CN108147397A - A kind of preparation method of N doping three-dimensional grapheme - Google Patents
A kind of preparation method of N doping three-dimensional grapheme Download PDFInfo
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- CN108147397A CN108147397A CN201810149167.2A CN201810149167A CN108147397A CN 108147397 A CN108147397 A CN 108147397A CN 201810149167 A CN201810149167 A CN 201810149167A CN 108147397 A CN108147397 A CN 108147397A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- 230000008569 process Effects 0.000 claims abstract description 15
- 239000000047 product Substances 0.000 claims abstract description 13
- 238000005119 centrifugation Methods 0.000 claims abstract description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 46
- 229910021389 graphene Inorganic materials 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 28
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 23
- 239000000463 material Substances 0.000 claims description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 239000012286 potassium permanganate Substances 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 239000012153 distilled water Substances 0.000 claims description 9
- 235000019441 ethanol Nutrition 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 150000003233 pyrroles Chemical class 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims description 4
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 238000001514 detection method Methods 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000010453 quartz Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 238000002525 ultrasonication Methods 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical class CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 238000000137 annealing Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000011946 reduction process Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims 3
- 238000007254 oxidation reaction Methods 0.000 claims 3
- 230000001934 delay Effects 0.000 claims 1
- 238000005485 electric heating Methods 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 4
- 239000000706 filtrate Substances 0.000 abstract description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 abstract 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 abstract 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 abstract 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 abstract 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 abstract 2
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 abstract 2
- 235000010216 calcium carbonate Nutrition 0.000 abstract 1
- 229910000019 calcium carbonate Inorganic materials 0.000 abstract 1
- 239000012141 concentrate Substances 0.000 abstract 1
- 238000006477 desulfuration reaction Methods 0.000 abstract 1
- 230000023556 desulfurization Effects 0.000 abstract 1
- 239000002002 slurry Substances 0.000 abstract 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- -1 molybdenum disulfide Compound Chemical class 0.000 description 4
- 239000002131 composite material Substances 0.000 description 3
- 238000004146 energy storage Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000008595 infiltration Effects 0.000 description 3
- 238000001764 infiltration Methods 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000004321 preservation Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001721 carbon Chemical group 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 229920000877 Melamine resin Polymers 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 150000007974 melamines Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052961 molybdenite Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen(.) Chemical compound [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 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
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/22—Electronic properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/30—Purity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
Abstract
The invention discloses a kind of preparation method of N doping three-dimensional grapheme, solves the problems, such as finished product water content that method of the prior art has cost higher and prepare or higher.The present invention includes (1) and cleans：In phosphoric acid by wet process, desulfurization is carried out with CaCO3, defluorinate is carried out, then neutralized with KOH with NaOH, makes the PH=6.5 of slurry, is filtered；(2) thermal phosphoric acid reaction is added in filtrate, PH is demodulated, makes solution PH=1.8~2.2, finally to concentrate again, is crystallized, centrifugation obtains potassium acid phosphate.The product index of potassium acid phosphate new product produced by the invention reaches foreign level, and moisture content is reduced to less than 0.2%；And phosphoric acid by wet process yield is made to reach more than 75%, more than 98% thermal phosphoric acid yield, more than 98% potassium hydroxide yield, effect is very notable.
Description
Technical field
The present invention relates to technical field of inorganic nonmetallic materials, and in particular to a kind of preparation side of N doping three-dimensional grapheme
Method.
Background technology
Graphene has conductivity, big specific surface area and ultra-high capacity, is a kind of ideal energy storage electrode material.But
It due to the stability and structural intergrity of graphene, results in graphene surface and is difficult to by electrolyte complete wetting, so as to shadow
Ring the chemical property of graphene.
In general, in addition to the Nomenclature Composition and Structure of Complexes of material, dimension is determining that it is vital that material structure also plays
Effect.It is reported that porous graphene material can not only improve the specific surface area of material, while increase its capacitance, and can be with
Regulate and control the flow of carrier.Due to based cellular structures, be conducive to infiltration and the hydrophilicity and hydrophobicity of electrolyte in electrode material, one
Determine to improve the electric property of electrode material in degree, can also be used as electrochemical lithium storage and store up the electrode material of magnesium.
Since nitrogen-atoms radius is approached with carbon atom, the integrality of graphene-structured can be destroyed by doped graphene,
By regulating and controlling atom doped process during doping, thus it is possible to vary grapheme material structure obtains two dimension, three-dimensional carbon material.
Graphene can influence the spin density and distribution of charges of carbon atom after N doping, and band structure has adjustment, leads to graphene
Surface generates " active site ", these active sites cause material electrochemical activity to be improved significantly；And multidimensional structure material
Similar sponge, can effectively improve its capacitance.CN201510289262 discloses a kind of three-dimensional nitrogen-doped graphene/molybdenum disulfide
Compound and preparation method thereof, using CaC2O4 as pore-foaming agent, bifunctional reagent thioacetamide provides nitrogen source and sulphur source, synthesis
Three-dimensional nitrogen-doped graphene/molybdenum disulfide composite material (3D G-N/MoS2).104475172 A of CN disclose one kind to aoxidize stone
Three-dimensional grapheme preparation method based on black alkene, hetero atom presoma, base metal salt and template, although these methods are all
The graphite of three-dimensional structure can be obtained, but is had the following disadvantages：
(1) in preparation process using metal as substrate, cause to influence electrode there are part metals ion in grapheme material
The capacitance and electric property of material；
(2) three-dimensional structure is not notable in grapheme material structure, and electric property changes unobvious；
(3) yield of graphene is not high in such method, simultaneously because environment and technical process, environment in course of industrialization
Aspect has certain influence.
Invention content
The technical problems to be solved by the invention are：Method of the prior art prepares three-dimensional grapheme material electricity
Performance change unobvious, the problem of cost is higher, the present invention provides a kind of preparation method of N doping three-dimensional grapheme, the party
The three-dimensional structure for the finished product that method obtains is very notable, and electric property changes apparent；The present invention is in hydro-thermal method with FeCl3To substitute
Precious metal basic mode plate saves production cost, also avoids preparation process metal residual in the product, while FeCl3To environment
Close friend influences production equipment and operating environment small.
The present invention is achieved through the following technical solutions：
A kind of preparation method of N doping three-dimensional grapheme, including：
(1) graphene oxide is obtained；
(2) FeC1 is added in the reduction process of graphene oxide again3.2H20 is main pore creating material, anti-in 75~85 DEG C of hydro-thermals
Should after by fully washing, be placed in the heat-treatment furnace under 500~800 DEG C of purity nitrogen atmosphere and be pyrolyzed 2~5 hours, you can obtain nitrogen
Adulterate three-dimensional grapheme.
A kind of relative ease, inexpensive, efficient synthetic technology prepares nitrogen-doped graphene material, and material is microcosmic to be passed through
Different process can regulate and control.The present invention is in hydro-thermal method with FeCl3It substitutes precious metal basic mode plate, saves production cost,
Avoid preparation process metal residual in the product, while FeCl3It is environmentally friendly, production equipment and operating environment are influenced
It is small.The method of the present invention is easy to operate, yield is higher, environmental-friendly, the three-dimensional nitrogen-doped graphene of preparation, purer to have conductivity
The advantages that high, hydrophilic infiltration, can be widely applied to the fields such as heat-conductive composite material, energy storage material, sorbing material.
Further, the specific preparation method of the step (1) is：
Graphite powder and sodium nitrate are taken, is put into container, then measures the concentrated sulfuric acid and pours into container and place it in and be placed with ice cube
In electric-heated thermostatic water bath, potassium permanganate is added in later using magnetic stirrer；Electric hot water bath is then turned on, by temperature
30~60 DEG C, after isothermal reaction are arranged on, distilled water is slowly added to and dilutes solution；It reacts, reacts after adding distilled water dilution
After be slowly added to potassium permanganate reaction, then water-bath is made to be warming up to 96~100 DEG C of isothermal reactions；
Hydrogen peroxide is added after container taking-up is cooled to room temperature, observation solution quickly becomes golden yellow and companion by brownish black
After there are a large amount of bubbles, the dispersion liquid being ultrasonically treated in ultrasonic cleaner is put into, dispersion liquid pours into centrifuge tube and centrifuged；
Rotating speed is adjusted to 3000~5000r/min during centrifugation repeatedly to be centrifuged, until solution is clarified, uses distilled water later
It is repeatedly centrifuged, until being in neutrality using pH meter detection centrifugate, takes out in centrifuge tube and precipitate；Finally, it puts the precipitate in
Mistake in baking oven, is dried to obtain graphene oxide.
Further, the mode of potassium permanganate is added in before opening electric hot water bath is：
Potassium permanganate adds in three times, a small amount of every time, ensures reaction temperature at 13~18 DEG C in adition process.
As one of which set-up mode, the detailed process that the graphene oxide prepares N doping three-dimensional grapheme is：
Graphene oxide solution with absolute ethyl alcohol is diluted, after supersound process, adds in 3- aminopropyl triethoxysilanes,
Magnetic stirrer, which continuously stirs down, is slowly added dropwise HC1 solution, and FeC1 is then slowly added dropwise again3.2H20 ethanol solution；Then will
Mixed liquor water-bath at a temperature of 50~80 DEG C, is then dried acquisition solid, by solid abrasive into powder, 400~600
It is pyrolyzed under DEG C nitrogen protective condition, obtained black powder, is cleaned with the mixed liquor acid containing water, HF, HC1 composition；Finally, will
Using neutrality is washed to, after heat treatment is dry again, you can obtain N doping three-dimensional grapheme.
As another set-up mode, the detailed process that the graphene oxide prepares N doping three-dimensional grapheme is：
Graphene oxide powder is stirred in deionized water and ultrasonication obtains the oxygen of uniform, a concentration of 1mg/mL
Graphite alkene dispersion liquid.Graphene dispersing solution is measured with graduated cylinder, dilute hydrochloric acid is added in and pH is adjusted to 1.0 by solution；Continue ultrasound simultaneously
It is stirred continuously, FeC1 is sequentially added into dispersion liquid3.2H20、H2C2O4(NH4)2SO4；After above-mentioned salt all dissolves, delay
The slow nitrogen source that pyrroles is added dropwise as graphene continues ultrasound and pours into mixed solution in hydrothermal reaction kettle after pyrroles scatter,
Reacted at 180 DEG C, after hydro-thermal reaction, take out room temperature product after cooling, centrifuge and respectively with acetone, deionized water,
Ethanol wash is multiple, and presoma is made in drying；Presoma obtained is positioned in quartz boat, be put into tube furnace and is passed through
Ar/H2Mixed gas controls airflow rate, and annealing is so as to obtain the three-dimensional structure graphene of N doping under the conditions of 600 DEG C.
The present invention has the advantage that and advantageous effect：
1st, the method for the present invention is easy to operate, yield is higher, environmental-friendly, the three-dimensional nitrogen-doped graphene of preparation, purer tool
There are conductivity height, hydrophilic infiltration, can be widely applied to the fields such as heat-conductive composite material, energy storage material, sorbing material；
2nd, the present invention in hydro-thermal method with FeCl3It substitutes precious metal basic mode plate, saves production cost, also avoid making
Standby process metal residual in the product, while FeCl3It is environmentally friendly, production equipment and operating environment are influenced small；
3rd, N doping mode of the present invention is various, both can be using pure nitrogen gas as nitrogen source, can also compound conduct doping nitrogen
Atom can obtain three-dimensional structure nitrogen-doped graphene material by preparation process；
4th, nitrogen-doped graphene material yield of the present invention is higher.
Description of the drawings
Attached drawing described herein is used for providing further understanding the embodiment of the present invention, forms one of the application
Point, do not form the restriction to the embodiment of the present invention.In the accompanying drawings：
Fig. 1 is the SEM electron-microscope scanning figures for the N doping three-dimensional grapheme that embodiment 2 obtains.
Fig. 2 is the SEM electron-microscope scanning figures for the N doping three-dimensional grapheme that embodiment 3 obtains.
Fig. 3 is the resistivity column schematic diagram of each embodiment finished product in the present invention.
Fig. 4 is the yield column schematic diagram of each embodiment finished product in the present invention.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiment, the present invention is made
Further to be described in detail, exemplary embodiment of the invention and its explanation are only used for explaining the present invention, are not intended as to this
The restriction of invention.
Embodiment 1
A kind of preparation method of graphene oxide is present embodiments provided, including：
2g graphite powders and 1g sodium nitrate are taken, is put into 500mL beakers.The 50mL concentrated sulfuric acids are measured again to pour into beaker and put
In the electric-heated thermostatic water bath for being placed with a large amount of ice cubes, magnetic stirrer 30min is used；Later plus people's potassium permanganate, will
6-12g potassium permanganate is added three times, and a small amount of every time, each interval time is 15min, this process ensures that reaction temperature exists
15 DEG C or so progress.Electric hot water bath is then turned on, by temperature setting at 30-60 DEG C, isothermal reaction 2h is slowly added to 300mL
Distilled water dilutes solution.30min is reacted after adding distilled water dilution, is slowly added to 2g potassium permanganate reaction 15min, then make water
Bath is warming up to 98 DEG C of isothermal reaction 30min.
Add the hydrogen peroxide of 50mL 30% after beaker taking-up is cooled to room temperature, observation solution colour variation, solution by
Brownish black quickly become it is golden yellow and with a large amount of bubbles after, be put into ultrasound 30min, obtained dispersion in ultrasonic cleaner
Liquid pours into centrifuge tube and is centrifuged in batches.Rotating speed is first adjusted to 4000r/min centrifugations 10min and removes large granular impurity, then
It is adjusted to 3000-5000r/min repeatedly to be centrifuged, each 10min, until being detected the filtrate of centrifugation with powder, solution
Still it clarifies.It is repeatedly centrifuged with distilled water, until being in neutrality using pH meter detection centrifugate, will be precipitated in centrifuge tube later
It is taken out with spoon.Finally, mistake in baking oven is put the precipitate in, dry duration is more than 36h, and obtained solid is graphene oxide
Sample.
Embodiment 2
A kind of preparation method of N doping three-dimensional grapheme, including：
The graphene oxide solution of a concentration of 6mg/mL of 10mL 100mL absolute ethyl alcohols are diluted, which is
For the graphene oxide sample obtained in embodiment 1, after being ultrasonically treated one hour, 3mL 3- aminopropyls three are added into above-mentioned solution
The HC1 solution of 0.5mL a concentration of 0.6% is slowly added dropwise in the case where magnetic stirrer continuously stirs for Ethoxysilane, then again slowly
0.5mL is added dropwise and is dissolved with 100mg FeC13.2H20 ethanol solution.Then by mixed liquor at a temperature of 50-80 DEG C water-bath
Then 3h is placed at 80 DEG C dry.It is hot under 400-600 DEG C of nitrogen protective condition by the solid abrasive of acquisition into powder
1h is solved, obtained black powder is used containing 20mL water, the mixed liquor pickling 12h of the HC1 compositions of 20mL HF, 20mL 37%.Most
Afterwards, obtained sample is washed to neutrality, heated again after dry, you can obtain N doping three-dimensional grapheme, such as Fig. 1
It is shown.
Embodiment 3
A kind of preparation method of N doping three-dimensional grapheme, including：
Graphene oxide powder is stirred in deionized water and ultrasonication obtains the oxygen of uniform, a concentration of 1mg/mL
Graphite alkene dispersion liquid, the graphene oxide powder in the present embodiment is the graphene oxide sample obtained in embodiment 1.With
Graduated cylinder measures 20mL graphene dispersing solutions, adds in 250 μ L dilute hydrochloric acid and the pH of solution is adjusted to 1.0.Continue ultrasound and be stirred continuously,
Load weighted 1.6g FeC1 are sequentially added into dispersion liquid3.2H20,2.0g H2C2O4With 6g (NH4)2SO4.Treat that above-mentioned salt is all complete
Nitrogen source of the 4mL pyrroles as graphene is slowly added dropwise after portion's dissolving.Continue ultrasound 10min, will be mixed after pyrroles scatter molten
Liquid pours into hydrothermal reaction kettle and after reaction 12h. hydro-thermal reactions, takes out room temperature product after cooling, centrifugation is simultaneously at 180 DEG C
Respectively with acetone, deionized water, ethanol wash 3 times, 70 DEG C of drying 6h in convection oven are placed in, will be made in this, as presoma
The presoma obtained is positioned in quartz boat, is put into tube furnace and is passed through Ar/H2Mixed gas, hydrogen volume in the mixed gas
Score is 5%, and control airflow rate is 60mL/min, and the 2h that anneals under the conditions of 600 DEG C is mutually pure and N doping so as to obtain
Three-dimensional structure graphene, as shown in Figure 2.
Embodiment 4
A kind of preparation method of N doping three-dimensional grapheme, wherein, graphene oxide dispersion is prepared with embodiment 2.
1g graphene oxides is taken to be mixed in grind into powder in Yan Portland with 5g melamines；It is to be ground by taupe paste
Put after object in rectangular crucible；Tube furnace is opened, after being passed through, releasing nitrogen three times, is passed through argon gas/nitrogen, three intrinsic standoff ratios all
It is 2：8.Temperature is risen very rapidly up into 200 DEG C of heat preservation 60min, then temperature rise, then will be in temperature to 500 DEG C of heat preservation 60min
Rise to 800 DEG C of heat preservation 60min.It obtains black powder substance to be placed in Yan Portland plus little water grinding 20min, then centrifuge washing
5 times, dry i.e. acquisition N doping three-dimensional grapheme is finally put in drying box.
The resistivity of N doping three-dimensional grapheme and yield made of above-described embodiment as shown in Figure 3 and Figure 4, pass through the figure
It can be with valid certificates：The three-dimensional structure for the finished product that method obtains is very notable, and electric property changes significantly, and yield is higher.
Basic principle of the invention and main feature and advantages of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the foregoing is merely the present invention specific embodiment, the protection model being not intended to limit the present invention
It encloses, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should be included in the present invention
Protection domain within.The scope of the present invention is defined by the appended claims and its equivalents.
Claims (5)
1. a kind of preparation method of N doping three-dimensional grapheme, which is characterized in that including：
(1) graphene oxide is obtained；
(2) FeC1 is added in the reduction process of graphene oxide again3.2H20 is main pore creating material, after 75~85 DEG C of hydro-thermal reactions
It by fully washing, is placed in the heat-treatment furnace under 500~800 DEG C of purity nitrogen atmosphere and is pyrolyzed 2~5 hours, you can obtain N doping
Three-dimensional grapheme.
A kind of 2. preparation method of N doping three-dimensional grapheme according to claim 1, which is characterized in that the step
(1) specific preparation method is：
Graphite powder and sodium nitrate are taken, is put into container, then measures the concentrated sulfuric acid and pours into container and place it in the electric heating for being placed with ice cube
In thermostat water bath, potassium permanganate is added in later using magnetic stirrer；Electric hot water bath is then turned on, by temperature setting
At 30~60 DEG C, after isothermal reaction, it is slowly added to distilled water and dilutes solution；It reacts after adding distilled water dilution, delays after reaction
It is slow to add in potassium permanganate reaction, then water-bath is made to be warming up to 96~100 DEG C of isothermal reactions；
Hydrogen peroxide is added after container taking-up is cooled to room temperature, observation solution quickly becomes golden yellow and with big by brownish black
After measuring bubble, the dispersion liquid being ultrasonically treated in ultrasonic cleaner is put into, dispersion liquid pours into centrifuge tube and centrifuged；
Rotating speed is adjusted to 3000~5000r/min during centrifugation repeatedly to be centrifuged, until solution is clarified, is carried out later with distilled water
Repeatedly centrifugation until being in neutrality using pH meter detection centrifugate, is taken out in centrifuge tube and precipitated；Finally, baking oven is put the precipitate in
Middle mistake, is dried to obtain graphene oxide.
3. the preparation method of a kind of N doping three-dimensional grapheme according to claim 2, which is characterized in that open electric hot water
The mode of potassium permanganate is added in before bath is：
Potassium permanganate adds in three times, a small amount of every time, ensures reaction temperature at 13~18 DEG C in adition process.
A kind of 4. preparation method of N doping three-dimensional grapheme according to claim 1, which is characterized in that the oxidation stone
The detailed process that black alkene prepares N doping three-dimensional grapheme is：
Graphene oxide solution with absolute ethyl alcohol is diluted, after supersound process, 3- aminopropyl triethoxysilanes are added in, in magnetic force
Blender, which continuously stirs down, is slowly added dropwise HC1 solution, and FeC1 is then slowly added dropwise again3.2H20 ethanol solution；It then will mixing
Liquid water-bath at a temperature of 50~80 DEG C, is then dried acquisition solid, by solid abrasive into powder, in 400~600 DEG C of nitrogen
It is pyrolyzed under the conditions of gas shielded, obtained black powder, is cleaned with the mixed liquor acid containing water, HF, HC1 composition；Finally, it will use
Neutrality is washed to, after heat treatment is dry again, you can obtain N doping three-dimensional grapheme.
A kind of 5. preparation method of N doping three-dimensional grapheme according to claim 1, which is characterized in that the oxidation stone
The detailed process that black alkene prepares N doping three-dimensional grapheme is：
Graphene oxide powder is stirred in deionized water and ultrasonication obtains the oxidation stone of uniform, a concentration of 1mg/mL
Black alkene dispersion liquid.Graphene dispersing solution is measured with graduated cylinder, dilute hydrochloric acid is added in and pH is adjusted to 1.0 by solution；Continue ultrasonic and continuous
Stirring, FeC1 is sequentially added into dispersion liquid3.2H20、H2C2O4(NH4)2SO4；After above-mentioned salt all dissolves, slowly drip
Add nitrogen source of the pyrroles as graphene, continue ultrasound and pour into mixed solution in hydrothermal reaction kettle after pyrroles scatter, 180
It is reacted at DEG C, after hydro-thermal reaction, takes out room temperature product after cooling, centrifuge and washed respectively with acetone, deionized water, alcohol
It washs repeatedly, presoma is made in drying；Presoma obtained is positioned in quartz boat, be put into tube furnace and is passed through Ar/H2It is mixed
Gas is closed, controls airflow rate, annealing is so as to obtain the three-dimensional structure graphene of N doping under the conditions of 600 DEG C.
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