CN104835654A - 3D nitrogen-doped graphene/molybdenum disulfide compound and preparation method thereof - Google Patents
3D nitrogen-doped graphene/molybdenum disulfide compound and preparation method thereof Download PDFInfo
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- CN104835654A CN104835654A CN201510289262.9A CN201510289262A CN104835654A CN 104835654 A CN104835654 A CN 104835654A CN 201510289262 A CN201510289262 A CN 201510289262A CN 104835654 A CN104835654 A CN 104835654A
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- molybdenum bisuphide
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 141
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 135
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- -1 molybdenum disulfide compound Chemical class 0.000 title claims abstract description 15
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title abstract description 9
- 239000002131 composite material Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 36
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000001556 precipitation Methods 0.000 claims abstract description 21
- 230000001588 bifunctional effect Effects 0.000 claims abstract description 15
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 15
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 58
- 229910052750 molybdenum Inorganic materials 0.000 claims description 58
- 239000011733 molybdenum Substances 0.000 claims description 58
- 230000000802 nitrating effect Effects 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 36
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 238000005406 washing Methods 0.000 claims description 20
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 17
- 150000002019 disulfides Chemical class 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 239000011684 sodium molybdate Substances 0.000 claims description 13
- 235000015393 sodium molybdate Nutrition 0.000 claims description 13
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 13
- 150000001875 compounds Chemical class 0.000 claims description 12
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 11
- 239000001110 calcium chloride Substances 0.000 claims description 11
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 11
- QXDMQSPYEZFLGF-UHFFFAOYSA-L calcium oxalate Chemical compound [Ca+2].[O-]C(=O)C([O-])=O QXDMQSPYEZFLGF-UHFFFAOYSA-L 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 9
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- 239000002253 acid Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- 239000006185 dispersion Substances 0.000 claims description 6
- 235000006408 oxalic acid Nutrition 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000011229 interlayer Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 4
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 235000011148 calcium chloride Nutrition 0.000 claims description 3
- 239000004567 concrete Substances 0.000 claims description 2
- 238000011978 dissolution method Methods 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 8
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 abstract description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 238000004090 dissolution Methods 0.000 abstract description 3
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 239000011148 porous material Substances 0.000 abstract description 3
- 239000011593 sulfur Substances 0.000 abstract description 3
- 229910052717 sulfur Inorganic materials 0.000 abstract description 3
- 239000002135 nanosheet Substances 0.000 abstract description 2
- 229910052961 molybdenite Inorganic materials 0.000 abstract 2
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 239000003795 chemical substances by application Substances 0.000 abstract 1
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- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 5
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- 235000011121 sodium hydroxide Nutrition 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000011160 research Methods 0.000 description 4
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- 239000011149 active material Substances 0.000 description 2
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- 229910052786 argon Inorganic materials 0.000 description 2
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- 238000013461 design Methods 0.000 description 2
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
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- 230000001105 regulatory effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 1
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- 229920000049 Carbon (fiber) Polymers 0.000 description 1
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- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
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- 229920000877 Melamine resin Polymers 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
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- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- SOIFLUNRINLCBN-UHFFFAOYSA-N ammonium thiocyanate Chemical compound [NH4+].[S-]C#N SOIFLUNRINLCBN-UHFFFAOYSA-N 0.000 description 1
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- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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- 229910001415 sodium ion Inorganic materials 0.000 description 1
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- 230000003381 solubilizing effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/84—Processes for the manufacture of hybrid or EDL capacitors, or components thereof
- H01G11/86—Processes for the manufacture of hybrid or EDL capacitors, or components thereof specially adapted for electrodes
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/24—Electrodes characterised by structural features of the materials making up or comprised in the electrodes, e.g. form, surface area or porosity; characterised by the structural features of powders or particles used therefor
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/26—Electrodes characterised by their structure, e.g. multi-layered, porosity or surface features
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G11/00—Hybrid capacitors, i.e. capacitors having different positive and negative electrodes; Electric double-layer [EDL] capacitors; Processes for the manufacture thereof or of parts thereof
- H01G11/22—Electrodes
- H01G11/30—Electrodes characterised by their material
- H01G11/32—Carbon-based
- H01G11/36—Nanostructures, e.g. nanofibres, nanotubes or fullerenes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Carbon And Carbon Compounds (AREA)
- Manufacturing & Machinery (AREA)
- Crystallography & Structural Chemistry (AREA)
- Nanotechnology (AREA)
Abstract
The invention discloses a 3D nitrogen-doped graphene/molybdenum disulfide compound and a preparation method thereof. A 3D nitrogen-doped graphene/molybdenum disulfide composite material (3D G-N/MoS2) is formed via synthesis under the alkaline condition in a homogeneous precipitation method by taking CaC2O4 as a pore forming agent and using a bifunctional reagent thioacetamide to provide a nitrogen source and a sulfur source. CaC2O4 in laminations is removed by ultrasonic dissolution under the acidic condition to form the 3D porous nitrogen-doped graphene/molybdenum disulfide composite material. The preparation method is simple and environment-friendly, MoS2 nano-sheets are uniformly distributed in the surface of graphene, the contact area with graphene is larger, the catalysis performance is high, and the method can be widely applied in the fields including electrocatalysis, photocatalysis and hydrogen evolution catalysis.
Description
Technical field
The present invention relates to technical field of nanometer material preparation.Be specifically related to a kind of three-dimensional nitrogen-doped graphene/molybendum disulfide complexes and preparation method thereof.
Background technology
The nano material (as Graphene, transition metal dichalcogenide) of two-dimensional layered structure is because of the particularity of its structure, show excellent performance in fields such as physics, chemistry, electricity and mechanics, there is important Research Significance and application prospect widely.Generally speaking, except the Nomenclature Composition and Structure of Complexes of material, dimension also serves vital effect in decision material fundamental property.Molybdenum bisuphide (MoS
2) be a kind of typical transition metal dichalcogenide, there is structure and the performance of very similar Graphene.Due to MoS
2combined by Van der Waals force between layers, allow to introduce external atom or molecule by intercalation at interlayer, can peel off simultaneously or directly synthesize the structure obtaining single or multiple lift class graphene nanometer sheet, showing the performance being different from Graphene.Research shows, the MoS of two-dimensional layered structure
2be a kind of promising new forms of energy electrode material, can be used as the electrode material of electrochemical lithium storage and storage magnesium.In recent years, nano level MoS
2show the performance of many excellences in fields such as electricity, light, liberation of hydrogen catalysis, also show wide application prospect in the field such as novel function nanometer material and device, become the study hotspot of current association area.
Previously for MoS
2the research of nano material mainly concentrates on the MoS of single-phase
2in nano material, relevant graphene-supported MoS
2the research of composite nano materials rarely has report.In view of MoS
2when electrode material as electrochemical reaction uses, its electric conductivity is poor, and Graphene has good conductive characteristic, therefore by graphene-supported MoS
2nano material forms compound, can obtain more excellent catalysis characteristics.MoS
2have unique and similar two-dimensional layer nanostructure with Graphene, both form new heterogeneous interlayer structure by compound, and this structure exists new interaction, contribute to obtaining new, more excellent performance.In addition, based on both matchings on crystal structure and microscopic appearance and the complementarity on electric property, estimate farthest to show cooperative effect therebetween by the novel nanocomposite materials prepared by this bi-material compound.Simultaneously, Graphene can affect spin density and the CHARGE DISTRIBUTION of carbon atom after N doping, and band structure has adjustment, causes graphenic surface to produce " avtive spot ", these avtive spots can participate in catalytic reaction directly, are improved significantly by the electro-chemical activity of N doping compound.Therefore, this novel nanocomposite materials has important application prospect in tribology, high-performance composite materials preparation, catalyst carrier, microprobe, biology sensor etc.
Shi etc. (Yumeng Shi, Wu Zhou,
*ang-Yu Lu, Wenjing Fang, Yi-Hsien Lee, Allen Long Hsu, etal., Van der Waals Epitaxy of MoS
2layers Using Graphene As Growth Templates, Nano Lett., 2012,12,2784-2791..) propose to cover Copper Foil for growth template with Graphene, chemical vapour deposition technique synthesis MoS
2the method of/Graphene mixed heterojunction structure, MoS
2graphenic surface grows the typical single crystal hexagonal foil of hundreds of nanometer to several microns.(the Ke-Jing Huang such as Huang
*, Lan Wang, Jing Li andYan-Ming Liu
*.Electrochemical sensingbased on layered MoS
2-graphene composites, Sensors and Actuators B, 2013,178,671-677.) the Liquid preparation methods stratiform MoS that utilizes Cys auxiliary
2-graphene complex, have studied the electrochemical response of this compound, shows the detectability of paracetamol excellence, and this is mainly owing to MoS
2excellent electrochemical performance and MoS
2and the cooperative effect between Graphene.
Patent (application number 201210437583.5) discloses a kind of preparation method of ion battery Graphene molybdenum sulfide nano composite anode material, ammonium thiomolybdate is joined in graphene oxide solution, make ammonium thiomolybdate and graphene oxide be reduced into MoS respectively simultaneously
2and Graphene, obtain the composite nano materials of molybdenum bisuphide/Graphene after heat treatment, then by the uniform pastel of 1-METHYLPYRROLIDONE solution furnishing of above-mentioned composite nano materials and carbon black and Kynoar, for subsequent use as composite negative pole material.Patent (application number 201410106133.7) discloses the preparation method of a kind of Graphene/molybdenum bisuphide composite material; with glucose and melamine for raw material; Graphene is prepared by high-temperature cracking method; by the mixed material of Graphene and molybdenum pentachloride and sulphur powder temperature reaction a period of time under argon gas atmosphere and lower pressure, then under argon shield, cooling obtains target product naturally.Patent (application number 201410141470.X) discloses a kind of MoS
2/ graphene lithium ion battery negative material and preparation method thereof, with sodium molybdate, thiocarbamide, graphene oxide for raw material, prepares sample by hydro thermal method, is then prepared into half-cell, and it is high that test display product has specific capacity, the feature of stable cycle performance.Patent (application number 201410473014.5) discloses a kind of graphene-supported sheet molybdenum disulfide nano compound and preparation method thereof, in order to solve due to MoS
2and between Graphene, compound area is little, and causes graphene-supported MoS
2nano particle, the problem that catalytic performance is poor.Using ammonium molybdate and thiocarbamide as starting material, under hydrothermal conditions can at the nanometer MoS of surface of graphene oxide carrier sheet stratiform
2; The sheet MoS of Graphene institute load after calcination process
2there is higher degree of crystallinity and photocatalysis efficiency.Patent (application number 201410571199.3) discloses the threadiness of an a kind of step hydrothermal reduction legal system for load three-dimensional flower-shaped Graphene/molybdenum bisuphide composite material to the method for electrode, molybdic acid or molybdenum oxide and ammonium thiocyanate and graphene oxide water solution are added in hydrothermal reactor, the while of carbon fiber, vertical immersion is in reactant liquor, at 160 ~ 200 DEG C, carry out hydrothermal reduction reaction 12 ~ 36h, the filamentary structure of prepared product forms DSSC photoelectric conversion rate to electrode assembling is apparently higher than by load MoS
2or the filamentary structure of platinum.
Patent (application number 201410682026.9) discloses the preparation method of a kind of molybdenum bisuphide/nitrogen-doped graphene three-dimensional composite material, using molybdenum disulfide powder as raw material, utilize 1-METHYLPYRROLIDONE as intercalation solution, by the few layer molybdenum disulfide nano sheet dispersion liquid of solvent heat intercalation ultrasonic stripping method preparation, mix with graphene oxide water solution again, under sodium ion effect, self assembly forms molybdenum bisuphide/graphene oxide composite construction, recycling hydrazine hydrate in-situ reducing obtains molybdenum bisuphide/redox graphene three-dimensional composite system, high temperature nitrogen doping process is carried out under ammonia atmosphere, obtain molybdenum bisuphide/nitrogen-doped graphene three-dimensional composite material.Patent (application number 201410519794.2) discloses a kind of nitrogen-doped graphene/molybdenum bisuphide composite material and Synthesis and applications thereof; by graphene oxide solution, nitrogenous precursor, sulfur-bearing with mix in the solution containing molybdenum presoma; obtain persursor material after removing solvent or heteroion, the heat treatment under inert gas shielding of this persursor material carried out N doping and crystallization thus obtain nitrogen-doped graphene/molybdenum bisuphide composite material.Although these two kinds of methods can both obtain nitrogen-doped graphene/molybdenum bisuphide composite material, do not obtain good loose structure in the process due to formation compound, surface area ratio is lower, and resistance to mass tranfer is comparatively large, is unfavorable for material diffusion and Charger transfer.
Based on above example, although relevant Graphene/MoS
2the preparation method of compound has been reported, but so far, there is not yet and adopt bifunctional reagent thioacetamide to be raw material, calcium oxalate homogeneous precipitation method prepares Graphene/MoS
2compound is correlated with the report of domestic and foreign literature and patent.The application's patent is intended adopting bifunctional reagent thioacetamide to be raw material, calcium oxalate homogeneous precipitation method, and obtained have Graphene/MoS that three-dimensional nitrating has loose structure
2compound, based on this easy preparation method, is beneficial to the loose structure of material diffusion and electronics fast transfer, can presents excellent chemical property, have important application prospect by fields such as electro-catalysis, photocatalysis, liberation of hydrogen catalysis.
Summary of the invention
The object of the present invention is to provide that a kind of technique is simple, productive rate is high, production cost is low, environmental protection, a kind of three-dimensional structure nitrogen-doped graphene/molybendum disulfide complexes of being easy to operate and control and preparation method thereof.
In order to realize foregoing invention object, the technical scheme of the embodiment of the present invention is as follows:
The present invention adopts following technical scheme:
A preparation method for three-dimensional nitrogen-doped graphene/molybendum disulfide complexes, comprises the steps:
1) in alkaline solution, at bifunctional reagent and Ca
2+with C
2o
4 2-under existence, adopt homogeneous precipitation method process graphene oxide, obtained interlayer deposits CaC
2o
4nitrating Graphene/molybdenum bisuphide/calcium oxalate the compound of particle;
2) in acid condition, the above-mentioned nitrating Graphene/molybdenum bisuphide/calcium oxalate compound of ultrasonic dissolution method process is adopted, obtained three-dimensional porous nitrating Graphene/molybdenum bisuphide composite material.
Further, the concrete steps of said method are:
A) utilize the Hummer legal system improved for graphene oxide;
B) by graphene oxide dispersion in aqueous, after ultrasonic disperse, add bifunctional reagent, sodium molybdate, calcium chloride, oxalic acid successively, continue ultrasonic process 1 ~ 6h;
C) by above-mentioned solution system Electromagnetic Heating to 25 ~ 90 DEG C, dropwise stir and add alkaline aqueous solution, adjust ph is to 9-11;
D) after continuing reaction 5-9h at 25 ~ 90 DEG C, precipitation is got, washing, dry, obtain nitrating Graphene/molybdenum bisuphide/calcium oxalate compound;
E) nitrating Graphene/molybdenum bisuphide/calcium oxalate is dissolved in 0.01 ~ 1.0mol L
-1aqueous hydrochloric acid solution in, ultrasonic 1 ~ 8h, water washing, to neutral, dried and is obtained three-dimensional nitrating Graphene/molybendum disulfide complexes.
Preferably, described bifunctional reagent is thioacetamide.
Preferably, step b) in, described graphene oxide is scattered in the aqueous solution in the ratio of mass volume ratio 1:1 ~ 1:10, and the ultrasonic agitation time is 30 ~ 120min.
Preferably, step b) in, described thioacetamide and graphene oxide mass ratio 1:1 ~ 5:1, the mol ratio of thioacetamide and sodium molybdate is 1:1 ~ 6:1, and calcium chloride and oxalic acid mol ratio are 1:1 ~ 1:5; Continue ultrasonic process 1 ~ 6h.
Preferably, step c) in, described alkaline aqueous solution is sodium hydrate aqueous solution.
Preferably, steps d) in, in described nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate compound, three components amount of substance is than being 1:1:1 ~ 1:5:5.
Three-dimensional nitrating Graphene/molybendum disulfide complexes prepared by above-mentioned method, its aperture size is 10 ~ 100nm.
Above-mentioned three-dimensional nitrating Graphene/molybendum disulfide complexes is preparing the application in ultracapacitor.
The present invention adopts thioacetamide as the bifunctional reagent of sulfur-bearing and nitrogenous source, and homogeneous precipitation method synthesizes three-dimensional structure nitrogen-doped graphene/molybdenum bisuphide composite material (3D G-N/MoS
2), the inventive method has following outstanding feature:
1) solution composition is: thioacetamide, Graphene, sodium molybdate, calcium chloride and oxalic acid;
2) when regulating pH value of solution to alkalescence, thioacetamide hydrolysis NH
3and S
2-, hydrolysate NH
3nitrogenous source can be provided, to realize the N doping of Graphene; Hydrolysate S
2-in nitrogen-doped graphene lamella, MoS is formed with sodium molybdate
2sandwich structure;
3) Ca
2+with C
2o
4 2-form CaC
2o
4crystal particle is deposited in nitrogen-doped graphene sheet and MoS
2on, watery hydrochloric acid regulates pH to time acid, and ultrasonic dissolution removes the CaC in lamella
2o
4, define three-dimensional porous nitrogen-doped graphene/molybdenum bisuphide composite material.
Confirm through literature survey, this adopts thioacetamide homogeneous precipitation method to synthesize three-dimensional porous nitrogen-doped graphene/molybdenum bisuphide composite material first.The inventive method is simple, environmental protection, be easy to operation, utilizes CaC
2o
4crystal particle prevents the reunion of bedded substance, avoids the use of hydrogen sulfide toxic gas.In addition, MoS
2nanometer sheet is evenly distributed at graphenic surface, large with Graphene contact area, therefore has higher catalytic performance, especially has a wide range of applications in fields such as electricity, light, liberation of hydrogen catalysis.
The compounding design thinking of this material is as follows:
First thioacetamide is hydrolyzed under the state of alkaline aqueous solution, decomposites NH
3and S
2-.NH
3as nitrogen containing component, realize the N doping (G-N) of Graphene; S
2-for forming MoS
2sulphur source; In the basic conditions, the Ca in solution
2+with C
2o
4 2-form CaC
2o
4crystal particle is deposited in nitrogen-doped graphene sheet and MoS
2on, overcome the model ylid bloom action power between bedded substance.Watery hydrochloric acid regulates pH to time acid, and ultrasonic dissolution removes the CaC in lamella
2o
4, define three-dimensional porous nitrating Graphene/molybdenum bisuphide composite material.It is characterized in that first according to Harmer or Hummers method, common graphite being oxidized to graphite oxide, it is ultrasonic, centrifugal after the graphite oxide aqueous dispersion of 0.1% for being mixed with mass percent concentration with graphite oxide again, obtains homodisperse graphite oxide aqueous dispersion; In graphite oxide aqueous dispersion, add " thioacetamide+sodium molybdate+calcium chloride+oxalic acid " mixture solution, regulate pH to alkalescence, electromagnetic oven adds thermal response a period of time, is cooled to room temperature, filter, obtain CaC
2o
4particle deposition is at the material (G-N/MoS of nitrating Graphene/molybdenum bisuphide
2/ CaC
2o
4); Again to G-N/MoS
2/ CaC
2o
4in add 5molL
-1aqueous hydrochloric acid solution, ultrasonic vibration, water washing, to neutral, dried and is obtained three-dimensional porous nitrating Graphene/molybdenum bisuphide composite material.
1) in alkaline solution, thioacetamide hydrolysis generates S
2-and NH
3, provide nitrogenous source and sulphur source, hydrolysis is as follows:
CH
3CSNH
2+3OH
-＝CH
3COO
-+NH
3+S
2-+H
2O
2) in alkaline solution, Ca
2+with C
2o
4 2-homogeneous precipitation forms CaC
2o
4precipitation, as pore-foaming agent, precipitation reaction is as follows:
Ca
2++C
2O
4 2--＝CaC
2O
4↓
3) in an acidic solution, CaC
2o
4dissolve with acid reaction, form pore space structure, precipitation solubilizing reaction is as follows:
CaC
2O
4↓+2HCl＝Ca
2++C
2O
4 2-+2Cl
-+2H
+
The present invention is owing to taking above technical scheme, and it has the following advantages:
1. adopt homogeneous precipitation method first, with CaC
2o
4for pore-foaming agent, bifunctional reagent thioacetamide provides nitrogenous source and sulphur source, and the nitrating Graphene/molybdenum bisuphide composite material of porous has been synthesized in regulation and control.According to literature survey, this is the nitrating Graphene/molybdenum bisuphide composite material adopting bifunctional reagent thioacetamide synthesizing porous first.
2. at bifunctional reagent thioacetamide and Ca
2+with C
2o
4 2-under existence, the CaC of generation
2o
4nitrating Graphene/molybdenum bisuphide sheet interlayer can be entered into, thus add the spacing of sheet layer material.By regulating pH to acid, dissolve CaC
2o
4, the three-dimensional nitrating Graphene/molybdenum bisuphide composite material of final obtained porous.CaC
2o
4precipitation belong to precipitation from homogeneous solution, gained CaC
2o
4there is good crystal formation, control CaC
2o
4the size of crystal formation, can obtain the three-dimensional nitrating Graphene/molybdenum bisuphide composite material of different pore size, the material prepared by us has excellent three-dimensional porous structure.
3. the NH of generation is hydrolyzed in the basic conditions by bifunctional reagent thioacetamide
3nitrogenous source is provided, in a heated condition, a large amount of functional groups of surface of graphene oxide, as functional group's decomposition-reductions such as carboxyl, epoxy radicals, hydroxyls, nitrogen enters in Graphene skeleton structure and N doping occurs, and its nitrogen content, up to 7.5% ~ 15.0%, makes the electro-chemical activity of compound be significantly improved.During electrode material as ultracapacitor, there is high ratio capacitance, superior high rate performance, after discharge and recharge 10000 times, capability retention up to 96.9%, at 0.5Ag
-1under current density, the specific capacity of the ultracapacitor of preparation and energy density are up to 340Fg
-1, 50.4Whkg
-1, show that three-dimensional nitrating Graphene/molybdenum bisuphide composite material prepared by the present invention has good high rate performance and super capacitor performance;
4. provide a kind of three-dimensional nitrating Graphene/molybdenum bisuphide composite material compounding design new approaches.The present invention produces the investigation and application of the adjustable inorganic pore-foaming agent of granular size in laminar composite synthesis by contributing to developing and development bifunctional reagent and homogeneous phase.
Accompanying drawing explanation
The Electronic Speculum figure of nitrating Graphene/molybdenum bisuphide composite material that Fig. 1 is three-dimensional porous
Embodiment
Mode by the following examples further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, conventionally selects with condition.
Embodiment 1
The Hummer legal system improved is for graphene oxide (GO): first, 2.5g expanded graphite and 5g sodium nitrate is added in 500mL beaker, then, add the concentrated sulfuric acid that 120mL mass concentration is 98% wherein, the mixture obtained is stirred 120min under condition of ice bath; Secondly, under the condition of strong stirring, slowly add 15g potassium permanganate and react in the mixture obtained, the temperature of described reaction controls below 20 DEG C, remove ice bath equipment after completing the adding of potassium permanganate, the product obtained at room temperature is stirred and spends the night; Then, 150mL intermediate water is dropwise added with vigorous stirring in beaker, reaction temperature rises to rapidly 98 DEG C, can be observed frothy generation, and the color of product becomes yellow in beaker, product is stirred 2h at 98 DEG C, then adds the hydrogen peroxide that 50mL mass concentration is 30% wherein, obtain the crude product of graphene oxide; Finally, be the salt acid elution of 5% successively by intermediate water and mass concentration by the crude product of the graphene oxide obtained, until cleaning solution is neutral; Wash with methyl alcohol and intermediate water, filter successively, the solid obtained is carried out drying under vacuum conditions, obtains graphene oxide.
The preparation of three-dimensional nitrating Graphene/molybdenum bisuphide composite material: get the pre-prepared GO of 100mg and be scattered in the 100mL aqueous solution (mass volume ratio is 1:1), after ultrasonic agitation 30min, add 0.5g calcium chloride and 0.41g oxalic acid powder, 0.5g thioacetamide and 0.25g sodium molybdate are dissolved in 50ml intermediate water simultaneously, ultrasonic 30min, by two kinds of solution mixing, ultrasonic 2h.When the electromagnetic oven transferring to 1300W is heated to 80 DEG C, dropwise drip NaOH (0.1molL
-1) pH of solution is adjusted to 10, continue heating simultaneously, after reaction 6h, get precipitation, after intermediate water washing for several times, vacuumize 24h at 60 DEG C, obtains nitrating Graphene/molybdenum bisuphide/calcium oxalate compound.Obtained nitrating Graphene/molybdenum bisuphide/calcium oxalate is dissolved in 5molL
-1aqueous hydrochloric acid solution in, ultrasonic vibration 1h, repeated washing three times, then with intermediate water washing for several times to neutral, filter, vacuumize 24h under the condition of 60 DEG C, obtains three-dimensional nitrating Graphene/molybdenum bisuphide composite material subsequently.
Embodiment 2
After preparing graphene oxide (GO) by the method identical with embodiment 1, getting the pre-prepared GO of 100mg is scattered in the 100mL aqueous solution (mass volume ratio is 1:1), after ultrasonic agitation 30min, add 1.0g calcium chloride and 0.82g oxalic acid powder, 1.0g thioacetamide and 0.32g sodium molybdate are dissolved in 50ml intermediate water simultaneously, ultrasonic 30min, by two kinds of solution mixing, ultrasonic 2h.When the electromagnetic oven transferring to 1000W is heated to 80 DEG C, dropwise drip NaOH (0.5molL
-1) pH of solution is adjusted to 11, continue heating simultaneously, after reaction 8h, get precipitation, after intermediate water washing for several times, vacuumize 24h at 60 DEG C, obtains nitrating Graphene/molybdenum bisuphide/calcium oxalate compound.Obtained nitrating Graphene/molybdenum bisuphide/calcium oxalate is dissolved in 5molL
-1aqueous hydrochloric acid solution in, ultrasonic vibration 1h, repeated washing three times, then with intermediate water washing for several times to neutral, filter, vacuumize 24h under the condition of 60 DEG C, obtains three-dimensional nitrating Graphene/molybdenum bisuphide composite material subsequently.
Embodiment 3
After preparing graphene oxide (GO) by the method identical with embodiment 1, getting the pre-prepared GO of 100mg is scattered in the 100mL aqueous solution (mass volume ratio is 1:1), after ultrasonic agitation 30min, add 0.5g calcium chloride and 0.41g oxalic acid powder, 1.0g thioacetamide and 0.96g sodium molybdate are dissolved in 50ml intermediate water simultaneously, ultrasonic 30min, by two kinds of solution mixing, ultrasonic 2h.When the electromagnetic oven transferring to 1300W is heated to 80 DEG C, dropwise drip ammonia spirit (0.1molL
-1) pH of solution is adjusted to 10, continue heating simultaneously, after reaction 6h, get precipitation, after intermediate water washing for several times, freeze drying 24h at-30 DEG C, obtains nitrating Graphene/molybdenum bisuphide/calcium oxalate compound.Obtained nitrating Graphene/molybdenum bisuphide/calcium oxalate is dissolved in 5molL
-1aqueous hydrochloric acid solution in, ultrasonic vibration 1h, repeated washing three times, then with intermediate water washing for several times to neutral, filter, freeze drying 24h at-30 DEG C subsequently, obtains three-dimensional nitrating Graphene/molybdenum bisuphide composite material.
Embodiment 4
Three-dimensional nitrogen-doped graphene/molybdenum bisuphide composite material that embodiment 1 is prepared by the present embodiment is applied to electrocatalytic hydrogen evolution test, and detailed process is:
Three-dimensional for 2mg nitrogen-doped graphene/molybdenum bisuphide composite material and 40 μ L Nafion solution (5wt%) are dispersed in l mL ethanolic solution, ultrasonic process 3h ~ 5h, 5 μ L sample dispersion drops are pipetted in glassy carbon electrode surface with liquid-transfering gun, after natural drying, by three electrode test systems at 0.5molL
-1h
2sO
4test in solution, sweep speed is 5mV/s.According to polarization curve analysis, the overpotential of the molybdenum bisuphide that we prepare/graphene complex modified electrode is 420mV, and take-off potential is about 130mV, superior performance, close to business-like platinum catalyst.
Embodiment 5
Three-dimensional nitrogen-doped graphene/molybdenum bisuphide composite material that embodiment 1 is prepared by the present embodiment, as super capacitor material, compares testing and analyzing to super capacitor performance.
Compare test and analysis to super capacitor performance: respectively composite material and appropriate absolute ethyl alcohol are mixed, be prepared into concentrated solution, propose after nickel foam collector (2cm × 1cm) immerses the several seconds, active material is made to be attached to inner hole wall and the outer surface of collector, vacuumize, 10MPa lower sheeting 30s, on each work electrode, the quality of active material is about 2mg, tests by three electrode test systems.Found that, at 0.5Ag
-1under A/g current density, the specific capacity of the ultracapacitor of preparation and energy density are up to 340Fg
-1, 50.4Whkg
-1.
Embodiment 6
After preparing graphene oxide (GO) by the method identical with embodiment 1, getting the pre-prepared GO of 100mg is scattered in the 100mL aqueous solution (mass volume ratio is 1:1), after ultrasonic agitation 30min, add 1.0g calcium chloride and 0.82g oxalic acid powder, 1.0g thioacetamide and 0.32g sodium molybdate are dissolved in 50ml intermediate water simultaneously, ultrasonic 30min, by two kinds of solution mixing, ultrasonic 2h.When the electromagnetic oven transferring to 1000W is heated to 25 DEG C, dropwise drip NaOH (0.5molL
-1) pH of solution is adjusted to 9, continue heating simultaneously, after reaction 5h, get precipitation, after intermediate water washing for several times, vacuumize 24h at 60 DEG C, obtains nitrating Graphene/molybdenum bisuphide/calcium oxalate compound.Obtained nitrating Graphene/molybdenum bisuphide/calcium oxalate is dissolved in 0.01mol L
-1aqueous hydrochloric acid solution in, ultrasonic vibration 1h, repeated washing three times, then with intermediate water washing for several times to neutral, filter, vacuumize 24h under the condition of 60 DEG C, obtains three-dimensional nitrating Graphene/molybdenum bisuphide composite material subsequently.
Embodiment 7
After preparing graphene oxide (GO) by the method identical with embodiment 1, getting the pre-prepared GO of 100mg is scattered in the 1000mL aqueous solution (mass volume ratio is 1:10), after ultrasonic agitation 30min, add 1.0g calcium chloride and 0.82g oxalic acid powder, 1.0g thioacetamide and 0.32g sodium molybdate are dissolved in 50ml intermediate water simultaneously, ultrasonic 30min, by two kinds of solution mixing, ultrasonic 2h.When the electromagnetic oven transferring to 1000W is heated to 90 DEG C, dropwise drip NaOH (0.5molL
-1) pH of solution is adjusted to 11, continue heating simultaneously, after reaction 9h, get precipitation, after intermediate water washing for several times, vacuumize 24h at 60 DEG C, obtains nitrating Graphene/molybdenum bisuphide/calcium oxalate compound.Obtained nitrating Graphene/molybdenum bisuphide/calcium oxalate is dissolved in 1.0mol L
-1aqueous hydrochloric acid solution in, ultrasonic vibration 8h, repeated washing three times, then with intermediate water washing for several times to neutral, filter, vacuumize 24h under the condition of 60 DEG C, obtains three-dimensional nitrating Graphene/molybdenum bisuphide composite material subsequently.
Although above-mentioned, the specific embodiment of the present invention is described; but not limiting the scope of the invention; one of ordinary skill in the art should be understood that; on the basis of technical scheme of the present invention, those skilled in the art do not need to pay various amendment or distortion that creative work can make still within protection scope of the present invention.
Claims (10)
1. a preparation method for three-dimensional nitrogen-doped graphene/molybendum disulfide complexes, is characterized in that, comprise the steps:
1) in alkaline solution, at bifunctional reagent and Ca
2+with C
2o
4 2-under existence, adopt homogeneous precipitation method process graphene oxide, obtained interlayer deposits CaC
2o
4nitrating Graphene/molybdenum bisuphide/calcium oxalate the compound of particle;
2) in acid condition, the above-mentioned nitrating Graphene/molybdenum bisuphide/calcium oxalate compound of ultrasonic dissolution method process is adopted, obtained three-dimensional porous nitrating Graphene/molybdenum bisuphide composite material.
2. the method for claim 1, is characterized in that, concrete steps are:
A) utilize the Hummer legal system improved for graphene oxide;
B) by graphene oxide dispersion in aqueous, after ultrasonic disperse, add bifunctional reagent, sodium molybdate, calcium chloride, oxalic acid successively, continue ultrasonic process 1 ~ 6h;
C) by above-mentioned solution system Electromagnetic Heating to 25 ~ 90 DEG C, dropwise stir and add alkaline aqueous solution, adjust ph is to 9-11;
D) after continuing reaction 5-9h at 25 ~ 90 DEG C, precipitation is got, washing, dry, obtain nitrating Graphene/molybdenum bisuphide/calcium oxalate compound;
E) nitrating Graphene/molybdenum bisuphide/calcium oxalate is dissolved in 0.01 ~ 1.0mol L
-1aqueous hydrochloric acid solution in, ultrasonic 1 ~ 8h, water washing, to neutral, dried and is obtained three-dimensional nitrating Graphene/molybendum disulfide complexes.
3. the preparation method of three-dimensional nitrating Graphene/molybendum disulfide complexes as claimed in claim 1 or 2, it is characterized in that, described bifunctional reagent is thioacetamide.
4. the preparation method of three-dimensional nitrating Graphene/molybendum disulfide complexes as claimed in claim 2, it is characterized in that, step b) in, described graphene oxide is scattered in the aqueous solution in the ratio of mass volume ratio 1:1 ~ 1:10, and the ultrasonic agitation time is 30 ~ 120min.
5. the preparation method of three-dimensional nitrating Graphene/molybendum disulfide complexes as claimed in claim 2, it is characterized in that, step b) in, described thioacetamide and graphene oxide mass ratio 1:1 ~ 5:1, the mol ratio of thioacetamide and sodium molybdate is 1:1 ~ 6:1, and calcium chloride and oxalic acid mol ratio are 1:1 ~ 1:5; Continue ultrasonic process 1 ~ 6h.
6. the preparation method of three-dimensional nitrating Graphene/molybendum disulfide complexes as claimed in claim 2, is characterized in that, step c) in, described alkaline aqueous solution is the aqueous solution of NaOH.
7. the preparation method of three-dimensional nitrating Graphene/molybendum disulfide complexes as claimed in claim 2, is characterized in that, steps d) in, in described nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate compound, three components amount of substance is than being 1:1:1 ~ 1:5:5.
8. three-dimensional nitrating Graphene/molybendum disulfide complexes of preparing of the arbitrary described method of claim 1-7.
9. three-dimensional nitrating Graphene/molybendum disulfide complexes as claimed in claim 8, is characterized in that, the aperture size of described three-dimensional nitrating Graphene molybdenum sulfide compound is 10 ~ 100nm.
10. three-dimensional nitrating Graphene/molybendum disulfide complexes according to claim 9 is preparing the application in ultracapacitor.
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