CN110342501A - A kind of method that pulsed high energy microwave quickly restores preparation high quality reduced graphene - Google Patents
A kind of method that pulsed high energy microwave quickly restores preparation high quality reduced graphene Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 147
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 94
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 26
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 54
- 239000010439 graphite Substances 0.000 claims abstract description 54
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 30
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 14
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 11
- 239000005457 ice water Substances 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 10
- 238000002604 ultrasonography Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 4
- 238000005554 pickling Methods 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- -1 oxygen Graphite alkene Chemical class 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 1
- 229910001882 dioxygen Inorganic materials 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 abstract description 7
- 230000003647 oxidation Effects 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 26
- 238000013019 agitation Methods 0.000 description 10
- 238000007710 freezing Methods 0.000 description 10
- 230000008014 freezing Effects 0.000 description 10
- 239000002002 slurry Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 238000001069 Raman spectroscopy Methods 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 125000000524 functional group Chemical group 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 241000446313 Lamella Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- OBOXTJCIIVUZEN-UHFFFAOYSA-N [C].[O] Chemical compound [C].[O] OBOXTJCIIVUZEN-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000001473 noxious effect Effects 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
Abstract
The present invention provides a kind of methods that pulsed high energy microwave quickly restores preparation high quality reduced graphene, key step includes: that crystalline flake graphite is added in fuming nitric aicd under ice-water bath, after hydrogen peroxide reaction a period of time is added, washing, drying, microwave bulking obtain expanded graphite；To expanded graphite and potassium permanganate is sequentially added in the mixed acid system of 0 DEG C of concentrated sulfuric acid and phosphoric acid, using the strong oxidizing property of potassium permanganate, by graphite oxidation at graphene oxide under 0 DEG C of low temperature；Graphene oxide is placed in isothermal holding in tube furnace, obtains prereduction graphene oxide powder；Finally prereduction graphene oxide powder is put into pulsed high energy microwave cavity, microwave is opened, obtains the reduced graphene product of high quality.Graphene oxide layer structural integrity prepared by the present invention, the reduced graphene quality most obtained after pulsed high energy microwave quickly restores afterwards is high, is the preparation of graphene oxide, composite, haves laid a good foundation.
Description
Technical field
The invention belongs to technical field of graphene, and in particular to a kind of pulsed high energy microwave quickly restores preparation high quality also
The method of former graphene.
Background technique
Graphene oxide is product of the powdered graphite after chemical oxidation and removing, and be otherwise known as functionalization graphene, is
The oxide of graphene, and the presoma of low cost, large scale preparation graphene.Compared with expensive carbon nanotube,
Graphene oxide it is cheap, preparation process is simple.Traditional Hummers method prepares graphene oxide, and there are three step, low temperature
Edge oxidation, medium temperature deep oxidation and pyrohydrolysis.But due to medium temperature Strong oxdiative, pyrohydrolysis, easily to the lamella knot of graphite
It is configured to irreversible influence, causes the missing of carbon atom, the performance and application of graphene oxide are affected, especially to oxidation
The quality that graphene restores to obtain reduced graphene product has a significant impact, and significantly limits graphene oxide and goes back
The application of former graphene oxide.However currently, the restoring method of graphene oxide is numerous, such as electronation etc., but pole
It is also easy to produce a large amount of by-product, technique is cumbersome.
Due to the uniform heating feature being rapidly heated of microwave radiation, it is applied to the quick preparation of graphene.At present
The research of Microwave-assisted Reduction is concentrated mainly on using pretreated graphite oxide, graphene oxide and reduction-oxidation graphite
Alkene does presoma, or is synthetically prepared graphene product by liquid phase ultrasound.Known patent CN108358191A discloses one kind
Low defect graphene oxide and preparation method thereof after slightly restoring graphene oxide, through microwave radiation, obtains high-quality
Graphene product.And patent CN105236398A provides a kind of microwave-assisted production method for preparing graphene, first will
Graphite, which is put into microwave expansion device, carries out rapid expanding, obtains quasiflake graphite, and quasiflake graphite is being carried out oxidation reaction,
Dry graphite oxide is obtained after washed, dry, dry graphite oxide is sent into microwave reduction device, in vacuum or lazy
Property gas shield under the conditions of simultaneously removed and restored, obtain dry graphene powder.But the processing time of these methods
It is all longer, there are also the graphene defect of by-product production and output is more, limit graphene product market into one
Step expands.Therefore, there is an urgent need to a kind of preparation methods of low defect graphene oxide, while in the base for simplifying reducing process as far as possible
On plinth, using and generating for noxious material is avoided, the graphene product of high quality is prepared.
Summary of the invention
The object of the present invention is to provide a kind of pulsed high energy microwaves quickly to restore the method for preparing high quality reduced graphene,
Simple process prepares the graphene product of high quality.
To achieve the above object, the present invention provides a kind of pulsed high energy microwave and quickly restores preparation high quality reduced graphene
Method, comprising the following steps:
1) crystalline flake graphite is added in a certain amount of fuming nitric aicd under the conditions of ice-water bath, is then added while stirring double
Oxygen water, after reacting a period of time, washing, drying, the extruding in tubular type micro-wave oven obtain expanded graphite；Wherein, the scale stone
The solid-to-liquid ratio of ink and fuming nitric aicd is 1g:20~25ml；
2) expanded graphite for obtaining step 1) is added in 0 DEG C of the concentrated sulfuric acid and the mixed acid of phosphoric acid, the concentrated sulfuric acid and phosphorus
Volume ratio 11:1~5 of acid, after being stirred to react 10~60min, are slowly added to a certain amount of potassium permanganate, in 0 DEG C of item after adding
24~72h is reacted under part, and dilute sulfuric acid is then slowly added dropwise and terminates reaction；Suitable hydrogen peroxide is subsequently added into not generating bubble,
Obtain graphite oxide solution；Wherein, the solid-to-liquid ratio of the expanded graphite and the concentrated sulfuric acid is 1g:90~130ml, the expanded graphite
Mass ratio with potassium permanganate is 1:3~7；
3) graphite oxide solution that step 2) obtains, successively through pickling, be washed to neutrality, ultrasound, centrifugation, dry, grinding
Obtain graphene oxide sample；
4) the graphene oxide sample that step 3) obtains is placed in isothermal holding in tube furnace, be cooled to room temperature, obtained pre-
The graphene oxide powder of reduction；
5) graphene oxide powder for the prereduction that step 4) obtains is put into the cavity of pulsed high energy microwave reactor,
1~5s of microwave reaction is opened, the reduced graphene product of high quality is obtained.
In step 1), the volume ratio of the fuming nitric aicd and hydrogen peroxide is 9~15:1, and microwave power is 100~1000w,
The microwave reaction time is 5~60s.
In step 2), the mass fraction of the phosphoric acid is >=50%, and the mass fraction of the dilute sulfuric acid is 5~15%.
In step 3), the process of the pickling is: with mass fraction be 5~10% dilute hydrochloric acid wash, removing metal from
Son.
In step 3), the power of the ultrasound is 50~500w, and the time is 30~120min.
In step 3), the drying is freeze-drying.
In step 4), the temperature of the tube furnace is 150~200 DEG C, and soaking time is 30~90min.
In step 5), the frequency of the pulsed high energy microwave is 2450MHz or 915MHz, and the peak power of microwave is higher than
100MW。
Compared with prior art, the invention has the following beneficial effects:
(1) for others prepare the method for graphene oxide, operation of the present invention is simple, and process control obtains
Graphene oxide product lamellar structure it is more complete.
(2) it is quickly restored through pulsed high energy microwave, the quality of reduced graphene is higher, and the recovery time foreshortens to 1~5s, together
When entire reduction process only generate a small amount of innocuous gas.
Detailed description of the invention
Fig. 1 is the XRD diagram of reduced graphene prepared by the embodiment of the present invention 1；
Fig. 2 is the x-ray photoelectron spectroscopy figure of reduced graphene prepared by the embodiment of the present invention 1；
Fig. 3 is the Raman spectrogram of reduced graphene prepared by the embodiment of the present invention 1.
Specific embodiment
Invention is further described in detail in the following with reference to the drawings and specific embodiments, it is pointed out that reality below
It applies example only and is to the explanation of laying down a definition property of the invention in a manner of example sentence, but protection of the invention is not limited to this, institute is capable
The staff in domain is spirit with the present invention, and the equivalence replacement done to the present invention each falls within protection scope of the present invention.
Embodiment 1
In the fuming nitric aicd that 1g crystalline flake graphite is added to 20mL under the conditions of ice-water bath, 2mL is then added while stirring
The hydrogen peroxide of mass fraction 30%, after reacting 40min, washing, dry, the extruding 10s in the tubular type micro-wave oven that power is 800w,
Obtain expanded graphite.
The burning of the mixed acid of the phosphoric acid of the concentrated sulfuric acid and 12ml mass fraction >=50% of 120ml mass fraction 98% will be filled
Cup is placed in 0 DEG C of low temperature water bath, and the expanded graphite for taking 1g to obtain is added in mix acid liquor, magnetic agitation 30min；Its
It is secondary, the potassium permanganate of 6g is slowly added into above-mentioned mixed system according to the speed of 1g/h, maintains the temperature of reaction system not
More than 20 DEG C (addition of potassium permanganate is unsuitable too fast, can multiple addition on a small quantity), the reaction was continued under 0 DEG C of low temperature 48h；So
0 DEG C of dilute sulfuric acid that 400ml mass fraction 5% is slowly added dropwise afterwards (drips, a drop is 0.05ml, 2h latter second three for initial one second one
Drop), keep the temperature of whole system to be no more than 15 DEG C；It is eventually adding the hydrogen peroxide of 10ml mass fraction 30%, with remaining oxygen
Agent potassium permanganate reacts completely, and the color of solution is changed into glassy yellow by grey and releases bubble at this time.To magnetic agitation
It after 30min, is washed twice, is repeatedly being washed with deionized water to filtrate in the hydrochloric acid that 500ml mass fraction is 5%
Property, solution is changed into the suspension of black by glassy yellow, obtains graphite oxide.Obtained graphite oxide is 100w ultrasound in power
After handling 90min in wave, it is centrifugated 15min under the centrifugal speed of 5000r/min, obtains graphene oxide slurry.Then
Graphene oxide slurry is frozen into ice fast in -50 DEG C of Cryo Equipment, then put it into cryogenic freezing case, after freezing 48h
Spongiform graphene oxide sample can be obtained.
The graphene oxide sample of low temperature preparation is kept the temperature into 60min in 200 DEG C of conventional tube furnace, obtains prereduction
Graphene oxide powder.Finally the prereduction graphene oxide powder of preparation is put into pulsed high energy microwave reactor cavity,
Unbalanced pulse microwave 2s, the frequency of microwave are 2450MHz, and the peak power of pulsed high energy microwave is higher than 100MW, height can be obtained
The reduced graphene product of quality.
The reduced graphene product that the present embodiment is prepared carries out XRD analysis, X-ray photoelectron spectroscopic analysis respectively
And Raman spectrum analysis, it is as a result as follows:
Fig. 1 is the XRD diagram of reduced graphene product prepared by the embodiment of the present invention 1, from fig. 1, it can be seen that this method preparation
After graphene oxide product is restored through pulsed high energy microwave, 2 θ of diffraction maximum of corresponding (002) crystal face is 26.4 ° of (scale stones
The corresponding diffraction maximum of ink is 26.5 °), show that the remaining oxygen-containing group of the reduced graphene of preparation is less, the reduction journey of product
Degree is high.
Fig. 2 is the XPS figure of reduced graphene product prepared by the embodiment of the present invention 1, as can be seen from Figure 2, micro- through high energy pulse
It is to respectively correspond non-oxygen carbon at 284.2,284.8eV to knit in electron binding energy: C=C, C-C functional group after wave reduction.In electricity
Son combination can be 285.7,286.6,287.9,288.8, respectively correspond C-O, C-O-C, C=O, O=C-O, π-π * at 291.4eV
Key.Compared with graphene oxide, the peak of C-O is decreased obviously, and illustrates that C-O group is thermally decomposed in microwave thermal removing reduction, oxygen-containing
Functional group significantly reduces, but still has a small amount of oxygen-containing functional group remaining, this is also consistent with the result of XRD.
Fig. 3 is the raman spectrum of reduced graphene product prepared by the embodiment of the present invention 1, as can be seen from Figure 3, this method preparation
Graphene oxide product restored through pulsed high energy microwave after, the corresponding I of reduced grapheneD:IGClose to 0.87, show product
Defect it is low, quality is high.
Embodiment 2
In the fuming nitric aicd that 1g crystalline flake graphite is added to 25mL under the conditions of ice-water bath, 2mL is then added while stirring
The hydrogen peroxide of mass fraction 30%, after reacting 60min, washing, dry, the extruding 30s in the tubular type micro-wave oven that power is 500w,
Obtain expanded graphite.
The burning of the mixed acid of the phosphoric acid of the concentrated sulfuric acid and 12ml mass fraction >=50% of 110ml mass fraction 98% will be filled
Cup is placed in 0 DEG C of low temperature water bath, and the expanded graphite for taking 1g to obtain is added in mix acid liquor, magnetic agitation 45min；Its
It is secondary, the potassium permanganate of 5g is slowly added into above-mentioned mixed system according to the speed of 1g/h, maintains the temperature of reaction system not
More than 20 DEG C (addition of potassium permanganate is unsuitable too fast, can multiple addition on a small quantity), the reaction was continued under 0 DEG C of low temperature 48h；So
0 DEG C of dilute sulfuric acid that 400ml mass fraction is 5% is slowly added dropwise afterwards (to drip within initial one second one, a drop is 0.05ml, 2h latter second three
Drop), keep the temperature of whole system to be no more than 15 DEG C；It is eventually adding the hydrogen peroxide of 10ml mass fraction 30%, with remaining oxygen
Agent potassium permanganate reacts completely, and the color of solution is changed into glassy yellow by grey and releases bubble at this time.To magnetic agitation
It after 30min, is washed twice, is repeatedly being washed with deionized water to filtrate in the hydrochloric acid that 500ml mass fraction is 5%
Property, solution is changed into the suspension of black by glassy yellow, obtains graphite oxide.Obtained graphite oxide is 100w ultrasound in power
After handling 90min in wave, it is centrifugated 15min under the centrifugal speed of 5000r/min, obtains graphene oxide slurry.Then
Graphene oxide slurry is frozen into ice fast in -50 DEG C of Cryo Equipment, then put it into cryogenic freezing case, after freezing 48h
Spongiform graphene oxide sample can be obtained.
The graphene oxide sample of low temperature preparation is kept the temperature into 60min in 180 DEG C of conventional tube furnace, obtains prereduction
Graphene oxide powder.Finally the prereduction graphene oxide powder of preparation is put into pulsed high energy microwave reactor cavity,
Unbalanced pulse microwave 3s, the frequency of microwave are 915MHz, and the peak power of pulsed high energy microwave is higher than 100MW, height can be obtained
The reduced graphene product of quality.
The XRD diagram of reduced graphene product manufactured in the present embodiment, XPS scheme and Raman spectrogram is similar to Example 1.
Embodiment 3
In the fuming nitric aicd that 1g crystalline flake graphite is added to 25mL under the conditions of ice-water bath, 2mL is then added while stirring
The hydrogen peroxide of mass fraction 30%, after reacting 60min, washing, dry, the extruding 15s in the tubular type micro-wave oven that power is 800w,
Obtain expanded graphite.
The burning of the mixed acid of the phosphoric acid of the concentrated sulfuric acid and 12ml mass fraction >=50% of 90ml mass fraction 98% will be filled
Cup is placed in 0 DEG C of low temperature water bath, and the expanded graphite for taking 1g to obtain is added in mix acid liquor, magnetic agitation 10min；Its
It is secondary, the potassium permanganate of 4g is slowly added into above-mentioned mixed system according to the speed of 1g/h, maintains the temperature of reaction system not
More than 10 DEG C (addition of potassium permanganate is unsuitable too fast, can multiple addition on a small quantity), the reaction was continued under 0 DEG C of low temperature 48h；So
The ice dilute sulfuric acid that 270ml mass fraction is 15% is slowly added dropwise afterwards (to drip within initial one second one, a drop is 0.05ml, 2h latter second three
Drop), keep the temperature of whole system to be no more than 15 DEG C；It is eventually adding the hydrogen peroxide of 10ml mass fraction 30%, with remaining oxygen
Agent potassium permanganate reacts completely, and the color of solution is changed into glassy yellow by grey and releases bubble at this time.To magnetic agitation
It after 30min, is washed twice, is repeatedly being washed with deionized water to filtrate in the hydrochloric acid that 500ml mass fraction is 5%
Property, solution is changed into the suspension of black by glassy yellow, obtains graphite oxide.Obtained graphite oxide is 50w ultrasound in power
After handling 120min in wave, it is centrifugated 15min under the centrifugal speed of 5000r/min, obtains graphene oxide slurry.Then
Graphene oxide slurry is frozen into ice fast in -50 DEG C of Cryo Equipment, then put it into cryogenic freezing case, after freezing 48h
Spongiform graphene oxide sample can be obtained.
The graphene oxide sample of low temperature preparation is kept the temperature into 30min in 200 DEG C of conventional tube furnace, obtains prereduction
Graphene oxide powder.Finally the prereduction graphene oxide powder of preparation is put into pulsed high energy microwave reactor cavity,
Unbalanced pulse microwave 1s, the frequency of microwave are 2450MHz, and the peak power of pulsed high energy microwave is higher than 100MW, height can be obtained
The reduced graphene product of quality.
The XRD diagram of reduced graphene product manufactured in the present embodiment, XPS scheme and Raman spectrogram is similar to Example 1.
Embodiment 4
In the fuming nitric aicd that 1g crystalline flake graphite is added to 21mL under the conditions of ice-water bath, 3mL is then added while stirring
The hydrogen peroxide of mass fraction 30%, after reacting 60min, washing, dry, the extruding 60s in the tubular type micro-wave oven that power is 100w,
Obtain expanded graphite.
The burning of the mixed acid of the phosphoric acid of the concentrated sulfuric acid and 12ml mass fraction >=50% of 100ml mass fraction 98% will be filled
Cup is placed in 0 DEG C of low temperature water bath, and the expanded graphite for taking 1g to obtain is added in mix acid liquor, magnetic agitation 30min；Its
It is secondary, the potassium permanganate of 3g is slowly added into above-mentioned mixed system according to the speed of 1g/h, maintains the temperature of reaction system not
More than 10 DEG C (addition of potassium permanganate is unsuitable too fast, can multiple addition on a small quantity), the reaction was continued under 0 DEG C of low temperature 48h；So
The ice dilute sulfuric acid that 400ml mass fraction is 10% is slowly added dropwise afterwards (to drip within initial one second one, a drop is 0.05ml, 2h latter second three
Drop), keep the temperature of whole system to be no more than 15 DEG C；It is eventually adding the hydrogen peroxide of 10ml mass fraction 30%, with remaining oxygen
Agent potassium permanganate reacts completely, and the color of solution is changed into glassy yellow by grey and releases bubble at this time.To magnetic agitation
It after 30min, is washed twice, is repeatedly being washed with deionized water to filtrate in the hydrochloric acid that 500ml mass fraction is 10%
Property, solution is changed into the suspension of black by glassy yellow, obtains graphite oxide.Obtained graphite oxide is 500w ultrasound in power
After handling 30min in wave, it is centrifugated 15min under the centrifugal speed of 5000r/min, obtains graphene oxide slurry.Then
Graphene oxide slurry is frozen into ice fast in -50 DEG C of Cryo Equipment, then put it into cryogenic freezing case, after freezing 72h
Spongiform graphene oxide sample can be obtained.
The graphene oxide sample of low temperature preparation is kept the temperature into 90min in 200 DEG C of conventional tube furnace, obtains prereduction
Graphene oxide powder.Finally the prereduction graphene oxide powder of preparation is put into pulsed high energy microwave reactor cavity,
Unbalanced pulse microwave 4s, the frequency of microwave are 2450MHz, and the peak power of pulsed high energy microwave is higher than 100MW, height can be obtained
The reduced graphene product of quality.
The XRD diagram of reduced graphene product manufactured in the present embodiment, XPS scheme and Raman spectrogram is similar to Example 1.
Embodiment 5
In the fuming nitric aicd that 1g crystalline flake graphite is added to 24mL under the conditions of ice-water bath, then it is added while stirring
The hydrogen peroxide of 1.6mL mass fraction 30%, after reacting 60min, washing, drying are swollen in the tubular type micro-wave oven that power is 1000w
Change 5s, obtains expanded graphite.
The burning of the mixed acid of the phosphoric acid of the concentrated sulfuric acid and 12ml mass fraction >=50% of 130ml mass fraction 98% will be filled
Cup is placed in 0 DEG C of low temperature water bath, and the expanded graphite for taking 1g to obtain is added in mix acid liquor, magnetic agitation 60min；Its
It is secondary, the potassium permanganate of 7g is slowly added into above-mentioned mixed system according to the speed of 1g/h, maintains the temperature of reaction system not
More than 10 DEG C (addition of potassium permanganate is unsuitable too fast, can multiple addition on a small quantity), the reaction was continued under 0 DEG C of low temperature 48h；So
The ice dilute sulfuric acid that 650ml mass fraction is 5% is slowly added dropwise afterwards (to drip within initial one second one, a drop is 0.05ml, 2h latter second three
Drop), keep the temperature of whole system to be no more than 15 DEG C；It is eventually adding the hydrogen peroxide of 10ml mass fraction 30%, with remaining oxygen
Agent potassium permanganate reacts completely, and the color of solution is changed into glassy yellow by grey and releases bubble at this time.To magnetic agitation
It after 30min, is washed twice, is repeatedly being washed with deionized water to filtrate in the hydrochloric acid that 500ml mass fraction is 10%
Property, solution is changed into the suspension of black by glassy yellow, obtains graphite oxide.Obtained graphite oxide is 200w ultrasound in power
After handling 60min in wave, it is centrifugated 15min under the centrifugal speed of 5000r/min, obtains graphene oxide slurry.Then
Graphene oxide slurry is frozen into ice fast in -50 DEG C of Cryo Equipment, then put it into cryogenic freezing case, after freezing 72h
Spongiform graphene oxide sample can be obtained.
The graphene oxide sample of low temperature preparation is kept the temperature into 90min in 150 DEG C of conventional tube furnace, obtains prereduction
Graphene oxide powder.Finally the prereduction graphene oxide powder of preparation is put into pulsed high energy microwave reactor cavity,
Unbalanced pulse microwave 5s, the frequency of microwave are 915MHz, and the peak power of pulsed high energy microwave is higher than 100MW, height can be obtained
The reduced graphene product of quality.
The XRD diagram of reduced graphene product manufactured in the present embodiment, XPS scheme and Raman spectrogram is similar to Example 1.
Claims (8)
1. a kind of method that pulsed high energy microwave quickly restores preparation high quality reduced graphene, which is characterized in that including following
Step:
1) crystalline flake graphite is added in a certain amount of fuming nitric aicd under the conditions of ice-water bath, dioxygen is then added while stirring
Water, after reacting a period of time, washing, drying, the extruding in tubular type micro-wave oven obtain expanded graphite；Wherein, the crystalline flake graphite
Solid-to-liquid ratio with fuming nitric aicd is 1g:20~25ml；
2) expanded graphite for obtaining step 1) is added in 0 DEG C of the concentrated sulfuric acid and the mixed acid of phosphoric acid, the concentrated sulfuric acid and phosphoric acid
Volume ratio 11:1~5 after being stirred to react 10~60min, are slowly added to a certain amount of potassium permanganate, after adding under the conditions of 0 DEG C
24~72h is reacted, dilute sulfuric acid is then slowly added dropwise and terminates reaction；Suitable hydrogen peroxide is subsequently added into bubble is not generated, is obtained
Graphite oxide solution；Wherein, the solid-to-liquid ratio of the expanded graphite and the concentrated sulfuric acid is 1g:90~130ml, the expanded graphite and height
The mass ratio of potassium manganate is 1:3~7；
3) graphite oxide solution that step 2) obtains successively through pickling, be washed to neutrality, ultrasound, centrifugation, dry, grinding obtain oxygen
Graphite alkene sample；
4) the graphene oxide sample that step 3) obtains is placed in isothermal holding in tube furnace, be cooled to room temperature, obtain prereduction
Graphene oxide powder；
5) graphene oxide powder for the prereduction that step 4) obtains is put into the cavity of pulsed high energy microwave reactor, is opened
1~5s of microwave reaction obtains the reduced graphene product of high quality.
2. the method that a kind of pulsed high energy microwave according to claim 1 quickly restores preparation high quality reduced graphene,
It is characterized in that, in step 1), the volume ratio of the fuming nitric aicd and hydrogen peroxide is 9~15:1, microwave power is 100~
1000w, microwave reaction time are 5~60s.
3. the method that a kind of pulsed high energy microwave according to claim 1 quickly restores preparation high quality reduced graphene,
It is characterized in that, the mass fraction of the phosphoric acid is >=50% in step 2), the mass fraction of the dilute sulfuric acid is 5~15%.
4. the method that a kind of pulsed high energy microwave according to claim 1 quickly restores preparation high quality reduced graphene,
It is characterized in that, the process of the pickling is in step 3): being washed with the dilute hydrochloric acid that mass fraction is 5~10%.
5. the method that a kind of pulsed high energy microwave according to claim 1 quickly restores preparation high quality reduced graphene,
It is characterized in that, the power of the ultrasound is 50~500w in step 3), the time is 30~120min.
6. the method that a kind of pulsed high energy microwave according to claim 1 quickly restores preparation high quality reduced graphene,
It is characterized in that, the drying is freeze-drying in step 3).
7. the method that a kind of pulsed high energy microwave according to claim 1 quickly restores preparation high quality reduced graphene,
It is characterized in that, the temperature of the tube furnace is 150~200 DEG C in step 4), soaking time is 30~90min.
8. the method that a kind of pulsed high energy microwave according to claim 1 quickly restores preparation high quality reduced graphene,
It is characterized in that, the frequency of the pulsed high energy microwave is 2450MHz or 915MHz in step 5), the peak power of microwave is high
In 100MW.
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