solid in Muffle furnace under argon gas protection, is ground into black
Toner is last to be added in the dilute hydrochloric acid that mass concentration is 8% and is stored at room temperature 25h after 55 DEG C of stir process 10h, after suction filtration, respectively
It is washed three times with water and tetrahydrofuran, filters in vacuum drying oven, be dried in vacuo at 95 DEG C, the organic material of the graphene can be obtained
Material.
Graphite oxide is dilute to be prepared using Hummers method, the specific steps are as follows:
It is added graphite powder and sodium nitrate under ice-water bath into the concentrated sulfuric acid, the mass ratio of graphite powder and sodium nitrate is 20:3, then
Potassium permanganate is added by several times, controls reaction temperature≤20 DEG C, is stirred to react 5h, is warming up to 40 DEG C, continues to stir 40min, then delay
Slowly appropriate hydrogen peroxide and deionized water is added, filters while hot, deionized water is washed until sulfate radical-free is detected to be in filtrate
Only, 80 DEG C of filter cake drying.
Application of the above-mentioned graphene organic material in gas sensor, the gas sensor can be used to detect CO,
CO2、H2、NO、NO2、CH4。
Embodiment 4:
A kind of graphene organic material, preparation method are as follows:
(1) it is added to graphite oxide is dilute in ethylene glycol, ultrasonic vibration processing makes it be completely dispersed and remove, and dries after filtering out
It is dry stand-by, then zinc acetate and sodium hydroxide are dissolved in ethylene glycol solution, magnetic agitation is to after being completely dissolved, by above-mentioned oxidation stone
The dilute addition 480r/min mechanical mixture 35min of ink, mixed material are transferred in autoclave, and reaction is heated at 160 DEG C
The product of generation is centrifuged by 26h, and acetone elutes after ethanol rinse, and 60 DEG C of oven drying 8h obtain zinc oxide/graphene
Compound；
(2) above-mentioned zinc oxide/graphene complex, terephthalonitrile and nano tin dioxide are mixed under argon gas protection, oxidation
The mass ratio of zinc/graphene complex, terephthalonitrile and nano tin dioxide three is 1:3:1.1, after ball milling 40min, will be mixed
Object is transferred in ceramic crucible, and 420 DEG C of heating reaction 40h obtain black solid in Muffle furnace under argon gas protection, is ground into black
Toner is last to be added in the dilute hydrochloric acid that mass concentration is 5% and is stored at room temperature 25h after 48 DEG C of stir process 5h, after suction filtration, respectively
It is washed three times with water and tetrahydrofuran, filters in vacuum drying oven, be dried in vacuo at 88 DEG C, the organic material of the graphene can be obtained
Material.
Graphite oxide is dilute to be prepared using Hummers method, the specific steps are as follows:
It is added graphite powder and sodium nitrate under ice-water bath into the concentrated sulfuric acid, the mass ratio of graphite powder and sodium nitrate is 10:2, then
Potassium permanganate is added by several times, controls reaction temperature≤20 DEG C, is stirred to react 2h, is warming up to 40 DEG C, continues to stir 35min, then delay
Slowly appropriate hydrogen peroxide and deionized water is added, filters while hot, deionized water is washed until sulfate radical-free is detected to be in filtrate
Only, 70 DEG C of filter cake drying.
Application of the above-mentioned graphene organic material in gas sensor, the gas sensor can be used to detect CO,
CO2、H2、NO、NO2、CH4。
Embodiment 5:
A kind of graphene organic material, preparation method are as follows:
(1) it is added to graphite oxide is dilute in ethylene glycol, ultrasonic vibration processing makes it be completely dispersed and remove, and dries after filtering out
It is dry stand-by, then zinc acetate and sodium hydroxide are dissolved in ethylene glycol solution, magnetic agitation is to after being completely dissolved, by above-mentioned oxidation stone
The dilute addition 400r/min mechanical mixture 40min of ink, mixed material are transferred in autoclave, and reaction is heated at 160 DEG C
The product of generation is centrifuged by 30h, and acetone elutes after ethanol rinse, and 65 DEG C of oven drying 7h obtain zinc oxide/graphene
Compound；
(2) above-mentioned zinc oxide/graphene complex, terephthalonitrile and nano tin dioxide are mixed under argon gas protection, oxidation
The mass ratio of zinc/graphene complex, terephthalonitrile and nano tin dioxide three is 1:4:1.1, after ball milling 38min, will be mixed
Object is transferred in ceramic crucible, and 400 DEG C of heating reaction 50h obtain black solid in Muffle furnace under argon gas protection, is ground into black
Toner is last to be added in the dilute hydrochloric acid that mass concentration is 7% and is stored at room temperature 25h after 40 DEG C of stir process 8h, after suction filtration, respectively
It is washed three times with water and tetrahydrofuran, filters in vacuum drying oven, be dried in vacuo at 85 DEG C, the organic material of the graphene can be obtained
Material.
Graphite oxide is dilute to be prepared using Hummers method, the specific steps are as follows:
It is added graphite powder and sodium nitrate under ice-water bath into the concentrated sulfuric acid, the mass ratio of graphite powder and sodium nitrate is 15:1, then
Potassium permanganate is added by several times, controls reaction temperature≤20 DEG C, is stirred to react 5h, is warming up to 36 DEG C, continues to stir 40min, then delay
Slowly appropriate hydrogen peroxide and deionized water is added, filters while hot, deionized water is washed until sulfate radical-free is detected to be in filtrate
Only, 70 DEG C of filter cake drying.
Application of the above-mentioned graphene organic material in gas sensor, the gas sensor can be used to detect CO,
CO2、H2、NO、NO2、CH4。
Embodiment 6:
A kind of graphene organic material, preparation method are as follows:
(1) it is added to graphite oxide is dilute in ethylene glycol, ultrasonic vibration processing makes it be completely dispersed and remove, and dries after filtering out
It is dry stand-by, then zinc acetate and sodium hydroxide are dissolved in ethylene glycol solution, magnetic agitation is to after being completely dissolved, by above-mentioned oxidation stone
The dilute addition 500r/min mechanical mixture 40min of ink, mixed material are transferred in autoclave, and reaction is heated at 160 DEG C
The product of generation is centrifuged by 30h, and acetone elutes after ethanol rinse, and 70 DEG C of oven drying 10h obtain zinc oxide/graphene
Compound；
(2) above-mentioned zinc oxide/graphene complex, terephthalonitrile and nano tin dioxide are mixed under argon gas protection, oxidation
The mass ratio of zinc/graphene complex, terephthalonitrile and nano tin dioxide three is 1:3:1.1, after ball milling 30min, will be mixed
Object is transferred in ceramic crucible, and 400 DEG C of heating reaction 40h obtain black solid in Muffle furnace under argon gas protection, is ground into black
Toner is last to be added in the dilute hydrochloric acid that mass concentration is 5% and is stored at room temperature 20h after 40 DEG C of stir process 5h, after suction filtration, respectively
It is washed three times with water and tetrahydrofuran, filters in vacuum drying oven, be dried in vacuo at 80 DEG C, the organic material of the graphene can be obtained
Material.
Graphite oxide is dilute to be prepared using Hummers method, the specific steps are as follows:
It is added graphite powder and sodium nitrate under ice-water bath into the concentrated sulfuric acid, the mass ratio of graphite powder and sodium nitrate is 20:3, then
Potassium permanganate is added by several times, controls reaction temperature≤20 DEG C, is stirred to react 5h, is warming up to 40 DEG C, continues to stir 40min, then delay
Slowly appropriate hydrogen peroxide and deionized water is added, filters while hot, deionized water is washed until sulfate radical-free is detected to be in filtrate
Only, 80 DEG C of filter cake drying.
Application of the above-mentioned graphene organic material in gas sensor, the gas sensor can be used to detect CO,
CO2、H2、NO、NO2、CH4。
Embodiment 7:
A kind of graphene organic material, preparation method are as follows:
(1) it is added to graphite oxide is dilute in ethylene glycol, ultrasonic vibration processing makes it be completely dispersed and remove, and dries after filtering out
It is dry stand-by, then zinc acetate and sodium hydroxide are dissolved in ethylene glycol solution, magnetic agitation is to after being completely dissolved, by above-mentioned oxidation stone
The dilute addition 400r/min mechanical mixture 40min of ink, mixed material are transferred in autoclave, and reaction is heated at 150 DEG C
The product of generation is centrifuged by 30h, and acetone elutes after ethanol rinse, and 60 DEG C of oven drying 10h obtain zinc oxide/graphene
Compound；
(2) above-mentioned zinc oxide/graphene complex, terephthalonitrile and nano tin dioxide are mixed under argon gas protection, oxidation
The mass ratio of zinc/graphene complex, terephthalonitrile and nano tin dioxide three is 1:3:1.2, after ball milling 30min, will be mixed
Object is transferred in ceramic crucible, and 450 DEG C of heating reaction 40h obtain black solid in Muffle furnace under argon gas protection, is ground into black
Toner is last to be added in the dilute hydrochloric acid that mass concentration is 8% and is stored at room temperature 20h after 40 DEG C of stir process 10h, after suction filtration, respectively
It is washed three times with water and tetrahydrofuran, filters in vacuum drying oven, be dried in vacuo at 95 DEG C, the organic material of the graphene can be obtained
Material.
Graphite oxide is dilute to be prepared using Hummers method, the specific steps are as follows:
It is added graphite powder and sodium nitrate under ice-water bath into the concentrated sulfuric acid, the mass ratio of graphite powder and sodium nitrate is 10:3, then
Potassium permanganate is added by several times, controls reaction temperature≤20 DEG C, is stirred to react 2h, is warming up to 40 DEG C, continues to stir 30min, then delay
Slowly appropriate hydrogen peroxide and deionized water is added, filters while hot, deionized water is washed until sulfate radical-free is detected to be in filtrate
Only, 80 DEG C of filter cake drying.
Application of the above-mentioned graphene organic material in gas sensor, the gas sensor can be used to detect CO,
CO2、H2、NO、NO2、CH4。
Embodiment 8:
A kind of graphene organic material, preparation method are as follows:
(1) it is added to graphite oxide is dilute in ethylene glycol, ultrasonic vibration processing makes it be completely dispersed and remove, and dries after filtering out
It is dry stand-by, then zinc acetate and sodium hydroxide are dissolved in ethylene glycol solution, magnetic agitation is to after being completely dissolved, by above-mentioned oxidation stone
The dilute addition 500r/min mechanical mixture 20min of ink, mixed material are transferred in autoclave, and reaction is heated at 160 DEG C
The product of generation is centrifuged by 25h, and acetone elutes after ethanol rinse, and 70 DEG C of oven drying 5h obtain zinc oxide/graphene
Compound；
(2) above-mentioned zinc oxide/graphene complex, terephthalonitrile and nano tin dioxide are mixed under argon gas protection, oxidation
The mass ratio of zinc/graphene complex, terephthalonitrile and nano tin dioxide three is 1:4:1.1, after ball milling 50min, will be mixed
Object is transferred in ceramic crucible, and 400 DEG C of heating reaction 50h obtain black solid in Muffle furnace under argon gas protection, is ground into black
Toner is last to be added in the dilute hydrochloric acid that mass concentration is 5% and is stored at room temperature 25h after 55 DEG C of stir process 5h, after suction filtration, respectively
It is washed three times with water and tetrahydrofuran, filters in vacuum drying oven, be dried in vacuo at 80 DEG C, the organic material of the graphene can be obtained
Material.
Graphite oxide is dilute to be prepared using Hummers method, the specific steps are as follows:
It is added graphite powder and sodium nitrate under ice-water bath into the concentrated sulfuric acid, the mass ratio of graphite powder and sodium nitrate is 20:1, then
Potassium permanganate is added by several times, controls reaction temperature≤20 DEG C, is stirred to react 5h, is warming up to 35 DEG C, continues to stir 40min, then delay
Slowly appropriate hydrogen peroxide and deionized water is added, filters while hot, deionized water is washed until sulfate radical-free is detected to be in filtrate
Only, 70 DEG C of filter cake drying.
Application of the above-mentioned graphene organic material in gas sensor, the gas sensor can be used to detect CO,
CO2、H2、NO、NO2、CH4。
It should be noted that, in this document, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or equipment
Intrinsic element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that
There is also other identical elements in process, method, article or equipment including the element.Above embodiments are only to say
Bright technical solution of the present invention, rather than its limitations；Although the present invention is described in detail referring to the foregoing embodiments, originally
The those of ordinary skill in field it is understood that it is still possible to modify the technical solutions described in the foregoing embodiments,
Or equivalent replacement of some of the technical features；And these are modified or replaceed, and do not make the sheet of corresponding technical solution
Matter departs from the spirit and scope of the technical scheme of various embodiments of the present invention.
Claims (9)
1. a kind of graphene organic material, which is characterized in that the preparation method is as follows:
(1) be added to graphite oxide is dilute in ethylene glycol, ultrasonic vibration processing makes it be completely dispersed and remove, after filtering out drying to
With, then zinc acetate and sodium hydroxide be dissolved in ethylene glycol solution, magnetic agitation is dilute by above-mentioned graphite oxide to after being completely dissolved
400-500r/min mechanical mixture 20-40min is added, mixed material is transferred in autoclave, heats at 150-160 DEG C
25-30h is reacted, the product of generation is centrifuged, acetone elutes after ethanol rinse, and 60-70 DEG C of oven drying 5-10h is obtained
Zinc oxide/graphene complex；
(2) above-mentioned zinc oxide/graphene complex, terephthalonitrile and nano tin dioxide are mixed under argon gas protection, ball milling 30-
After 50min, mixture is transferred in ceramic crucible, 40-50h is reacted in 400-450 DEG C of heating in Muffle furnace under argon gas protection
Black solid is obtained, is ground into after black powder to be added in dilute hydrochloric acid and is stored at room temperature 20-25h after stir process 5-10h, is filtered
Afterwards, it is washed three times with water and tetrahydrofuran respectively, filters in vacuum drying oven, be dried in vacuo at 80-95 DEG C, the stone can be obtained
Black alkene organic material.
2. graphene organic material as described in claim 1, which is characterized in that dilute graphite oxide is using Hummers
What method was prepared.
3. graphene organic material as claimed in claim 2, which is characterized in that it is dilute that the Hummers method prepares graphite oxide
Specific step is as follows:
Graphite powder and sodium nitrate is added under ice-water bath into the concentrated sulfuric acid, then potassium permanganate is added by several times, controls reaction temperature≤20
DEG C, it is stirred to react 2-5h, is warming up to 35-40 DEG C, continues to stir 30-40min, is slow added into appropriate hydrogen peroxide and deionization
Water filters while hot, and deionized water is washed until sulfate radical-free is detected in filtrate, 70-80 DEG C of filter cake drying.
4. graphene organic material as claimed in claim 3, which is characterized in that the mass ratio of graphite powder and sodium nitrate is 10-
20:1-3.
5. graphene organic material as described in claim 1, which is characterized in that zinc oxide/graphene complex, terephthalonitrile
Mass ratio with nano tin dioxide three is 1:3-4:1.1-1.2.
6. graphene organic material as described in claim 1, which is characterized in that the mass concentration of dilute hydrochloric acid is 5-8%.
7. graphene organic material as described in claim 1, which is characterized in that the temperature of dilute hydrochloric acid stir process is 40-55
℃。
8. such as application of the graphene organic material of any of claims 1-7 in gas sensor.
9. application of the graphene organic material as claimed in claim 8 in gas sensor, which is characterized in that the gas
Sensor can be used to detect CO, CO2、H2、NO、NO2、CH4。
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