CN105195067B - A kind of graphene aerogel microballoon and its production and use - Google Patents
A kind of graphene aerogel microballoon and its production and use Download PDFInfo
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Abstract
The invention discloses a kind of graphene aerogel microballoon and its production and use, it is characterized in：(1) graphite oxide is prepared；(2) graphene oxide aqueous dispersions are prepared；(3) graphene oxide aqueous dispersions are atomized into graphene oxide drop microballoon by spray-on process, while the reception liquid by being placed in cooling bath is collected；(4) filtering reception liquid obtains graphene oxide ice microballoon, and freeze-drying obtains graphite oxide aerogel microballoon；(5) gained graphite oxide aerogel microballoon obtains graphene aerogel microballoon by thermal reduction.The preparation method is simple and convenient, non-environmental-pollution, and gained graphene aerogel microballoon size is more homogeneous, and specific surface area is big, has the multi-pore channel network structure of stable center divergent shape, is adsorbed for environmental contaminants.
Description
Technical field
The present invention relates to a kind of graphene aerogel microballoon and its production and use, belong to field of functional materials.
Background technology
Graphene is a kind of New Two Dimensional material of carbon atom regular arrangement form in a manner of cellular.With superior power
Performance, electric property, optical property, thermal property are learned, therefore receives the extensive concern of each field personage.By the graphite of two dimension
Alkene is configured to the graphene macroscopic material of three-dimensional, under conditions of the excellent properties for ensureing graphene are not destroyed, makes graphite
Alkene really can be applied in industrial production, have the important method and approach of practical use.Wherein, as three-dimensional graphite
The graphene aerogel that alkene macroscopic material represents can not only retain the huge specific surface area of graphene and excellent properties, also
There can be the performances such as the unique porous of aeroge, ultralow density, low-k simultaneously, therefore, graphene aerogel draws
Play the very big attention of researcher and start to be widely applied to energy conversion with storing, High-performance catalyst carrier,
Environmental protection and purification, biomaterial and biotechnology field.
Aerogel microball has a series of more excellent properties compared to aerogel block body, such as：As catalyst carrier
With bigger specific surface area, more active reaction centers can be provided；As packing material there is good fluidity to be easy to uniform
It is scattered, it is not easy to cause stress concentration etc..Therefore it can largely improve the service efficiency of aeroge and widen aeroge
Application field.Aerogel microball common at present has SiO2Aerogel microball, carbon aerogels microballoon and macromolecule aerogel-like are micro-
Ball, but without the report on graphene aerogel microballoon.Graphene aerogel is prepared as graphene aerogel microballoon, no
It is only capable of increasing actual application value for graphene aerogel, moreover it is possible to for following development exploration of graphene and open up a new way
Footpath.
The porous of aeroge causes it to have the characteristic of the relatively low easily fragmentation of mechanical strength so for preparing the good size of shape
Homogeneous aerogel microball can not use the mechanical processes such as simple such as ball milling, shearing.Therefore the system of current aerogel microball
Most of standby process is that the lower sol gel original position of quick stirring prepares hydrogel microsphere to obtain aeroge after drying again micro-
Ball.But this preparation method operation is complex, and production efficiency is relatively low, and is not adapted to prepare graphene hydrogel microsphere
Sol gel reagent, therefore it is not appropriate for the preparation of graphene aerogel microballoon.Therefore, there is presently no on graphene gas
The patent document of gel micro-ball or the report of non-patent literature.
The content of the invention
The purpose of the present invention is a kind of graphene aerogel microballoon developed and its preparation in view of the shortcomings of the prior art
Method and purposes.It is characterized in that the graphene aerogel microballoon size is more homogeneous, there is abundant oxygen-containing functional group, be easy to change
Property and load, there is the multi-pore channel network structure of stable center divergent shape, light weight density is small and preparation method is simple and convenient,
Non-environmental-pollution, cost of material is low, and production efficiency is high.The graphene aerogel microballoon adsorbs suitable for environmental contaminants.
The purpose of the present invention is realized by following technical measures, wherein the raw material number is unless otherwise specified, it is weight
Number.
The initiation material of graphene aerogel microballoon is made up of following components：
100 parts of deionized water
Graphite oxide 0.05-2 parts
The preparation method of graphene aerogel microballoon comprises the following steps：
(1) preparation of graphite oxide
Native graphite is prepared into graphite oxide through chemical oxidization method, wherein chemical oxidization method is Brodie oxidizing process,
Staudemaier oxidizing process, any of Hummer methods or improved Hummer methods；
(2) preparation of graphene oxide aqueous dispersions
By 100 parts of deionized water, 20-50min is peeled off through 200-400W ultrasounds after the uniform mixing of graphite oxide 0.05-2 parts
Prepared composition dispersion liquid, concentration 0.5-20mg/ml；
(3) graphene oxide aqueous dispersions are atomized into by graphene oxide drop microballoon by spray-on process, and it is cold by being placed in
But the reception liquid in bathing is collected, wherein, spray-on process is press atomization, any of ullrasonic spraying or electrostatic spray；
(4) filter above-mentioned reception liquid and obtain graphene oxide ice microballoon, graphite oxide aerogel is obtained after freeze-drying
Microballoon；
(5) above-mentioned graphite oxide aerogel microballoon is obtained into graphene aerogel microballoon by thermal reduction.
The pressure of the press atomization is 10-200Mpa, and the ultrasonic power of ullrasonic spraying is 10-150kHz, electrostatic spray
Voltage be 5-20kv.
The cooling bath is that ice/sodium chloride is bathed, any of dry ice/acetone batch or liquid nitrogen/ethyl acetate bath.
The reception liquid is ethyl acetate, toluene, at least one of n-hexane and normal heptane；
The thermal reduction is Muffle furnace Program heating thermal reduction or microwave irradiation thermal reduction under inert gas shielding.
Described program heating thermal reduction is warming up to 800 DEG C and keeps 2-5h for 5-10 DEG C/min, and microwave irradiation thermal reduction is
Power is 600-800W and keeps 1-10min.
Graphene aerogel microballoon adsorbs for environmental contaminants.
Structural characterization and performance test：
1st, the pattern of graphene aerogel microballoon is observed using JSM-5900LV types SEM, SEM
Figure is the results detailed in shown in Fig. 3.
As a result show：Graphene aerogel microballoon good sphericity, there is porous cross-linked structure.
2nd, adsorption capacity of the graphene aerogel microball to organic solvent is tested using gravimetry, the results detailed in Fig. 4
It is shown.
As a result show：Graphene aerogel microballoon has excellent adsorption capacity to organic solvent, and highest adsorbance reaches
178g chloroforms/g graphene aerogel microballoons.
The present invention has advantages below：
1. the present invention is prepared for a kind of graphene aerogel microballoon
2. the graphene aerogel microspherulite diameter that the preparation method of the present invention is prepared is controllable, particle diameter distribution can pass through mist
The adjustment of change method and parameter is controlled in 10-1000 μm of any range, and specific surface area height (is more than 200m2/ g), porosity exists
More than 95%, there is abundant oxygen-containing functional group, be easy to modified and load, there is the multi-pore channel network of stable center divergent shape
Structure, light weight density are small.
3. the technology that aerogel microball is dried to obtain after the snap frozen atomized drop microballoon that the present invention uses is convenient and swift,
It is easy to operate, continuous production, efficiency high can be realized.
4. graphene aerogel microballoon prepared by the present invention adsorbs for environmental contaminants.The graphene aerogel microballoon energy
A variety of organic solvents and oils are adsorbed, its adsorption capacity is high, hence it is evident that better than the bulk graphene aerogel reported.And by
In the characteristic that graphene aerogel microballoon lightweight is easily spread, make preferably collect suction in the environmental accidents such as its oil leak at sea
Attached environmental contaminants.
Brief description of the drawings
Fig. 1 is the process flow diagram that the present invention prepares graphene aerogel microballoon；
1. prepare graphite oxide；2. prepare graphene oxide dispersion；3. spraying and snap frozen；4. filtering；5. freezing
Dry；6. thermal reduction.
Fig. 2 is the preparation technology schematic diagram of the graphite oxide aerogel microballoon of the embodiment of the present invention 1
Fig. 3 is the scanning electron microscope (SEM) photograph of the graphene aerogel microballoon of the embodiment of the present invention 1；
Fig. 4 is schematic diagram of the graphene aerogel of the embodiment of the present invention 2 to the adsorbance of organic solvent.
Embodiment
The present invention is specifically described below by embodiment, it is necessary to it is pointed out here that be the present embodiment only for
The present invention is further described, it is impossible to is interpreted as limiting the scope of the invention, the person skilled in the art in the field can
To make some nonessential modifications and adaptations according to the content of the invention described above.
Embodiment 1
(1) graphite oxide is prepared：Native graphite is prepared as graphite oxide through Brodie oxidizing process.
(2) graphene oxide aqueous dispersions are prepared：At room temperature, by 0.75g Brodie oxidizing process prepare graphite oxide and
100ml deionized waters are mixed, and are placed in ultrasonic washing instrument, and 200W ultrasonic disperses are stirred overnight after 20 minutes, are obtained scattered equal
The even graphene oxide aqueous dispersions in dark-brown 7.5mg/ml.
(3) trash ice is placed in the good open Dewar bottle of insulation, adds sodium chloride powder, stir to be formed trash ice/
Sodium chloride cooling bath.Beaker equipped with ethyl acetate is put into trash ice/sodium chloride cooling bath as reception liquid.Meanwhile it will match somebody with somebody
The 7.5mg/ml made graphene oxide aqueous dispersions are fitted into the syringe on electrostatic atomizer, adjust syringe nozzle
Highly it is allowed to after being separated by suitable distance with reception liquid, regulation voltage is 15Kv, starts to spray and quickly cool down in reception liquid
Drop microballoon.As shown in Figure 2.
(4) brownish black graphene oxide ice microballoon is obtained with sieve fast filtering ethyl acetate reception liquid, it is dry is transferred to freezing
In dry machine, under the conditions of vacuum 20Pa, -50 DEG C of temperature, dry 24h and obtain brown oxidation graphene aerogel microballoon.
(5) obtained graphite oxide aerogel microballoon is placed in Muffle furnace under inert gas shielding by 5 DEG C/min
Programming rate be warming up to 800 degrees Celsius and keep obtaining black light graphite alkene aerogel microball in 5 hours, as shown in Figure 3.
Average grain diameter is 247 μm, density 5.0kg/m3。
Embodiment 2
(1) graphite oxide is prepared：The improved HUMMER methods of native graphite are prepared as graphite oxide.
(2) graphene oxide aqueous dispersions are prepared：At room temperature, the graphite oxide that prepared by the improved HUMMER methods of 1.5g and
100ml deionized waters mix, and are placed in ultrasonic washing instrument, are stirred overnight, are uniformly dispersed after 400W ultrasonic disperses 35min
In dark-brown 15mg/ml graphene oxide aqueous dispersions.
(3) ethyl acetate is placed in the good open Dewar bottle of insulation, adds a large amount of liquid nitrogen while stirring, until being formed
Slush shape liquid nitrogen/ethyl acetate cooling bath.Beaker equipped with toluene and n-hexane is put into cold in liquid nitrogen/ethyl acetate cooling bath
But it is used as reception liquid.Meanwhile the note for loading the 15mg/ml prepared graphene oxide aqueous dispersions on ultrasonic spray apparatus
In emitter, regulation syringe nozzle is highly allowed to after being separated by suitable distance with reception liquid, and regulation supersonic frequency is 150kHz, is opened
Begin spraying and the quick cooling drop microballoon in reception liquid.
(4) brownish black graphene oxide ice microballoon is obtained with sieve fast filtering reception liquid, be transferred in freeze drier,
Vacuum 20Pa, under the conditions of -50 DEG C of temperature, dry 24h and obtain brown oxidation graphene aerogel microballoon.
(5) obtained graphite oxide aerogel microballoon is placed in Muffle furnace under inert gas shielding by 10 DEG C/min
Programming rate be warming up to 800 DEG C and keep obtaining black light graphite alkene aerogel microball in 5 hours.Average grain diameter is 15 μ
M, density 6.8kg/m3。
Embodiment 3
(1) graphite oxide is prepared：Native graphite is prepared as graphite oxide through HUMMER methods.
(2) graphene oxide aqueous dispersions are prepared：At room temperature, by 0.5mg HUMMER methods prepare graphite oxide and
100ml deionized waters mix, and are placed in ultrasonic washing instrument, are stirred overnight, are uniformly dispersed after 300W ultrasonic disperses 30min
In dark-brown 5mg/ml graphene oxide aqueous dispersions.
(3) acetone is placed in the good open Dewar bottle of insulation, adds dry ice fragment while stirring, until substantially can not
Agitation, that is, form sticky dry ice/acetone cooling bath.Beaker equipped with ethyl acetate and normal heptane is put into dry ice/acetone
Cooling is used as reception liquid in cooling bath.Meanwhile the 5mg/ml prepared graphene oxide aqueous dispersions are loaded into press atomization
In pressure chamber on device, adjusting shower nozzle is highly allowed to after being separated by suitable distance with reception liquid, is opened compression pump and is adjusted and arrives
40Mpa, start spraying and drop microballoon is quickly cooled down in reception liquid.
(4) brownish black graphene oxide ice microballoon is obtained with sieve fast filtering reception liquid, be transferred in freeze drier,
Vacuum 20Pa, under the conditions of -50 DEG C of temperature, dry 24h and obtain brown oxidation graphene aerogel microballoon.
(5) the 600W microwave powers irradiation thermal reduction under inert gas shielding by obtained graphite oxide aerogel microballoon
10min, that is, obtain black light graphite alkene aerogel microball.Average grain diameter is 87 μm, density 3.9kg/m3。
Embodiment 4
(1) graphite oxide is prepared：Native graphite is prepared as graphite oxide through HUMMER methods.
(2) graphene oxide aqueous dispersions are prepared：At room temperature, by 0.6mg HUMMER methods prepare graphite oxide and
100ml deionized waters are mixed, and are placed in ultrasonic washing instrument, and 200W ultrasonic disperses are stirred overnight after 35 minutes, are obtained scattered equal
The even graphene oxide aqueous dispersions in dark-brown 6mg/ml.
(3) ethyl acetate is placed in the good open Dewar bottle of insulation, adds a large amount of liquid nitrogen while stirring, until being formed
Slush shape liquid nitrogen/ethyl acetate cooling bath.N-hexane will be housed, ethyl acetate, be put into liquid nitrogen/acetic acid second in the beaker of normal heptane
Cooling is used as reception liquid in ester cooling bath.Meanwhile the 6mg/ml prepared graphene oxide aqueous dispersions are loaded into electrostatic
In syringe on mist device, regulation syringe nozzle is highly allowed to after being separated by suitable distance with reception liquid, and regulation voltage is
8Kv, start spraying and drop microballoon is quickly cooled down in reception liquid.
(4) brownish black graphene oxide ice microballoon is obtained with sieve fast filtering reception liquid, be transferred in freeze drier,
Vacuum 20Pa, under the conditions of -50 DEG C of temperature, dry 24h and obtain brown oxidation graphene aerogel microballoon.
(5) obtained graphite oxide aerogel microballoon is placed in Muffle furnace under inert gas shielding by 6 DEG C/min
Programming rate be warming up to 800 DEG C and keep obtaining black light graphite alkene aerogel microball in 4 hours.Average grain diameter is 180 μ
M, density 4.5kg/m3。
Embodiment 5
(1) graphite oxide is prepared：The improved HUMMER methods of native graphite are prepared as graphite oxide.
(2) graphene oxide aqueous dispersions are prepared：At room temperature, the graphite oxide prepared by the improved HUMMER methods of 0.2mg
Mixed with 100ml deionized waters, be placed in ultrasonic washing instrument, be stirred overnight after 200W ultrasonic disperses 20min, obtained scattered equal
The even graphene oxide aqueous dispersions in dark-brown 2mg/ml.
(3) trash ice is placed in the good open Dewar bottle of insulation, adds sodium chloride powder, stir to be formed trash ice/
Sodium chloride cooling bath.Beaker equipped with n-hexane and toluene is put into trash ice/sodium chloride cooling bath as reception liquid.Meanwhile
The 2mg/ml prepared graphene oxide aqueous dispersions are fitted into the syringe on ultrasonic spray apparatus, regulation syringe spray
Grease head highness is allowed to after being separated by suitable distance with reception liquid, and regulation supersonic frequency is 20kHz, starts to spray and fast in reception liquid
Quickly cooling but drop microballoon.
(4) brownish black graphene oxide ice microballoon is obtained with sieve fast filtering reception liquid, be transferred in freeze drier,
Vacuum 20Pa, under the conditions of -50 DEG C of temperature, dry 24h and obtain brown oxidation graphene aerogel microballoon.
(5) the 800W microwave powers irradiation thermal reduction under inert gas shielding by obtained graphite oxide aerogel microballoon
1min, that is, obtain black light graphite alkene aerogel microball.Average grain diameter is 118 μm, density 1.2kg/m3。
Embodiment 6
(1) graphite oxide is prepared：The improved HUMMER methods of native graphite are prepared as graphite oxide.
(2) graphene oxide aqueous dispersions are prepared：At room temperature, the graphite oxide prepared by the improved HUMMER methods of 0.15mg
Mixed with 100ml deionized waters, be placed in ultrasonic washing instrument, be stirred overnight after 200W ultrasonic disperses 20min, obtained scattered equal
The even graphene oxide aqueous dispersions in dark-brown 1.5mg/ml.
(3) acetone is placed in the good open Dewar bottle of insulation, adds dry ice fragment while stirring, until substantially can not
Agitation, that is, form sticky dry ice/acetone cooling bath.Beaker equipped with toluene and normal heptane is put into dry ice/acetone cooling
Cooling is used as reception liquid in bath.Meanwhile the 1.5mg/ml prepared graphene oxide aqueous dispersions are loaded into press atomization dress
In the pressure chamber put, adjusting shower nozzle is highly allowed to after being separated by suitable distance with reception liquid, is opened compression pump and is adjusted and arrives
10Mpa, start spraying and drop microballoon is quickly cooled down in reception liquid.
(4) brownish black graphene oxide ice microballoon is obtained with sieve fast filtering reception liquid, be transferred in freeze drier,
Vacuum 20Pa, under the conditions of -50 DEG C of temperature, dry 24h and obtain brown oxidation graphene aerogel microballoon.
(5) the 700W microwave powers irradiation thermal reduction under inert gas shielding by obtained graphite oxide aerogel microballoon
5min, that is, obtain black light graphite alkene aerogel microball.Average grain diameter is 340 μm, density 1.4kg/m3。
Embodiment 7
(1) graphite oxide is prepared：Native graphite is prepared as graphite oxide through Brodie oxidizing process.
(2) graphene oxide aqueous dispersions are prepared：At room temperature, by 0.85g Brodie methods prepare graphite oxide and
100ml deionized waters mix, and are placed in ultrasonic washing instrument, are stirred overnight, are uniformly dispersed after 400W ultrasonic disperses 40min
In dark-brown 8.5mg/ml graphene oxide aqueous dispersions.
(3) trash ice is placed in the good open Dewar bottle of insulation, adds sodium chloride powder, stir to be formed trash ice/
Sodium chloride cooling bath.Beaker equipped with n-hexane and ethyl acetate is put into trash ice/sodium chloride cooling bath and cooled down as reception
Liquid.Meanwhile the 8.5mg/ml prepared graphene oxide aqueous dispersions are fitted into the syringe on ultrasonic spray apparatus, adjust
Section syringe nozzle is highly allowed to after being separated by suitable distance with reception liquid, and regulation supersonic frequency is 60kHz, start to spray and
Drop microballoon is quickly cooled down in reception liquid.
(4) brownish black graphene oxide ice microballoon is obtained with sieve fast filtering reception liquid, be transferred in freeze drier,
Vacuum 20Pa, under the conditions of -50 DEG C of temperature, dry 24h and obtain brown oxidation graphene aerogel microballoon.
(5) the 700W microwave powers irradiation thermal reduction under inert gas shielding by obtained graphite oxide aerogel microballoon
3min, that is, obtain black light graphite alkene aerogel microball.Average grain diameter is 47 μm, density 7.1kg/m3。
Embodiment 8
(1) graphite oxide is prepared：Native graphite is prepared as graphite oxide through Brodie oxidizing process.
(2) graphene oxide aqueous dispersions are prepared：At room temperature, by 0.05g Brodie methods prepare graphite oxide and
100ml deionized waters mix, and are placed in ultrasonic washing instrument, are stirred overnight, are uniformly dispersed after 200W ultrasonic disperses 20min
In dark-brown 0.5mg/ml graphene oxide aqueous dispersions.
(3) acetone is placed in the good open Dewar bottle of insulation, adds dry ice fragment while stirring, until substantially can not
Agitation, that is, form sticky dry ice/acetone cooling bath.It is cold that beaker equipped with ethyl acetate and toluene is put into dry ice/acetone
But cooling is used as reception liquid in bathing.Meanwhile the 0.5mg/ml prepared graphene oxide aqueous dispersions are loaded into electrostatic spray
In syringe on device, regulation syringe nozzle is highly allowed to after being separated by suitable distance with reception liquid, and regulation voltage is
5Kv, start spraying and drop microballoon is quickly cooled down in reception liquid.
(4) brownish black graphene oxide ice microballoon is obtained with sieve fast filtering reception liquid, be transferred in freeze drier,
Vacuum 20Pa, under the conditions of -50 DEG C of temperature, dry 24h and obtain brown oxidation graphene aerogel microballoon.
(5) the 800W microwave powers irradiation thermal reduction under inert gas shielding by obtained graphite oxide aerogel microballoon
7min, that is, obtain black light graphite alkene aerogel microball.Average grain diameter is 220 μm, density 0.35kg/m3。
Embodiment 9
(1) graphite oxide is prepared：Native graphite is prepared as graphite oxide through Staudemaier oxidizing process.
(2) graphene oxide aqueous dispersions are prepared：At room temperature, the graphite oxide prepared by 0.35g Staudemaier methods
Mixed with 100ml deionized waters, be placed in ultrasonic washing instrument, be stirred overnight after 400W ultrasonic disperses 25min, obtained scattered equal
The even graphene oxide aqueous dispersions in dark-brown 3.5mg/ml.
(3) ethyl acetate is placed in the good open Dewar bottle of insulation, adds a large amount of liquid nitrogen while stirring, until being formed
Slush shape liquid nitrogen/ethyl acetate cooling bath.Beaker equipped with n-hexane and normal heptane is put into liquid nitrogen/ethyl acetate cooling bath
Cooling is used as reception liquid.Meanwhile the 3.5mg/ml prepared graphene oxide aqueous dispersions are loaded on press atomization device
Pressure chamber in, adjusting shower nozzle is highly allowed to after being separated by suitable distance with reception liquid, is opened compression pump and is adjusted and arrives 200Mpa,
Start spraying and drop microballoon is quickly cooled down in reception liquid.
(4) brownish black graphene oxide ice microballoon is obtained with sieve fast filtering reception liquid, be transferred in freeze drier,
Vacuum 20Pa, under the conditions of -50 DEG C of temperature, dry 24h and obtain brown oxidation graphene aerogel microballoon.
(5) obtained graphite oxide aerogel microballoon is placed in Muffle furnace under inert gas shielding by 10 DEG C/min
Programming rate be warming up to 800 DEG C and keep obtaining black light graphite alkene aerogel microball in 2 hours.Average grain diameter is 45 μ
M, density 2.3kg/m3。
Embodiment 10
(1) graphite oxide is prepared：Native graphite is prepared as graphite oxide through Staudemaier oxidizing process.
(2) graphene oxide aqueous dispersions are prepared：At room temperature, by 2g Staudemaier methods prepare graphite oxide and
100ml deionized waters mix, and are placed in ultrasonic washing instrument, are stirred overnight, are uniformly dispersed after 400W ultrasonic disperses 50min
In dark-brown 20mg/ml graphene oxide aqueous dispersions.
(3) trash ice is placed in the good open Dewar bottle of insulation, adds sodium chloride powder, stir to be formed trash ice/
Sodium chloride cooling bath.Beaker equipped with n-hexane and normal heptane is put into trash ice/sodium chloride cooling bath and cooled down as reception liquid.
Meanwhile the 20mg/ml prepared graphene oxide aqueous dispersions are fitted into the syringe on electrostatic atomizer, regulation note
Injector spray tip is highly allowed to after being separated by suitable distance with reception liquid, and regulation voltage is 20Kv, starts spraying and in reception liquid
Quick cooling drop microballoon.
(4) brownish black graphene oxide ice microballoon is obtained with sieve fast filtering reception liquid, be transferred in freeze drier,
Vacuum 20Pa, under the conditions of -50 DEG C of temperature, dry 24h and obtain brown oxidation graphene aerogel microballoon.
(5) obtained graphite oxide aerogel microballoon is placed in Muffle furnace under inert gas shielding by 8 DEG C/min
Programming rate be warming up to 800 DEG C and keep obtaining black light graphite alkene aerogel microball in 4 hours.Average grain diameter is 176 μ
M, density 16.7kg/m3。
Application example 1
Graphene aerogel microballoon 100mg prepared by embodiment 3 is weighed, laboratory is put into and common are solvent as third
Ketone, toluene, tetrahydrofuran, adsorb in Isosorbide-5-Nitrae dioxane and chloroform 10min to after saturation, weigh adsorbed it is micro- after organic solvent
The quality of ball, respectively 6.2g, 8.7g, 9.1g, 15.2g and 17.9g, therefore adsorbance is respectively 6.1g, 8.6g, 9.0g, 15.1g
And 17.8g.It is respectively 61g/g, 86g/g, 90g/g, 151g/g and 178g/g by the adsorption capacity Q that microballoon is calculated.Knot
Fruit is detailed as shown in Figure 4.As a result show, graphene aerogel microballoon has excellent adsorption capacity to organic solvent.
Application example 2
Graphene aerogel microballoon 100mg prepared by embodiment 4 is weighed, is put into the common oil for easily causing environmental pollution
Class is diesel oil, gasoline, and 10-15min is adsorbed in waste vegetable oil and pump oil to after saturation, weighing the matter of having adsorbed microballoon after oil product
Amount, respectively 8.8g, 8.0g, 10.0g and 10.6g, therefore adsorbance is respectively 8.7g, 7.9g, 9.9g and 10.5g.Pass through calculating
The adsorption capacity Q for obtaining microballoon is respectively 87g/g, 79g/g, 99g/g and 105g/g.As a result show, graphene aerogel microballoon
There is excellent adsorption capacity to oils.
Claims (7)
1. a kind of preparation method of graphene aerogel microballoon, it is characterised in that this method comprises the following steps：
(1) preparation of graphite oxide
Native graphite is prepared into graphite oxide through chemical oxidization method, wherein chemical oxidization method is Brodie oxidizing process,
Staudemaier oxidizing process, any of Hummer methods or improved Hummer methods；
(2) preparation of graphene oxide aqueous dispersions
By 100 parts of deionized water, graphite oxide 0.05-2 parts are peeled off 20-50min through 200-400W ultrasounds after uniformly mixing and prepared
Into dispersion liquid, concentration 0.5-20mg/mL；
(3) graphene oxide aqueous dispersions are atomized into by graphene oxide drop microballoon by spray-on process, be placed in cooling bath
Reception liquid collect, wherein, spray-on process is press atomization, any of ullrasonic spraying or electrostatic spray；
(4) filter above-mentioned reception liquid and obtain graphene oxide ice microballoon, graphite oxide aerogel microballoon is obtained after freeze-drying；
(5) above-mentioned graphite oxide aerogel microballoon is obtained into graphene aerogel microballoon by thermal reduction.
2. the preparation method of graphene aerogel microballoon according to claim 1, it is characterised in that the pressure of press atomization is
10-200MPa, the ultrasonic power of ullrasonic spraying is 10-150kHz, and the voltage of electrostatic spray is 5-20kv.
3. the preparation method of graphene aerogel microballoon according to claim 1, it is characterised in that cooling bath is ice/sodium chloride
Any of bath, dry ice/acetone batch or liquid nitrogen/ethyl acetate bath.
4. the preparation method of graphene aerogel microballoon according to claim 1, it is characterised in that reception liquid is ethyl acetate,
Toluene, at least one of n-hexane and normal heptane.
5. the preparation method of graphene aerogel microballoon according to claim 1, it is characterised in that thermal reduction is in inertia
Muffle furnace Program heating thermal reduction or microwave irradiation thermal reduction under gas shield.
6. the preparation method of graphene aerogel microballoon according to claim 5, it is characterised in that temperature programming, which heat-treats, is
5-10 DEG C/min is warming up to 800 DEG C, and keeps 2-5h；Microwave irradiation thermal reduction is that power is 600-800W and keeps 1-10min.
7. the graphene aerogel microballoon that the preparation method of graphene aerogel microballoon is prepared according to claim 1.
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