CN108083266A - A kind of zinc powder reduction graphene oxide prepares the method with absorbing property graphene - Google Patents
A kind of zinc powder reduction graphene oxide prepares the method with absorbing property graphene Download PDFInfo
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Abstract
A kind of zinc powder reduction graphene oxide prepares the method with absorbing property graphene：1) concentrated sulfuric acid mixing of natural flake graphite, potassium peroxydisulfate, phosphorus pentoxide and mass concentration 98%, after water bath with thermostatic control reaction；Drying grinding is filtered, graphite presoma must be pre-oxidized；2) pre-oxidation graphite presoma with 98% concentrated sulfuric acid of mass concentration in ice-water bath is mixed, potassium permanganate is added in, in isoperibol, the viscous liquid for fully reacting blackish green；During temperature≤45 DEG C, add in deionized water for a period of time, add ionized water and hydrogen peroxide, obtain bright yellow solution；Washing obtains mixed liquor to PH=6~6.8；Drying grinding obtains graphite oxide reaction and drives body；3) graphite oxide is reacted drive body be sufficiently mixed with deionized water, obtains brown suspension；Ultrasonic oscillation obtains graphene oxide dispersion；4) water bath with thermostatic control, zinc powder add in graphene oxide dispersion, obtain the mixture with black precipitate；Drying grinding is filtered, obtains the graphene with absorbing property.
Description
Technical field
The invention belongs to New Radar Absorbing nano material manufacturing field, prepared by more particularly to a kind of zinc powder reduction graphene oxide
Method with absorbing property graphene.
Background technology
Graphene be by a kind of tightly packed new carbonaceous material into bi-dimensional cellular shape crystal structure of single layer of carbon atom, from
Most thin a kind of material in right boundary known materials.This two-dimensional material maintains the crystal structure of almost Perfect and excellent crystal
Property is learned, has contained abundant and novel physical phenomenon, there is important theoretical research and application value.Due to it possess it is excellent
Intensity, flexible, conductive, heat conduction, optical characteristics, in fields such as physics, materialogy, electronic information, computer, aerospaces
It is obtained for significant progress.
Traditional chemical reduction method uses chemical reagent-hydrazine hydrate (N2H4·H2) etc. O it is reducing agent, this kind of reducing agent
It is toxic, human body is damaged, the waste water after reaction can cause environmental pollution.And zinc powder reduction graphene oxide will not endanger
Body, pollution environment, and the Zn-ef ficiency being attached to after reducing on graphene plays an important role of to enhance absorbing property, it is effective to improve
The absorbing property of material entirety.
The main method for preparing graphene at present has：It is micromechanics stripping method, chemical vapour deposition technique, solvent stripping method, molten
Hot method of agent etc..These method complex process, environmental requirement is harsh and cost is very high, is unfavorable for large-scale industrial production.This hair
Bright using oxidation-reduction method to prepare the feasible process of graphene, manufacturing cost cheap, obtains stable graphene suspension, solves
Graphene of having determined is not easy scattered problem.Oxidation-reduction method refers to give birth to native graphite and the reaction of strong acid and oxidizing species
Into graphite oxide (GO), graphene oxide (mono-layer graphite oxide) is prepared by ultrasonic disperse, adds in reducing agent removal oxidation
The oxygen-containing group of graphite surface such as carboxyl, epoxy group and hydroxyl, obtains graphene.Zinc powder enhances graphene as reducing agent
Absorbing property.The defects of being generated in oxidation-reduction process can generate the dielectric relaxor of defect and group's electronics dipole relaxation, this
The infiltration and absorption of electromagnetic wave can be increased, shortcoming is become into advantage.This method is simple, at low cost, reaction condition is mildly easy
Control.
At present, tend to graphene for most of the study of radar absorbing property of graphene and carry out compound, example with other materials
Such as ferrite.So that the absorbing material production cost prepared is very high, it is unfavorable for commercial introduction in daily life.In low, middle and high frequency
Section is respectively provided with absorbing property, wherein in the range of 2-6GHz, peak value reaches -12.13dB.
The content of the invention
In view of the deficiencies of the prior art, being prepared the present invention provides a kind of zinc powder reduction graphene oxide has absorbing property
The method of graphene the method achieve absorbing property of the graphene in multifrequency wave band, be that a kind of method is simple, at low cost, anti-
Answer that condition is easily-controllable, environmental protection and energy saving, in the preparation method of the good graphene of multifrequency wave band (2-18GHz) absorbing property.
The zinc powder reduction graphene oxide of the present invention prepares the method with absorbing property graphene, comprises the following steps：
Step 1, reaction of formation pre-oxidation graphite presoma：
(1) stoichiometrically, natural flake graphite (C): potassium peroxydisulfate (K2S2O8): phosphorus pentoxide (P2O5): quality
Fraction is 98% concentrated sulfuric acid (H2SO4)=(8~10): (4~6): (3~5): (38~40) weigh above-mentioned 4 kinds of raw materials respectively；
(2) after 4 kinds of raw materials are mixed, under agitation, 60~80 DEG C of water bath with thermostatic control is placed in, reacts 6~8h；
(3) diluted with deionized water and wash neutrality, be filtered by vacuum, ground after drying at room temperature, pre-oxidation is made
Graphite presoma；
Step 2, secondary oxidation prepares graphite oxide：
(1) by pre-oxidation graphite presoma (g): mass fraction is 98% concentrated sulfuric acid (mL): potassium permanganate (g)=(1~
3): pre-oxidation graphite presoma is first by (13~15): (4~8) measure or take respectively above-mentioned 3 kinds of raw materials with mass fraction
98% concentrated sulfuric acid mixes in ice-water bath, and stirring is slowly added to potassium permanganate simultaneously, obtains mixture；
(2) mixture is placed in 30~40 DEG C of isoperibol, fully reacts 2~4h, be made blackish green thick
Liquid；
(3) by volume, the material quality fraction in step 2 (1) is 98% concentrated sulfuric acid: first part of deionized water=(1
~3): (2~4) measure first part of deionized water, the material quality fraction in step 2 (1) is 98% concentrated sulfuric acid by volume
: second part of deionized water: hydrogen peroxide=(28~30): (1~3) measures second part of deionized water and hydrogen peroxide；
It controls temperature≤45 DEG C of blackish green viscous liquid, adds in first part of deionized water, after 12~18min, add
Enter second part of deionized water and hydrogen peroxide, bright yellow solution is made；
(3) by bright yellow solution, filter and washed with dilute hydrochloric acid, be washed with deionized to PH=6~6.8, must mix
Liquid；
(4) by mixed liquor, ground after drying, graphite oxide reaction is made and drives body.
Step 3, graphene oxide dispersion is prepared：
(1) body (g): deionized water (mL)=(1~3): (2000~5000) is driven by graphite oxide reaction, by graphite oxide
Reaction is driven body and is sufficiently mixed with deionized water at 30~50 DEG C, and brown suspension is made；
(2) by brown suspension ultrasonic oscillation, make its fully dispersed, the graphene oxide dispersion of brown is made；
Step 4, zinc powder reduction graphene oxide prepares graphene：
(1) graphene oxide dispersion (mL): zinc powder (g)=(190~210): (0.5~2) is pressed, measures or measures respectively
Graphene oxide dispersion and zinc powder in 30~50 DEG C of waters bath with thermostatic control, zinc powder are added in graphene oxide dispersion, is filled
Divide mixing, the mixture with black precipitate is made；
(2) by the mixture with black precipitate, suction filtration obtains filter cake, is ground after drying, is made with absorbing property
Graphene.
Above-mentioned zinc powder reduction graphene oxide prepares the method with absorbing property graphene, wherein：
In the step 1 (1), potassium peroxydisulfate, phosphorus pentoxide, the concentrated sulfuric acid are that analysis is pure.
In the step 1 (2), mixing speed is 150~270r/min.
In the step 1 (2), react and carried out in four-hole boiling flask.
It is that potassium permanganate is exploded by thermal decomposition in order to prevent using ice-water bath in the step 2 (1).
In the step 2 (1), the speed being slowly added to is 0.5~1g/min.
In the step 2 (2), isoperibol is water bath with thermostatic control.The water bath with thermostatic control carries out in thermostat water bath.
In the step 2 (2), the method fully reacted is auxiliary electric stirring mixture.
In the step 2 (3), the mass concentration of dilute hydrochloric acid is 5~15%.
In the step 2 (3), metal ion is washed away using dilute hydrochloric acid.
In the step 2 (4), dried using air dry oven.
In the step 3 (1), well-mixed method is, using electric stirring.
In the step 3 (2), ultrasonic vibration carries out in ultrasonic oscillation device.
In the step 3 (2), 4~6h of ultrasonic vibration.
In the step 4 (1), well-mixed method is electric stirring.
In the step 4 (2), dried using air dry oven.
Prepared by preparation method of the present invention has absorbing property graphene, inhales wave reflection rate -36.2dB.
The zinc powder reduction graphene oxide of the present invention prepares the method with absorbing property graphene, with prior art phase
Than, the advantage of the invention is that：
Mildly under conditions of, by the use of water as solvent, and by the use of metallic zinc as reducing agent, cost is reduced,.Due to matching somebody with somebody
Material less and is easy to get, at low cost and do not pollute the environment while will not introduce other impurities.By controlling oxidant, intercalation
The conditions such as agent, reaction time, reaction temperature, so as to prepare the good graphene nano material of electromagnetic performance.By then passing through
Graphene prepared by oxide-reduction method can generate the dielectric relaxor of defect and group's electricity in oxidation-reduction process the defects of generation
Sub- dipole relaxation, these can all increase the infiltration and absorption of electromagnetic wave.Preparation method is simple, at low cost, and reaction condition is easily-controllable, ring
Protect energy saving, product quality is light, and dielectric loss and magnetic hystersis loss are provided with and well, suitable for industrialized production.Pattern is divided
Analysis needs to detect electronic scanner microscope after preparing sample, and network vector point is detected after sample need to be prepared to the analysis of absorbing property
Analyzer.
Description of the drawings
The zinc powder reduction graphene oxide of Fig. 1 embodiment of the present invention 1~6 prepares the method with absorbing property graphene
Process flow chart；
Scanning electron microscopic picture with absorbing property graphene prepared by Fig. 2 embodiment of the present invention 1；
Scanning electron microscopic picture with absorbing property graphene prepared by Fig. 3 embodiment of the present invention 2；
Scanning electron microscopic picture with absorbing property graphene prepared by Fig. 4 embodiment of the present invention 3；
Scanning electron microscopic picture with absorbing property graphene prepared by Fig. 5 embodiment of the present invention 4；
Scanning electron microscopic picture with absorbing property graphene prepared by Fig. 6 embodiment of the present invention 5；
Scanning electron microscopic picture with absorbing property graphene prepared by Fig. 7 embodiment of the present invention 6；
Reflectance loss figure with absorbing property graphene prepared by Fig. 8 embodiment of the present invention 1；
Reflectance loss figure with absorbing property graphene prepared by Fig. 9 embodiment of the present invention 2；
Reflectance loss figure with absorbing property graphene prepared by Figure 10 embodiment of the present invention 3；
Reflectance loss figure with absorbing property graphene prepared by Figure 11 embodiment of the present invention 4；
Reflectance loss figure with absorbing property graphene prepared by Figure 12 embodiment of the present invention 5；
Reflectance loss figure with absorbing property graphene prepared by Figure 13 embodiment of the present invention 6；
Specific embodiment：
The technique that the zinc powder reduction graphene oxide of example 1 below~6 prepares the method with absorbing property graphene
Flow chart is shown in attached drawing 1.
In following embodiment, in the step 1 (1), potassium peroxydisulfate, phosphorus pentoxide, the concentrated sulfuric acid are that analysis is pure.
Embodiment 1
A kind of zinc powder reduction graphene oxide prepares the method with absorbing property graphene, comprises the following steps：
Step 1, reaction of formation pre-oxidation graphite presoma：
(1) stoichiometrically 8: 4: 3: 38,16g natural flake graphites (C), 8g potassium peroxydisulfates (K are weighed respectively2S2O8)、
6g phosphorus pentoxides (P2O5) and 76mL mass concentrations 98% the concentrated sulfuric acid, totally 4 kinds of raw materials；
(2) after 4 kinds of raw materials are mixed in four-hole boiling flask, under agitation, 70 DEG C of water bath with thermostatic control is placed in, reacted
6h, mixing speed 150r/min；
(3) diluted with deionized water and wash neutrality, vacuum pump filters, and is ground after drying at room temperature, and pre- oxygen is made
Graphite presoma；
Step 2, secondary oxidation prepares graphite oxide：
(1) 2g pre-oxidation graphite presomas (g), the concentrated sulfuric acid (mL) and the 4g permanganic acid that 26mL mass fractions are 98% are weighed
Potassium (g) will first pre-oxidize the concentrated sulfuric acid that graphite presoma and mass fraction are 98% and be mixed in ice-water bath, stirring and meanwhile with
1g/min is slowly added to potassium permanganate, obtains mixture；
(2) mixture is placed in 35 DEG C of water bath with thermostatic control, electric stirring fully reacts 2h, is made blackish green thick
Liquid；
(3) first part of deionized water of 92mL, second part of deionized water of 280mL and 8g hydrogen peroxide are measured；
It controls temperature≤45 DEG C of blackish green viscous liquid, adds in first part of deionized water, after 15min, add in the
Bright yellow solution is made in two parts of deionized waters and hydrogen peroxide；
(3) by bright yellow solution, filter and washed with mass concentration for 10% dilute hydrochloric acid, is washed with deionized to PH=
6.5 obtain mixed liquor；
(4) by mixed liquor, ground after air dry oven drying, graphite oxide reaction is made and drives body.
Step 3, graphene oxide dispersion is prepared：
(1) body (g): deionized water (mL)=1: 2000 is driven by graphite oxide reaction, 0.1g graphite oxides is reacted and drive body
It with deionized water at 30 DEG C, is sufficiently mixed under the conditions of electric stirring, brown suspension is made；
(2) by brown suspension in ultrasonic oscillation device, ultrasonic vibration 4h makes its fully dispersed, and the oxidation of brown is made
Graphene dispersing solution；
Step 4, zinc powder reduction graphene oxide prepares graphene：
(1) measure respectively or measure 200mL graphene oxide dispersions and 0.5g zinc powders, in 30~50 DEG C of water bath with thermostatic control
In, zinc powder is added in graphene oxide dispersion, is sufficiently mixed under electric stirring, the mixture with black precipitate is made；
(2) by the mixture with black precipitate, suction filtration obtains filter cake, is ground after being dried in air dry oven, is made
Graphene with absorbing property.
Manufactured in the present embodiment to have absorbing property graphene, scanning electron microscopic picture is shown in attached drawing 2, and reflectance loss figure is shown in attached
Fig. 8, the graphene are 0.63 in the magnetic conductivity real part of 4.57GHz Frequency points, imaginary part 0.09；Real part of permittivity is
123.69 imaginary part 77.24.
Embodiment 2
A kind of zinc powder reduction graphene oxide prepares the method with absorbing property graphene, comprises the following steps：
Step 1, reaction of formation pre-oxidation graphite presoma：
(1) stoichiometrically 9: 5: 4: 39,18g natural flake graphites (C), 10g potassium peroxydisulfates are weighed respectively
(K2S2O8), 8g phosphorus pentoxides (P2O5) and 78mL mass concentrations 98% the concentrated sulfuric acid, totally 4 kinds of raw materials；
(2) after 4 kinds of raw materials are mixed in four-hole boiling flask, under agitation, 70 DEG C of water bath with thermostatic control is placed in, reacted
7h, mixing speed 270r/min；
(3) diluted with deionized water and wash neutrality, vacuum pump filters, and is ground after drying at room temperature, and pre- oxygen is made
Graphite presoma；
Step 2, secondary oxidation prepares graphite oxide：
(1) 2g pre-oxidation graphite presomas (g), the concentrated sulfuric acid (mL) and the 6g permanganic acid that 28mL mass fractions are 98% are weighed
Potassium (g) will first pre-oxidize the concentrated sulfuric acid that graphite presoma and mass fraction are 98% and be mixed in ice-water bath, stirring and meanwhile with
1g/min is slowly added to potassium permanganate, obtains mixture；
(2) mixture is placed in 35 DEG C of water bath with thermostatic control, electric stirring fully reacts 3h, is made blackish green thick
Liquid；
(3) first part of deionized water of 92mL, second part of deionized water of 280mL and 9mL hydrogen peroxide are measured；
It controls temperature≤45 DEG C of blackish green viscous liquid, adds in first part of deionized water, after 15min, add in the
Bright yellow solution is made in two parts of deionized waters and hydrogen peroxide；
(3) by bright yellow solution, filter and washed with mass concentration for 10% dilute hydrochloric acid, is washed with deionized to PH=
6.5, obtain mixed liquor；
(4) by mixed liquor, ground after air dry oven drying, graphite oxide reaction is made and drives body.
Step 3, graphene oxide dispersion is prepared：
(1) body (g): deionized water (mL)=1: 2000 is driven by graphite oxide reaction, 0.1g graphite oxides is reacted and drive body
It with deionized water at 30 DEG C, is sufficiently mixed under the conditions of electric stirring, brown suspension is made；
(2) by brown suspension in ultrasonic oscillation device, ultrasonic vibration 5h makes its fully dispersed, and the oxidation of brown is made
Graphene dispersing solution；
Step 4, zinc powder reduction graphene oxide prepares graphene：
(1) measure respectively or measure 200mL graphene oxide dispersions and 1g zinc powders, it, will in 30 DEG C of water bath with thermostatic control
Zinc powder is added in graphene oxide dispersion, is sufficiently mixed under electric stirring, and the mixture with black precipitate is made；
(2) by the mixture with black precipitate, suction filtration obtains filter cake, is ground after being dried in air dry oven, is made
Graphene with absorbing property.
Manufactured in the present embodiment to have absorbing property graphene, scanning electron microscopic picture is shown in attached drawing 3, and reflectance loss figure is shown in attached
Fig. 9, the graphene are 0.75 in the magnetic conductivity real part of 17.49GHz Frequency points, imaginary part 0.24；Real part of permittivity for-
12.77, imaginary part 88.65.
Embodiment 3
A kind of zinc powder reduction graphene oxide prepares the method with absorbing property graphene, comprises the following steps：
Step 1, reaction of formation pre-oxidation graphite presoma：
(1) stoichiometrically 10: 6: 5: 40,20g natural flake graphites (C), 12g potassium peroxydisulfates are weighed respectively
(K2S2O8), 10g phosphorus pentoxides (P2O5) and 80mL mass concentrations 98% the concentrated sulfuric acid, totally 4 kinds of raw materials；
(2) after 4 kinds of raw materials are mixed in four-hole boiling flask, under agitation, 80 DEG C of water bath with thermostatic control is placed in, reacted
8h, mixing speed 180r/min；
(3) diluted with deionized water and wash neutrality, vacuum pump filters, and is ground after drying at room temperature, and pre- oxygen is made
Graphite presoma；
Step 2, secondary oxidation prepares graphite oxide：
(1) 6g pre-oxidation graphite presomas (g), the concentrated sulfuric acid (mL) and the 8g permanganic acid that 30mL mass fractions are 98% are weighed
Potassium (g) will first pre-oxidize the concentrated sulfuric acid that graphite presoma and mass fraction are 98% and be mixed in ice-water bath, stirring and meanwhile with
1g/min is slowly added to potassium permanganate, obtains mixture；
(2) mixture is placed in 35 DEG C of water bath with thermostatic control, electric stirring fully reacts 4h, is made blackish green thick
Liquid；
(3) first part of deionized water of 92mL, second part of deionized water of 280mL and 10mL hydrogen peroxide are measured；
It controls temperature≤45 DEG C of blackish green viscous liquid, adds in first part of deionized water, after 15min, add in the
Bright yellow solution is made in two parts of deionized waters and hydrogen peroxide；
(3) by bright yellow solution, filter and washed with mass concentration for 10% dilute hydrochloric acid, is washed with deionized to PH=
6.5, obtain mixed liquor；
(4) by mixed liquor, ground after air dry oven drying, graphite oxide reaction is made and drives body.
Step 3, graphene oxide dispersion is prepared：
(1) body (g): deionized water (mL)=3: 5000 is driven by graphite oxide reaction, 0.3g graphite oxides is reacted and drive body
It with deionized water at 50 DEG C, is sufficiently mixed under the conditions of electric stirring, brown suspension is made；
(2) by brown suspension in ultrasonic oscillation device, ultrasonic vibration 6h makes its fully dispersed, and the oxidation of brown is made
Graphene dispersing solution；
Step 4, zinc powder reduction graphene oxide prepares graphene：
(1) measure respectively or measure 200mL graphene oxide dispersions and 2g zinc powders, it, will in 30 DEG C of water bath with thermostatic control
Zinc powder is added in graphene oxide dispersion, is sufficiently mixed under electric stirring, and the mixture with black precipitate is made；
(2) by the mixture with black precipitate, suction filtration obtains filter cake, is ground after being dried in air dry oven, is made
Graphene with absorbing property.
Manufactured in the present embodiment to have absorbing property graphene, scanning electron microscopic picture is shown in attached drawing 4, and reflectance loss figure is shown in attached
Figure 10, the graphene 17.49GHz Frequency points magnetic conductivity real part for 0.93., imaginary part 0.29；Real part of permittivity for-
17.43, imaginary part 87.35.
Embodiment 4
A kind of zinc powder reduction graphene oxide prepares the method with absorbing property graphene, comprises the following steps：
Step 1, reaction of formation pre-oxidation graphite presoma：
(1) stoichiometrically 8: 4: 3: 38,16g natural flake graphites (C), 8g potassium peroxydisulfates (K are weighed respectively2S2O8)、
6g phosphorus pentoxides (P2O5) and 76mL mass concentrations 98% the concentrated sulfuric acid, totally 4 kinds of raw materials；
(2) after 4 kinds of raw materials are mixed in four-hole boiling flask, under agitation, 60 DEG C of water bath with thermostatic control is placed in, reacted
6h, mixing speed 150r/min；
(3) diluted with deionized water and wash neutrality, vacuum pump filters, and is ground after drying at room temperature, and pre- oxygen is made
Graphite presoma；
Step 2, secondary oxidation prepares graphite oxide：
(1) 2g pre-oxidation graphite presomas (g), the concentrated sulfuric acid (mL) and the 4g permanganic acid that 26mL mass fractions are 98% are weighed
Potassium (g) will first pre-oxidize the concentrated sulfuric acid that graphite presoma and mass fraction are 98% and be mixed in ice-water bath, stirring and meanwhile with
1g/min is slowly added to potassium permanganate, obtains mixture；
(2) mixture is placed in 35 DEG C of water bath with thermostatic control, electric stirring fully reacts 2h, is made blackish green thick
Liquid；
(3) first part of deionized water of 92mL, second part of deionized water of 280mL and 8mL hydrogen peroxide are measured；
It controls temperature≤45 DEG C of blackish green viscous liquid, adds in first part of deionized water, after 15min, add in the
Bright yellow solution is made in two parts of deionized waters and hydrogen peroxide；
(3) by bright yellow solution, filter and washed with mass concentration for 10% dilute hydrochloric acid, is washed with deionized to PH=
6.5, obtain mixed liquor；
(4) by mixed liquor, ground after air dry oven drying, graphite oxide reaction is made and drives body.
Step 3, graphene oxide dispersion is prepared：
(1) body (g): deionized water (mL)=3: 5000 is driven by graphite oxide reaction, 0.3g graphite oxides is reacted and drive body
It with deionized water at 30 DEG C, is sufficiently mixed under the conditions of electric stirring, brown suspension is made；
(2) by brown suspension in ultrasonic oscillation device, ultrasonic vibration 4h makes its fully dispersed, and the oxidation of brown is made
Graphene dispersing solution；
Step 4, zinc powder reduction graphene oxide prepares graphene：
(1) measure respectively or measure 200mL graphene oxide dispersions and 0.5g zinc powders, in 50 DEG C of water bath with thermostatic control,
Zinc powder is added in graphene oxide dispersion, is sufficiently mixed under electric stirring, the mixture with black precipitate is made；
(2) by the mixture with black precipitate, suction filtration obtains filter cake, is ground after being dried in air dry oven, is made
Graphene with absorbing property.
Manufactured in the present embodiment to have absorbing property graphene, scanning electron microscopic picture is shown in attached drawing 5, and reflectance loss figure is shown in attached
Figure 11, the graphene 17.49GHz Frequency points magnetic conductivity real part for 0.52., imaginary part 0.34；Real part of permittivity for-
4.93, imaginary part 70.40.
Embodiment 5
A kind of zinc powder reduction graphene oxide prepares the method with absorbing property graphene, comprises the following steps：
Step 1, reaction of formation pre-oxidation graphite presoma：
(1) stoichiometrically 9: 5: 4: 39,18g natural flake graphites (C), 10g potassium peroxydisulfates are weighed respectively
(K2S2O8), 8g phosphorus pentoxides (P2O5) and 78mL mass concentrations 98% the concentrated sulfuric acid, totally 4 kinds of raw materials；
(2) after 4 kinds of raw materials are mixed in four-hole boiling flask, under agitation, 70 DEG C of water bath with thermostatic control is placed in, reacted
7h, mixing speed 270r/min；
(3) diluted with deionized water and wash neutrality, vacuum pump filters, and is ground after drying at room temperature, and pre- oxygen is made
Graphite presoma；
Step 2, secondary oxidation prepares graphite oxide：
(1) 2g pre-oxidation graphite presomas (g), the concentrated sulfuric acid (mL) and the 6g permanganic acid that 28mL mass fractions are 98% are weighed
Potassium (g) will first pre-oxidize the concentrated sulfuric acid that graphite presoma and mass fraction are 98% and be mixed in ice-water bath, stirring and meanwhile with
1g/min is slowly added to potassium permanganate, obtains mixture；
(2) mixture is placed in 35 DEG C of water bath with thermostatic control, electric stirring fully reacts 3h, is made blackish green thick
Liquid；
(3) first part of deionized water of 92mL, second part of deionized water of 280mL and 9mL hydrogen peroxide are measured；
It controls temperature≤45 DEG C of blackish green viscous liquid, adds in first part of deionized water, after 15min, add in the
Bright yellow solution is made in two parts of deionized waters and hydrogen peroxide；
(3) by bright yellow solution, filter and washed with mass concentration for 10% dilute hydrochloric acid, is washed with deionized to PH=
6.5, obtain mixed liquor；
(4) by mixed liquor, ground after air dry oven drying, graphite oxide reaction is made and drives body.
Step 3, graphene oxide dispersion is prepared：
(1) body (g): deionized water (mL)=2: 4000 is driven by graphite oxide reaction, 0.2g graphite oxides is reacted and drive body
It with deionized water at 40 DEG C, is sufficiently mixed under the conditions of electric stirring, brown suspension is made；
(2) by brown suspension in ultrasonic oscillation device, ultrasonic vibration 4h makes its fully dispersed, and the oxidation of brown is made
Graphene dispersing solution；
Step 4, zinc powder reduction graphene oxide prepares graphene：
(1) measure respectively or measure 200mL graphene oxide dispersions and 1g zinc powders, it, will in 50 DEG C of water bath with thermostatic control
Zinc powder is added in graphene oxide dispersion, is sufficiently mixed under electric stirring, and the mixture with black precipitate is made；
(2) by the mixture with black precipitate, suction filtration obtains filter cake, is ground after being dried in air dry oven, is made
Graphene with absorbing property.
Manufactured in the present embodiment to have absorbing property graphene, scanning electron microscopic picture is shown in attached drawing 6, and reflectance loss figure is shown in attached
Figure 12, the graphene 17.49GHz Frequency points magnetic conductivity real part for 0.55., imaginary part 0.17；Real part of permittivity for-
15.66, imaginary part 103.44.
Embodiment 6
A kind of zinc powder reduction graphene oxide prepares the method with absorbing property graphene, comprises the following steps：
Step 1, reaction of formation pre-oxidation graphite presoma：
(1) stoichiometrically 10: 6: 5: 40,20g natural flake graphites (C), 12g potassium peroxydisulfates are weighed respectively
(K2S2O8), 10g phosphorus pentoxides (P2O5) and 80mL mass concentrations 98% the concentrated sulfuric acid, totally 4 kinds of raw materials；
(2) after 4 kinds of raw materials are mixed in four-hole boiling flask, under agitation, 80 DEG C of water bath with thermostatic control is placed in, reacted
8h, mixing speed 180r/min；
(3) diluted with deionized water and wash neutrality, vacuum pump filters, and is ground after drying at room temperature, and pre- oxygen is made
Graphite presoma；
Step 2, secondary oxidation prepares graphite oxide：
(1) 2g pre-oxidation graphite presomas (g), the concentrated sulfuric acid (mL) and the 8g permanganic acid that 30mL mass fractions are 98% are weighed
Potassium (g) will first pre-oxidize the concentrated sulfuric acid that graphite presoma and mass fraction are 98% and be mixed in ice-water bath, stirring and meanwhile with
1g/min is slowly added to potassium permanganate, obtains mixture；
(2) mixture is placed in 35 DEG C of water bath with thermostatic control, electric stirring fully reacts 4h, is made blackish green thick
Liquid；
(3) first part of deionized water of 92mL, second part of deionized water of 280mL and 10mL hydrogen peroxide are measured；
It controls temperature≤45 DEG C of blackish green viscous liquid, adds in first part of deionized water, after 15min, add in the
Bright yellow solution is made in two parts of deionized waters and hydrogen peroxide；
(3) by bright yellow solution, filter and washed with mass concentration for 10% dilute hydrochloric acid, is washed with deionized to PH=
6.5, obtain mixed liquor；
(4) by mixed liquor, ground after air dry oven drying, graphite oxide reaction is made and drives body.
Step 3, graphene oxide dispersion is prepared：
(1) body (g): deionized water (mL)=3: 5000 is driven by graphite oxide reaction, 0.3g graphite oxides is reacted and drive body
It with deionized water at 50 DEG C, is sufficiently mixed under the conditions of electric stirring, brown suspension is made；
(2) by brown suspension in ultrasonic oscillation device, ultrasonic vibration 6h makes its fully dispersed, and the oxidation of brown is made
Graphene dispersing solution；
Step 4, zinc powder reduction graphene oxide prepares graphene：
(1) measure respectively or measure 200mL graphene oxide dispersions and 2g zinc powders, it, will in 50 DEG C of water bath with thermostatic control
Zinc powder is added in graphene oxide dispersion, is sufficiently mixed under electric stirring, and the mixture with black precipitate is made；
(2) by the mixture with black precipitate, suction filtration obtains filter cake, is ground after being dried in air dry oven, is made
Graphene with absorbing property.
Manufactured in the present embodiment to have absorbing property graphene, scanning electron microscopic picture is shown in attached drawing 7, and reflectance loss figure is shown in attached
Figure 13, the graphene 5.08GHz Frequency points magnetic conductivity real part for 0.35., imaginary part 0.04；Real part of permittivity is
178.26 imaginary part 102.53.
Claims (8)
1. a kind of zinc powder reduction graphene oxide prepares the method with absorbing property graphene, which is characterized in that including following
Step：
Step 1, reaction of formation pre-oxidation graphite presoma：
(1) stoichiometrically, natural flake graphite (C): potassium peroxydisulfate (K2S2O8): phosphorus pentoxide (P2O5): mass fraction
For 98% concentrated sulfuric acid (H2SO4)=(8~10): (4~6): (3~5): (38~40) weigh above-mentioned 4 kinds of raw materials respectively；
(2) after 4 kinds of raw materials are mixed, under agitation, 60~80 DEG C of water bath with thermostatic control is placed in, reacts 6~8h；
(3) diluted with deionized water and wash neutrality, be filtered by vacuum, ground after drying at room temperature, pre-oxidation graphite is made
Presoma；
Step 2, secondary oxidation prepares graphite oxide：
(1) by pre-oxidation graphite presoma (g): mass fraction is 98% concentrated sulfuric acid (mL): potassium permanganate (g)=(1~3):
Pre-oxidation graphite presoma is first by (13~15): (4~8) measure or take respectively above-mentioned 3 kinds of raw materials with mass fraction
98% concentrated sulfuric acid mixes in ice-water bath, and stirring is slowly added to potassium permanganate simultaneously, obtains mixture；
(2) mixture is placed in 30~40 DEG C of isoperibol, fully reacts 2~4h, blackish green viscous liquid is made；
(3) by volume, the material quality fraction in step 2 (1) is 98% concentrated sulfuric acid: first part of deionized water=(1~3)
: (2~4) measure first part of deionized water, and the material quality fraction in step 2 (1) is 98% concentrated sulfuric acid by volume：The
Two parts of deionized waters: hydrogen peroxide=(28~30): (1~3) measures second part of deionized water and hydrogen peroxide；
It controls temperature≤45 DEG C of blackish green viscous liquid, adds in first part of deionized water, after 12~18min, add in the
Bright yellow solution is made in two parts of deionized waters and hydrogen peroxide；
(3) by bright yellow solution, filter and washed with dilute hydrochloric acid, be washed with deionized to PH=6~6.8, obtain mixed liquor；
(4) by mixed liquor, ground after drying, graphite oxide reaction is made and drives body.
Step 3, graphene oxide dispersion is prepared：
(1) body (g): deionized water (mL)=(1~3): (2000~5000) react graphite oxide is driven by graphite oxide reaction
It drives body to be sufficiently mixed at 30~50 DEG C with deionized water, brown suspension is made；
(2) by brown suspension ultrasonic oscillation, make its fully dispersed, the graphene oxide dispersion of brown is made；
Step 4, zinc powder reduction graphene oxide prepares graphene：
(1) graphene oxide dispersion (mL): zinc powder (g)=(190~210): (0.5~2) is pressed, measures or measure oxidation respectively
In 30~50 DEG C of water bath with thermostatic control, zinc powder is added in graphene oxide dispersion for graphene dispersing solution and zinc powder, fully mixed
It closes, the mixture with black precipitate is made；
(2) by the mixture with black precipitate, suction filtration obtains filter cake, is ground after drying, and the graphite with absorbing property is made
Alkene.
2. zinc powder reduction graphene oxide according to claim 1 prepares the method with absorbing property graphene, special
Sign is, in the step 1 (1), potassium peroxydisulfate, phosphorus pentoxide, the concentrated sulfuric acid are that analysis is pure.
3. zinc powder reduction graphene oxide according to claim 1 prepares the method with absorbing property graphene, special
Sign is, in the step 1 (2), mixing speed is 150~270r/min.
4. zinc powder reduction graphene oxide according to claim 1 prepares the method with absorbing property graphene, special
Sign is, in the step 1 (2), reacts and is carried out in four-hole boiling flask；In the step 2 (2), isoperibol is water bath with thermostatic control；
In the step 2 (4), dried using air dry oven；In the step 3 (2), ultrasonic vibration is in ultrasonic oscillation device
It carries out；In the step 4 (2), dried using air dry oven.
5. zinc powder reduction graphene oxide according to claim 1 prepares the method with absorbing property graphene, special
Sign is, in the step 2 (1), the speed being slowly added to is 0.5~1g/min.
6. zinc powder reduction graphene oxide according to claim 1 prepares the method with absorbing property graphene, special
Sign is, in the step 2 (2), the method fully reacted is auxiliary electric stirring mixture；In the step 3 (1), fully
The method of mixing is, using electric stirring；In the step 4 (1), well-mixed method is electric stirring.
7. zinc powder reduction graphene oxide according to claim 1 prepares the method with absorbing property graphene, special
Sign is, in the step 2 (3), the mass concentration of dilute hydrochloric acid is 5~15%.
8. zinc powder reduction graphene oxide according to claim 1 prepares the method with absorbing property graphene, special
Sign is, in the step 3 (2), 4~6h of ultrasonic vibration.
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