CN104835654B - A kind of three-dimensional nitrogen-doped graphene/molybendum disulfide complexes and preparation method thereof - Google Patents

A kind of three-dimensional nitrogen-doped graphene/molybendum disulfide complexes and preparation method thereof Download PDF

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CN104835654B
CN104835654B CN201510289262.9A CN201510289262A CN104835654B CN 104835654 B CN104835654 B CN 104835654B CN 201510289262 A CN201510289262 A CN 201510289262A CN 104835654 B CN104835654 B CN 104835654B
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doped graphene
nitrogen
graphene
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molybdenum bisuphide
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赵凯
王宗花
赵春芹
桂日军
杨敏
金辉
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Shandong Zhonghe Holding Group Co Ltd
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Qingdao University
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Abstract

The invention discloses a kind of three-dimensional nitrogen-doped graphene/molybendum disulfide complexes and preparation method thereof.Adopt homogeneous precipitation method, under alkali condition, with CaC 2o 4for pore-foaming agent, bifunctional reagent thioacetamide provides nitrogenous source and sulphur source, synthesize three-dimensional nitrogen-doped graphene/molybdenum bisuphide composite material (3D? G-N/MoS 2).Under acid condition, ultrasonic dissolution removes the CaC in lamella 2o 4, define three-dimensional porous nitrogen-doped graphene/molybdenum bisuphide composite material.Preparation method is simple, environmental protection, MoS 2nanometer sheet is evenly distributed at graphenic surface, has larger contact area with Graphene, therefore has high catalytic performance, has a wide range of applications in fields such as electro-catalysis, photocatalysis, liberation of hydrogen catalysis.

Description

A kind of three-dimensional nitrogen-doped graphene/molybendum disulfide complexes and preparation method thereof
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. (YumengShi, WuZhou, *ang-YuLu, WenjingFang, Yi-HsienLee, AllenLongHsu, etal., VanderWaalsEpitaxyofMoS 2layersUsingGrapheneAsGrowthTemplates, NanoLett., 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.(Ke-JingHuang*, LanWang, the JingLiandYan-MingLiu*.Electrochemicalsensingbasedonlayer edMoS such as Huang 2-graphenecomposites, SensorsandActuatorsB, 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 N doping 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 4nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate the compound of particle;
2) in acid condition, the above-mentioned nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate compound of ultrasonic dissolution method process is adopted, obtained three-dimensional porous nitrogen-doped 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 8-11;
D) after continuing reaction 5-9h at 25 ~ 90 DEG C, precipitation is got, washing, dry, obtain nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate compound;
E) nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate is dissolved in 0.01 ~ 1.0molL -1aqueous hydrochloric acid solution in, ultrasonic 1 ~ 8h, water washing, to neutral, dried and is obtained three-dimensional nitrogen-doped graphene/molybendum disulfide complexes.
Preferably, described bifunctional reagent is thioacetamide.
Preferably, step b) in, described graphene oxide is scattered in quality and volume ratio is in the aqueous solution of 1:1 ~ 1:10, and the ultrasonic disperse time is 30 ~ 120min.
Preferably, step b) in, described bifunctional reagent and graphene oxide mass ratio 1:1 ~ 5:1, the mol ratio of bifunctional reagent 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 nitrogen-doped graphene/molybendum disulfide complexes prepared by above-mentioned method, its aperture size is 10 ~ 100nm.
Above-mentioned three-dimensional nitrogen-doped 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 (3DG-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, and alkaline environment 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 nitrogen-doped 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 nitrogen-doped 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 nitrogen-doped 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 nitrogen-doped graphene/molybdenum bisuphide composite material of porous has been synthesized in regulation and control.According to literature survey, this is the nitrogen-doped 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 4nitrogen-doped 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 nitrogen-doped 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 nitrogen-doped 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 nitrogen-doped 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 nitrogen-doped 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 nitrogen-doped 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 nitrogen-doped graphene/molybdenum bisuphide composite material: get the pre-prepared GO of 100mg and be scattered in the 100mL aqueous solution (quality and volume ratio are 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 nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate compound.Obtained nitrogen-doped 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 nitrogen-doped 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 nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate compound.Obtained nitrogen-doped 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 nitrogen-doped 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 (quality and volume ratio are 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 nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate compound.Obtained nitrogen-doped 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 nitrogen-doped 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 LNafion solution (5wt%) are dispersed in 1mL 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 (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 nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate compound.Obtained nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate is dissolved in 0.01molL -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 nitrogen-doped 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 100mL aqueous solution (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 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 nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate compound.Obtained nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate is dissolved in 1.0molL -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 nitrogen-doped 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 (9)

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 thioacetamide and Ca 2+with C 2o 4 2-under existence, adopt homogeneous precipitation method process graphene oxide, obtained interlayer deposits CaC 2o 4nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate the compound of particle;
2) in acid condition, the above-mentioned nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate compound of ultrasonic dissolution method process is adopted, obtained three-dimensional porous nitrogen-doped graphene/molybdenum bisuphide composite material.
2. the preparation method of three-dimensional nitrogen-doped graphene/molybendum disulfide complexes as claimed in claim 1, it 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 thioacetamide, 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 nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate compound;
E) nitrogen-doped graphene/molybdenum bisuphide/calcium oxalate is dissolved in 0.01 ~ 1.0molL -1aqueous hydrochloric acid solution in, ultrasonic 1 ~ 8h, water washing, to neutral, dried and is obtained three-dimensional nitrogen-doped graphene/molybendum disulfide complexes.
3. the preparation method of three-dimensional nitrogen-doped graphene/molybendum disulfide complexes as claimed in claim 2, it is characterized in that, step b) in, described graphene oxide is scattered in quality and volume ratio is in the aqueous solution of 1:1 ~ 1:10, and the ultrasonic disperse time is 30 ~ 120min.
4. the preparation method of three-dimensional nitrogen-doped 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.
5. the preparation method of three-dimensional nitrogen-doped 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.
6. the preparation method of three-dimensional nitrogen-doped 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, the ratio of three components amount of substance is 1:1:1 ~ 1:5:5.
7. three-dimensional nitrogen-doped graphene/molybendum disulfide complexes of preparing of the arbitrary described method of claim 1-6.
8. three-dimensional nitrogen-doped graphene/molybendum disulfide complexes as claimed in claim 7, is characterized in that, the aperture size of described three-dimensional nitrogen-doped graphene/molybendum disulfide complexes is 10 ~ 100nm.
9. three-dimensional nitrogen-doped graphene/molybendum disulfide complexes according to claim 8 is preparing the application in ultracapacitor.
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