CN104649253A - Preparing methods of porous graphene and porous graphene film - Google Patents
Preparing methods of porous graphene and porous graphene film Download PDFInfo
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- CN104649253A CN104649253A CN201310581279.2A CN201310581279A CN104649253A CN 104649253 A CN104649253 A CN 104649253A CN 201310581279 A CN201310581279 A CN 201310581279A CN 104649253 A CN104649253 A CN 104649253A
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Abstract
The invention provides a preparing method of porous graphene. The method includes: mixing graphene and/or graphene oxide with an etching agent to obtain a mixture; and under oxygen-free conditions, subjecting the mixture to a carbothermic reaction and performing acid processing to remove the reacted and unreacted etching agent, wherein the etching agent is one or more of oxometallate, metal hydroxide and metal oxide. Based on the preparing method of the porous graphene, the invention also provides a preparing method of a porous graphene film by etching a graphene film. By dispersing an etching agent on the graphene film, and performing pore forming research through high-temperature treatment or electron beam radiation, a porous graphene film material is prepared. The pore size on the surface of the prepared porous graphene ranges from 1 nm to 200 nm, and can be regulated and controlled by adjusting the concentration or the size of the etching agent. The porous graphene is high in yield. Operation equipment is simple. A production cost is low.
Description
Technical field
The present invention relates to the preparation method of a kind of porous graphene and porous graphene film.
Background technology
Graphene has excellent electricity, calorifics and mechanical property, and (calculated value is 2600m to have higher theoretical specific surface area
2/ g).In the past few years, a lot of methods is used to prepare Graphene, comprises chemical Vapor deposition process, epitaxial growth method, physics stripping method, chemical reduction method, the ultrasonic stripping method of liquid phase and synthesis method from bottom to top.Wherein, chemical reduction method is the most popular method preparing Graphene of current material science.Chemical reduction method, also referred to as reduced graphene oxide serving method, can be divided into chemical reagent reduction, electrochemical reduction, high-temperature hot reduction, solvothermal and photoreduction according to reduction mode.Graphene oxide surface is containing multiple oxygen-containing functional group and defect, and after reduction, most oxygen-containing functional group can be removed, but defect still can be stayed on graphene sheet layer.In order to obtain more perfectly Graphene, the methods such as chemical vapour deposition are used to the defect of repairing the graphenic surface prepared by chemical reduction method.
Porous graphene is on graphene film Rotating fields, introduce nano level hole (Xu, P.; Yang, J.; Wang, K.; Zhou, Z.; Shen, P.Porous Graphene:Properties, Preparation, and Potential Applications.Chin.Sci.Bull.2012,57 (23), 2948-2955.), namely graphenic surface " defect " is designed and processes the product obtained.For the research of porous graphene, it is the utilization to its surface imperfection structure.Based on excellent properties and the two-dimensional nanostructure of Graphene, the pore structure on porous graphene surface can give its new performance and application, such as, and the isolation and purification of gas, DNA sequencing, sea water desalinization, ionic channel.
At present, porous graphene mainly utilizes anakinetomer to bombard or radiation graphene sheet layer, and etching occurs and obtains nano level pore structure, these anakinetomers have helium ion, electron beam and laser.But because these methods need certain equipment, cost is high, productive rate is low, therefore, the research work of porous graphene mainly concentrates on computational science and device research field, relatively less to its performance study at Material Field.Therefore, develop a kind of method preparing porous graphene simply, efficiently, realize a large amount of preparations of porous graphene, very large in the meaning of the investigation and application of material science for porous graphene.
Summary of the invention
The object of this invention is to provide a kind of method preparing porous graphene simply, efficiently, and prepare the method for porous graphene film.
Carbon-thermal reduction is a kind of chemical reaction of classics, and under the condition of high temperature, the compound that the overwhelming majority contains metal and oxygen element can be reduced to metal oxide or the metal simple-substance of lower valency by carbon, even form metallic carbide.In carbon-thermal reduction, carbon, as reductive agent, is generated carbon monoxide or carbonic acid gas by the compound oxidation containing metal and oxygen element.The present inventor is surprised to find that, nano material has higher surface energy, and Graphene, as a kind of carbon nanomaterial of two dimension, at relatively low temperature carbon-thermal reduction can occur with the compound nano-particle of metal and oxygen element.Because Graphene is the two-dimensional nanostructure formed by monolayer carbon atom, after surface carbon atom is oxidized, leave defect on surface, i.e. pore structure, form porous graphene.
Based on above-mentioned discovery, the invention provides a kind of preparation method of porous graphene, wherein, the method comprises, and Graphene and/or graphene oxide is mixed with etching agent, obtains mixture; Under anaerobic, carbon-thermal reduction is carried out to mixture, and carry out acid treatment to remove unreacted or reacted etching agent; Described etching agent is one or more in oxometallate, metal hydroxides and metal oxide.
Present invention also offers a kind of preparation method of porous graphene film, wherein, the method comprises, etching agent is dispersed on Graphene and/or graphene oxide film, carry out carbon-thermal reduction or electron beam lithography under anaerobic, and carry out acid treatment with the etching agent after dereaction or after etching; Described etching agent is one or more in oxometallate, metal hydroxides and metal oxide.
Porous graphene provided by the invention, aperture is between 1-200nm, and going out porosity can reach 5-80%.
The category of Graphene derivative has been enriched in the research of porous graphene, effectively make use of the defect structure on Graphene derivative surface, relate in the system of components migrate at lithium ion battery, electrode of super capacitor, catalytic material etc., effectively can improve diffusion and the migration of electrolytic solution or reactant, be conducive to the raising of material property.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for specification sheets, is used from explanation the present invention, but is not construed as limiting the invention with embodiment one below.In the accompanying drawings:
Fig. 1 is the TEM photo of the porous graphene sample that embodiment 1.1 prepares;
Fig. 2 is the TEM photo of the porous graphene sample that embodiment 2.7 prepares;
Fig. 3 is the SEM photo of the porous graphene sample that embodiment 3.1 prepares;
Fig. 4 is the SEM photo of porous graphene film sample prepared by embodiment 6.1;
Fig. 5 is the SEM photo of porous graphene film sample prepared by embodiment 7.1.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
In the present invention, term " graphene oxide " is the Graphene with oxygen-containing functional group.
The invention provides a kind of preparation method of porous graphene, wherein, the method comprises, and Graphene and/or graphene oxide is mixed with etching agent, obtains mixture; Under anaerobic, carbon-thermal reduction is carried out to mixture, and carry out acid treatment to remove unreacted and reacted etching agent; Described etching agent is one or more in oxometallate, metal hydroxides and metal oxide.
According to method of the present invention, as long as Graphene and/or graphene oxide are mixed with etching agent, carry out carbon-thermal reduction under anaerobic and carry out acid treatment can obtaining porous graphene to remove unreacted and reacted etching agent, the consumption of the present invention to Graphene and/or graphene oxide and etching agent does not specially require, under preferable case, the mass ratio of described Graphene and/or graphene oxide and etching agent is 0.1-10:1, when being more preferably 0.5-2:1, hole size, pore distribution adjustable porous Graphene can be obtained.
In the present invention, the application form of Graphene and/or graphene oxide is not specially required, such as, Graphene and/or graphene oxide can mix with etching agent with powder, also can mix with etching agent with the form of dispersion liquid, under preferable case, described Graphene and/or graphene oxide mix with etching agent with the form of dispersion liquid, so that make that Graphene and/or graphene oxide mix with etching agent evenly, thus obtain the adjustable porous graphene of pore distribution.
When described Graphene and/or graphene oxide mix with etching agent with the form of dispersion liquid, the concentration of the dispersion liquid of described Graphene and/or graphene oxide is preferably 0.1-20mg/mL, is more preferably 0.5-4mg/mL.The dispersion liquid of described Graphene and/or graphene oxide can be dispersed in dispersion medium by Graphene and/or graphene oxide and be formed.The present invention does not specially require described dispersion medium, as long as can form the dispersion liquid of described Graphene and/or graphene oxide, under preferable case, described dispersion medium is water, methyl alcohol, ethanol or DMF.The method of the present invention to the dispersion liquid forming described Graphene and/or graphene oxide does not specially require, alternatively, carry out supersound process after described Graphene and/or graphene oxide can also being mixed with dispersion medium, the dispersion liquid of more uniform described Graphene and/or graphene oxide can be obtained.
In the present invention, described etching agent can mix with Graphene and/or graphene oxide with powder, also can mix with Graphene and/or graphene oxide with the form of solution or dispersion liquid, under preferable case, described etching agent mixes with Graphene and/or graphene oxide with the form of solution or dispersion liquid.The concentration of etchant solution or etching agent dispersion liquid is preferably 0.01-10mol/L, is more preferably 0.1-1mol/L.The formation of described etchant solution or etching agent dispersion liquid is determined by described etching agent.When described etching agent can be dissolved in dispersion liquid, namely form described etchant solution, when described etching agent is insoluble to dispersion liquid, namely form etching agent dispersion liquid.
In the present invention, Graphene and/or graphene oxide are mixed with etching agent, obtain mixture, in order to keep the laminated structure of Graphene and/or graphene oxide in mixture, under preferable case, use freeze drier to carry out drying to the mixture that Graphene and/or graphene oxide and etching agent are mixed to form, obtain dried product, and then carbon-thermal reduction is carried out to dried product.The present invention does not specially require described cryodesiccated condition, can adopt cryodesiccated condition well known by persons skilled in the art.Under preferable case, described cryodesiccated condition comprises: temperature is (-80)-(-50) DEG C, and the time is 6-72h.
In the present invention, Graphene and graphene oxide can be directly commercially available, and also can be prepared according to method known to those skilled in the art and obtain, the present invention does not specially require.Such as, described graphene oxide can prepare (Hummers, W. by Hummers method; Offeman, R.Preparation of Graphitic Oxide.J.Am.Chem.Soc.1958,80 (6), 1339.); Described Graphene can by the method preparation such as reduced graphene oxide serving method (method of reducing comprises, chemical reagent reduction, electrochemical reduction, high-temperature hot reduction, water/solvothermal), chemical Vapor deposition process, physical separation methods, ultrasonic dispersion, axial epitaxy.
In the present invention, described oxygen free condition refers to does not have oxygen existent condition, and to avoid in the presence of oxygen, carbon is oxidized to CO and/or CO
2cause carbon consumption.Described oxygen free condition can be rare gas element (such as nitrogen and/or argon gas) existent condition, and can be also vacuum condition, the present invention specially require.
Described acid treatment, refers to the product acid soak through carbon-thermal reduction, to remove unreacted and reacted etching agent.Described acid can adopt any one acid well known by persons skilled in the art, and such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid etc., be preferably hydrochloric acid.Consumption the present invention of described acid does not specially require, as long as unreacted and reacted etching agent can be removed completely, under preferable case, described acid is 10-50:1 with the mol ratio of the etching agent added at first.
According to method of the present invention, the kind of the present invention to described oxometallate does not specially require, and under preferable case, described oxometallate can be Sodium orthomolybdate, potassium molybdate, lithium tungstate, sodium wolframate, potassium wolframate, lithium stannate, sodium stannate, potassium stannate, lithium aluminate, sodium aluminate, potassium aluminate, lithium titanate, sodium titanate, potassium titanate, lithium titanate, vanadic acid sodium, potassium vanadate, bismuthic acid lithium, sodium bismuthate, bismuthic acid potassium, high manganese lithium, potassium permanganate, sodium permanganate, lithium manganate, potassium manganate, sodium manganate, potassium bichromate, sodium dichromate 99, lithium chromate, potassiumchromate, Sodium chromate, lithium zirconate, sodium zirconate, potassium zirconium, ferrate-lithium, Na2Fe04, potassium ferrate, zincic acid lithium, sodium zincate, potassium zincate, Lithium niobium trioxide, sodium columbate, potassium niobate, cobalt acid lithium, cobalt acid sodium, cobalt acid potassium, lithium nickelate, nickel acid sodium, nickel acid potassium, silicomolybdic acid, silicotungstic acid, silicon vanadic acid, ammonium molybdate, ammonium tungstate, ammonium vanadate, mangaic acid ammonium, ammonium dichromate, ammonium chromate, nickel acid ammonium, phospho-wolframic acid, one or more in phospho-molybdic acid and phosphorus vanadic acid.
According to method of the present invention, the kind of the present invention to described metal hydroxides does not specially require, under preferable case, described metal hydroxides can be one or more the oxyhydroxide in the IIth A, III A, I B, II B, IV B, V B, VI B, VIII race and lanthanide series metal.More preferably, in situation, described metal hydroxides is the oxyhydroxide of one or more metals in magnesium, aluminium, copper, zinc, cadmium, titanium, zirconium, vanadium, niobium, molybdenum, iron, cobalt, nickel, ruthenium and lanthanum.
According to method of the present invention, the kind of the present invention to described metal oxide does not specially require, and under preferable case, described metal oxide is one or more the oxide compound in the IIIth A, I B, II B, IV B, V B and VIII race's metal.More preferably, in situation, described metal oxide is the oxide compound of one or more metals in aluminium, copper, zinc, chromium, zirconium, vanadium and iron, cobalt and nickel.
In the present invention, although adopt above-mentioned oxometallate, metal hydroxides or metal oxide particle as the object having etching agent can realize the present invention to prepare porous graphene.But because oxometallate has water-soluble preferably, utilize the chemisorption between metallate and Graphene, metallate is easy to form nanostructure (based on nano particle) in graphenic surface assembling, thus, by the size and dimension of regulator solution concentration regulation and control etching agent, the regulation and control of porous graphene surface pore structure can be realized further.Therefore the present invention preferably uses oxometallate to prepare porous graphene as etching agent.Further, for cost consideration, the especially preferred described etching agent of the present invention is sodium aluminate, Sodium orthomolybdate and sodium wolframate.
According to method of the present invention, described carbon-thermal reduction condition can be any one reaction conditions well known by persons skilled in the art, as long as can enable Graphene and/or graphene oxide and etching agent that carbon-thermal reduction occurs, under preferable case, described carbon-thermal reduction condition comprises: temperature 300-1000 DEG C, be preferably 350-650 DEG C, the time is 5-300 minute, is preferably 30-120 minute.
The preferred preparation method of a kind of porous graphene can be as follows:
(1) dispersion liquid of graphene oxide is prepared
At 20-30 DEG C of temperature, natural flake graphite and SODIUMNITRATE are joined in the vitriol oil, then in 0-2 DEG C of ice-water bath, cool 30-120 minute, after cooling, under 2-10 DEG C of condition, add potassium manganate, ice-water bath is withdrawn, keep 2-200 hour, obtain the mixture of brown.Wherein, the weight ratio that each material adds is natural flake graphite: SODIUMNITRATE: the vitriol oil: potassium permanganate=1:0.5-1:80-150:3-5.
Add ultrapure water (ultrapure water, also three water are, higher than the purity of deionized water, its specific conductivity is 18.2M Ω cm, in addition, deionized water, pure water or tap water can also be added) dilution (ultrapure water: natural flake graphite=100-200:1, mass ratio), keep 20-120min, then add hydrogen peroxide ultrapure water solution (1-10 quality %), until the Manganse Dioxide generated in remaining potassium permanganate and reaction is all transformed into manganous sulfate, obtain jonquilleous suspension.Finally there is no sulfate ion with in ultrapure water repetitive scrubbing to suspension.By centrifugal, suspension is separated (2000-6000 × g, 5-10min), remove the precipitation bottom centrifuge tube, the solution obtained is graphene oxide ultrapure water dispersion liquid.
(2) presoma-1 is prepared: graphene oxide and Sodium orthomolybdate mixture
The graphene oxide ultrapure water solution (0.1-20mg/mL) step (1) obtained mixes with sodium molybdate solution (0.01-10mol/L), and vibrate 6-24 hour in shaking table, and rotating speed is 50-200rpm.With liquid nitrogen bath by after freezing for mixing solutions 5-20 minute, use freeze drier to carry out drying (12-48 hour, temperature is-50 DEG C, and pressure is 7.5Pa), prepare the mixture of Graphene and Sodium orthomolybdate.
(3) intermediate-1 is prepared: Graphene-molybdenum oxide hybrid material
The graphene oxide obtain step (2) and the mixture of Sodium orthomolybdate, as presoma, are placed in tube furnace, under the condition of nitrogen protection; be warming up to 300-1000 DEG C; temperature rise rate is 5-20 DEG C/min, and insulation 5-300 minute, naturally cools to room temperature.
(4) porous graphene is prepared
By the intermediate-1 obtained, be dispersed in (0.1-1mol/L, 50mL) in dilute hydrochloric acid, stir 1-7 days, collecting by filtration, use milli-Q water three times, once, 60-120 DEG C of dry 6-24 hour, the black solid powder obtained is porous graphene sample to alcohol flushing.
On the other hand, present invention also offers a kind of preparation method of porous graphene film, wherein, the method comprises, etching agent is dispersed on Graphene and/or graphene oxide film, carries out carbon-thermal reduction under anaerobic, and carry out acid treatment to remove unreacted and reacted etching agent; Described etching agent is one or more in oxometallate, metal hydroxides and metal oxide.
According to method of the present invention, as long as etching agent is dispersed on Graphene and/or graphene oxide film, carry out carbon-thermal reduction or electron beam lithography under anaerobic and carry out acid treatment can obtaining porous graphene film after removing unreacted or reaction, the consumption of the present invention to Graphene and/or graphene oxide and etching agent does not specially require, under preferable case, the mass ratio of described Graphene and/or graphene oxide and etching agent is 0.1-10:1, when being more preferably 0.5-2:1, hole size can be obtained, the porous graphene that pore distribution is more homogeneous.
In the present invention, described Graphene and/or graphene oxide film can deposit a layer graphene and/or the acquisition of graphene oxide film by Graphene and/or graphene oxide dispersion liquid in matrix.The present invention to the not requirement of described matrix, such as, can be silicon, glass, quartz and metal (copper, nickel, iron) substrate.Thickness the present invention also not requirement of described Graphene and/or graphene oxide film, can select according to actual needs, and under preferable case, the thickness of described Graphene and/or graphene oxide film is 5-50nm.
In the present invention, the application form of Graphene and/or graphene oxide is not specially required, Graphene and/or graphene oxide can mix with etching agent with powder, also can mix with etching agent with the form of dispersion liquid, under preferable case, described Graphene and/or graphene oxide mix with etching agent with the form of dispersion liquid, so as to make that Graphene and/or graphene oxide mix with etching agent evenly, thus obtain pore distribution evenly porous graphene.
When described Graphene and/or graphene oxide mix with etching agent with the form of dispersion liquid, the concentration of the dispersion liquid of described Graphene and/or graphene oxide is preferably 0.1-20mg/mL, is more preferably 0.5-4mg/mL.The dispersion liquid of described Graphene and/or graphene oxide can be dispersed in dispersion medium by Graphene and/or graphene oxide and be formed.Described dispersion medium the present invention does not specially require, as long as can form the dispersion liquid of described Graphene and/or graphene oxide, under preferable case, described dispersion medium can be water, methyl alcohol, ethanol or DMF.The method the present invention forming the dispersion liquid of described Graphene and/or graphene oxide does not specially require, under preferable case, carry out supersound process after described Graphene and/or graphene oxide being mixed with dispersion medium, the dispersion liquid of more uniform described Graphene and/or graphene oxide can be obtained.
In the present invention, described etching agent can be dispersed on Graphene and/or graphene oxide film with powder, also can be dispersed on Graphene and/or graphene oxide film with the form of solution or dispersion liquid, under preferable case, described etching agent is dispersed on Graphene and/or graphene oxide film with the form of solution or dispersion liquid, finally realizes etching agent and is dispersed on Graphene and/or graphene oxide film.The concentration of etchant solution or etching agent dispersion liquid is preferably 0.01-10mol/L, is more preferably 0.1-1mol/L.The formation of described etchant solution or etching agent dispersion liquid is determined by described etching agent.When described etching agent can be dissolved in dispersion liquid, namely form described etchant solution, when described etching agent is insoluble to dispersion liquid, namely form etching agent dispersion liquid.
In the present invention, etching agent being dispersed on Graphene and/or graphene oxide film, obtaining mixture, in order to keep the laminated structure of Graphene and/or graphene oxide film in mixture, under preferable case, lyophilize being carried out to described mixture.Described cryodesiccated condition the present invention does not specially require, and can adopt cryodesiccated condition well known by persons skilled in the art.Under preferable case, described cryodesiccated condition comprises: temperature is (-80)-(-50) DEG C, and the time is 6-72h.
According to method of the present invention, described carbon-thermal reduction condition can be any one reaction conditions well known by persons skilled in the art, as long as can enable Graphene and/or graphene oxide and etching agent that carbon-thermal reduction occurs, under preferable case, described carbon-thermal reduction condition comprises: temperature 300-1000 DEG C, be preferably 350-650 DEG C, the time is 5-300 minute, is preferably 30-120 minute.
In the present invention, in the preparation method of porous graphene film, can use the method acquisition treatment temp as above of heating, in addition, the present invention can also use the method for electron beam lithography to make reaction system reach the condition of carbon-thermal reduction to provide energy.Electron beam can be thermal electron, field emission electron and Schottkey Injection electronics three kinds of electron beams, and it can be produced high-octane electron beam and obtain by the high pressure between cathode in electron gun and anodic filament.The condition optimization of described electron beam lithography comprises: etching voltage is 1-20KV, and be preferably 6-10KV, the time is 0.5-10 minute, and the time is 3-5 minute.
In the present invention, described oxygen free condition refers to does not have oxygen existent condition, in order to avoid in the presence of oxygen, carbon is oxidized to CO and/or CO
2cause carbon consumption.Described oxygen free condition can be rare gas element (such as nitrogen and/or argon gas) existent condition can be also vacuum condition, and the present invention does not specially require.
Described acid treatment, refers to the product acid soak through carbon-thermal reduction, to remove unreacted or reacted etching agent.Described acid can adopt any one acid well known by persons skilled in the art, and such as hydrochloric acid, phosphoric acid, sulfuric acid, nitric acid etc., be preferably hydrochloric acid.Consumption the present invention of described acid does not specially require, as long as unreacted in the product of described carbon-thermal reduction or reacted etching agent can be removed completely, under preferable case, described acid is 10-50:1 with the mol ratio of the etching agent added at first.
In the present invention, Graphene, graphene oxide, oxometallate, metal hydroxides and metal oxide, can as previously mentioned, not repeat them here.
According to method of the present invention, described carbon-thermal reduction condition can be any one reaction conditions well known by persons skilled in the art, as long as can enable Graphene and/or graphene oxide and etching agent that carbon-thermal reduction occurs, under preferable case, described carbon-thermal reduction condition comprises: temperature 300-1000 DEG C, be preferably 350-650 DEG C, the time is 5-300 minute, is preferably 30-120 minute.
Below will be described the present invention by embodiment.
preparative Example 1prepare the ultrapure water solution of graphene oxide
At 20 DEG C, getting 2.0g fineness is that 325 object flaky graphites and 1.5g SODIUMNITRATE are added in the 80mL vitriol oil (98 % by weight), to be placed on by the mixture obtained in the beaker of 500mL and with 0 DEG C of ice-water bath cooling 30min, to be 8 DEG C, to obtain suspension to temperature.
At 5 DEG C, under the stirring velocity of 700rpm (size of stirrer: 6cm), 9.0g potassium permanganate is added in above-mentioned suspension and (added once every 15 minutes, add 1.5g at every turn), then ice-water bath is withdrawn, keep 120 hours, 150mL ultrapure water is added (added once every 5 minutes, add 50mL at every turn), after half an hour, add the hydrogen peroxide of 250mL3 quality %, obtain jonquilleous solution.With ultrapure water centrifuge washing to there is no sulfate ion in jonquilleous solution, then solution centrifugal is separated (2560 × g, 3000rpm), obtain the graphene oxide ultrapure water solution of 6mg/mL, then add the graphene oxide ultrapure water solution that ultrapure water dilution obtains 4mg/mL, the carbonatoms of graphene oxide and the ratio of oxygen atomicity are C/O=2.
preparative Example 2prepare Graphene
preparative Example 2.1
Hydrothermal method prepares Graphene
The graphene oxide ultrapure water solution dilution obtained by Preparative Example 1 is to 2mg/mL, get 30mL, ultrasonic 30 minutes (power 80W), loading volume is the autoclave of 50mL, 180 DEG C are heated 6 hours, obtain black solid, collecting by filtration, with milli-Q water once, with liquid nitrogen bath after freezing 15 minutes, freeze drier is used to carry out drying (48 hours, temperature is-50 DEG C, and pressure is 7.5Pa).Finally obtain 42mg Graphene black solid.
preparative Example 2.2
High-temperature hot method of reducing prepares Graphene
The graphene oxide ultrapure water solution liquid nitrogen bath obtained by Preparative Example 1, after freezing 15 minutes, uses freeze drier to carry out drying (48 hours, temperature is-50 DEG C, and pressure is 7.5Pa).Being placed on by the graphene oxide obtained (100mg) is placed in tube furnace, under the condition of nitrogen protection, is warming up to 650 DEG C, and temperature rise rate is 10 DEG C/min, is incubated 120 minutes, naturally cools to room temperature.Finally obtain 69mg Graphene black solid.
preparative Example 2.3
Hydrazine hydrate reduction prepares Graphene
The graphene oxide ultrapure water solution dilution that Preparative Example 1 obtains, to 2mg/mL, gets 30mL, ultrasonic 30 minutes (power 80W), and add 0.5mL hydrazine hydrate solution (85 quality %), temperature is 40 DEG C, stirs 12 hours.Collecting by filtration, uses milli-Q water three times, and once, 60 DEG C of dryings 12 hours, finally obtain 40mg Graphene black solid to alcohol flushing.。
preparative Example 3prepare metal hydroxides nano particle
preparative Example 3.1
Prepare cerium hydroxide nano particle suspension liquid
The ultrapure water solution (25mol/L) of sodium hydroxide is added drop-wise in the ultrapure water solution of cerous nitrate (1mol/L, 50mL), regulator solution pH to 10, stirs 30 minutes, obtain the cerium hydroxide nano particle suspension liquid of 1mol/L white.
preparative Example 3.2-3.21
The method of metal hydroxides is prepared according to Preparative Example 3.1, unlike, the metal-salt used becomes ferrous sulfate, iron protochloride, ferric sulfate, aluminum chloride, zinc chloride, ruthenium chloride, magnesium chloride, molybdic chloride, molybdous chloride, zirconium chloride, copper sulfate, cupric chloride, titanium tetrachloride, nickelous chloride, nickelous chloride, Cadmium chloride fine powder, Lanthanum trichloride, cobalt chloride, vanadium chloride, niobium chloride from cerous nitrate, prepares corresponding hydroxide nanoparticles suspension.
preparative Example 3.22-3.25
Prepare cerium hydroxide nano particle according to the method for Preparative Example 3.1, the concentration unlike cerous nitrate ultrapure water solution is 0.01mol/L, 0.1mol/L, 0.5mol/L and 10mol/L.
preparative Example 4prepare metal oxide nanoparticles
preparative Example 4.1
Prepare ferroferric oxide nano granules
By iron acetylacetonate dissolves at N, in dinethylformamide (DMF), strength of solution is 0.5mol/L, stirs after 4 hours, getting 30mL loading volume is the autoclave of 50mL, 200 DEG C are heated 24 hours, obtain black solid, collecting by filtration, with milli-Q water once, washing with alcohol three times, 60 DEG C of dryings 12 hours, obtain ferroferric oxide nano granules.
preparative Example 4.2-4.9
Metal oxide nanoparticles is prepared according to the method for embodiment 4.1, the metal precursor used unlike step (1) is different, and namely metal complexes is aluminium acetylacetonate, vanadium acetylacetonate, acetylacetonate nickel, methyl ethyl diketone zirconium, acetylacetone cobalt, zinc acetylacetonate, acetylacetone copper, chromium acetylacetonate respectively.Obtain corresponding metal oxide nanoparticles.
preparative Example 4.10-4.12
Ferroferric oxide nano granules is prepared according to the method for Preparative Example 4.1, unlike, the concentration of the DMF solution of ferric acetyl acetonade is respectively 0.1mol/L, 1mol/L and 10mol/L.
preparative Example 5prepare graphene oxide film and graphene film
preparative Example 5.1
Spin-coating method prepares graphene oxide film
Graphene oxide film adopts spin coating method preparation, uses silicon chip or sheet glass to be substrate (specification: 1cm × 1cm).Substrate is being immersed in the mixing solutions of the vitriol oil (98 weight) and hydrogen peroxide (30 weight) (vitriol oil: hydrogen peroxide=7:3, volume ratio), and 70 DEG C are reacted 30 minutes, after naturally cooling to room temperature, use ultrapure water.The graphene oxide that Preparative Example 1 prepares is mixed with the water that concentration is 1.5mg/mL and alcohol mixed solution (volume ratio of water and ethanol is 1:3), gets 30mL, ultrasonic 30 minutes (power 80W).Drop in substrate by 0.5mL graphene oxide solution, (even glue speed is 100rpm, 15s to start spin coating instrument; Spin speed is 3000rpm, 60s), spin-coating step repeats 3 times.Put by the graphene oxide film prepared dry in an oven, temperature is 60 DEG C.
preparative Example 5.2
Graphene film is prepared in high-temperature hot reduction
The graphene oxide film prepared by Preparative Example 5.1 is placed in tube furnace, under the condition of nitrogen protection, is warming up to 400 DEG C, and temperature rise rate is 10 DEG C/min, is incubated 30 minutes, naturally cools to room temperature.Obtain the graphene film of black.
preparative Example 5.3
Hydrothermal reduction prepares graphene film
The graphene oxide membrane suspension prepared by Preparative Example 5.1 is in reactor (volume is 50mL), add 15mL ultrapure water (graphene oxide film is not immersed in ultrapure water) in a kettle., reactor is placed in baking oven, and 180 DEG C are heated 6 hours.Obtain the graphene film of black.
preparative Example 5.4
Graphene film is prepared in hydrazine hydrate steam reduction
The graphene oxide film prepared by Preparative Example 5.1 is placed in hydrazine hydrate steam (saturated vapor pressure), under temperature is 40 DEG C of conditions, reacts 6 hours.Obtain the graphene film of black.
preparative Example 5.5
Physical separation methods prepares graphene film
Use high directed cracking graphite to be raw material, the method using adhesive tape to tear graphite prepares single-layer graphene, and is transferred in silicon base (1cm × 1cm).
preparative Example 5.6
Process for preparing graphenes by chemical vapour deposition film
Use Copper Foil or nickel foil to be substrate, use methane or acetylene (high-purity gas) to be carbon source, growth temperature is 1000 DEG C, and carrier gas is the mixed gas (1:99) of hydrogen and argon gas, and cooling rate is 10 DEG C/min.
(1) porous graphene is prepared
embodiment 1oxometallate is used to prepare porous graphene (route one) for etching agent
embodiment 1.1
(1) mixture of graphene oxide and Sodium orthomolybdate is prepared
Graphene oxide ultrapure water solution (4mg/mL, 50mL) obtained by Preparative Example 1 and Sodium orthomolybdate ultrapure water solution (0.02mol/L, 50mL) mix.Vibrate 12 hours in shaking table, rotating speed is 100rpm.With liquid nitrogen bath by after freezing for mixing solutions 15 minutes, use freeze drier to carry out drying (48 hours, temperature is-50 DEG C, and pressure is 7.5Pa), prepare the mixture of graphene oxide and Sodium orthomolybdate.
(2) porous graphene is prepared
The graphene oxide obtain step (1) and the mixture of Sodium orthomolybdate are placed in tube furnace as presoma (200mg), and under the condition of nitrogen protection, be warming up to 650 DEG C, temperature rise rate is 10 DEG C/min, are incubated 120 minutes, naturally cool to room temperature.By the black solid obtained, be dispersed in (0.5mol/L, 50mL) in dilute hydrochloric acid, stir 3 days, collecting by filtration, use milli-Q water three times, alcohol flushing is once, 60 DEG C of dryings 12 hours, the black solid powder obtained is porous graphene sample, and sample quality is about 45mg.The TEM(Tecnai G of the porous graphene sample obtained
220S-TWIN transmission electron microscope, FEI Co. of the U.S.), photo is as shown in Figure 1.
embodiment 1.2-1.5
Porous graphene sample is prepared according to the method for embodiment 1.1, unlike, the concentration of the Sodium orthomolybdate ultrapure water solution that step (1) uses is 0.01mol/L, 0.1mol/L, 1mol/L and 10mol/L.Obtain black solid and be respectively 50mg, 49,46 and 43mg.
embodiment 1.6-1.8
Porous graphene sample is prepared according to the method for embodiment 1.1, unlike, the temperature that step (2) high temperature processing step uses is respectively 300 DEG C, 350 DEG C and 1000 DEG C, obtains black solid and is respectively 54mg, 54mg and 34mg.
embodiment 1.9-1.11
Porous graphene sample is prepared according to the method for embodiment 1.1, unlike, the time of step (2) pyroprocessing is respectively 5 minutes, 60 minutes and 300 minutes, obtains black solid and is respectively 53mg, 40mg and 34mg.
embodiment 1.12-1.16
Porous graphene sample is prepared according to the method for embodiment 1.1, unlike, the graphene oxide ultrapure water strength of solution that step (1) uses is respectively 0.5mg/mL, 2mg/mL, 8mg/mL, 10mg/mL and 20mg/mL.Obtain black solid and be respectively 52mg, 53mg, 53mg, 52mg and 54mg.
embodiment 1.17-1.77
Porous graphene sample is prepared according to the method for embodiment 1.1, unlike, the oxometallate that step (1) uses is potassium molybdate respectively, lithium tungstate, sodium wolframate, potassium wolframate, lithium stannate, sodium stannate, potassium stannate, lithium aluminate, sodium aluminate, potassium aluminate, lithium titanate, sodium titanate, potassium titanate, lithium titanate, vanadic acid sodium, potassium vanadate, bismuthic acid lithium, sodium bismuthate, bismuthic acid potassium, high manganese lithium, potassium permanganate, sodium permanganate, lithium manganate, potassium manganate, sodium manganate, potassium bichromate, sodium dichromate 99, lithium chromate, potassiumchromate, Sodium chromate, lithium zirconate, sodium zirconate, potassium zirconium, ferrate-lithium, Na2Fe04, potassium ferrate, zincic acid lithium, sodium zincate, potassium zincate, Lithium niobium trioxide, sodium columbate, potassium niobate, cobalt acid lithium, cobalt acid sodium, cobalt acid potassium, lithium nickelate, nickel acid sodium, nickel acid potassium, silicomolybdic acid, silicotungstic acid, silicon vanadic acid, ammonium molybdate, ammonium tungstate, ammonium vanadate, mangaic acid ammonium, ammonium dichromate, ammonium chromate, nickel acid ammonium, phospho-wolframic acid, phosphorus molybdenum and phosphorus vanadic acid.The black solid quality obtained is about 51,53,46,47,53,47,46,45,49,47,49,53,55,53,49,50,51,47,54,54,51,53,49,46,47,51,51,47,53,47,54,46,46,53,53,49,46,47,50,51,47,53,51,49,54,46,51,53,46,47,50,51,47,51,47,50,51,47,53,51 and 53mg.
embodiment 1.77
Porous graphene sample is prepared according to the method for embodiment 1.1, unlike, in step (2), nitrogen protection condition becomes vacuum condition (being less than 10Pa).
embodiment 2oxometallate is used to prepare porous graphene (route two) for etching agent
embodiment 2.1
(1) mixture of Graphene and Sodium orthomolybdate is prepared
Porous graphene sample is prepared according to the method for embodiment 1, unlike, the Graphene (200mg) for Preparative Example 2.1 acquisition used in the present embodiment.The black solid powder obtained, quality is 56mg.
embodiment 2.2-2.3
Porous graphene sample is prepared according to the method for embodiment 2.1, unlike, what the Graphene that step (1) uses used is the Graphene that Preparative Example 2.2 and 2.3 prepares respectively, and the quality obtaining black solid is respectively 55mg and 57mg.
embodiment 2.4-2.6
Porous graphene sample is prepared according to the method for embodiment 2.1, unlike, the concentration of the Sodium orthomolybdate ultrapure water solution that step (1) uses is respectively 0.01mol/L, 0.5mol/L and 10mol/L, and the quality obtaining black solid is respectively 60mg, 48mg and 34mg.
embodiment 2.7-2.9
Porous graphene sample is prepared according to the method for embodiment 2.1, unlike, the temperature that step (2) high temperature processing step uses is respectively 450 DEG C, 300 DEG C and 1000 DEG C, obtains black solid and is respectively 56mg, 55mg and 37mg.Wherein, the TEM(Tecnai G of 450 DEG C of porous graphene samples prepared
220S-TWIN transmission electron microscope, FEI Co. of the U.S.), wherein, the how empty Graphene prepared at 450 DEG C is as shown in Figure 2.
embodiment 2.10-2.12
Porous graphene sample is prepared according to the method for embodiment 2.1, unlike, the time of step (2) pyroprocessing is respectively 5 minutes, 60 minutes and 300 minutes, obtains black solid and is respectively 56mg, 52mg and 37mg.
embodiment 2.13-2.73
Porous graphene sample is prepared according to the method for embodiment 2.1, unlike, the oxometallate that step (1) uses is potassium molybdate respectively, lithium tungstate, sodium wolframate, potassium wolframate, lithium stannate, sodium stannate, potassium stannate, lithium aluminate, sodium aluminate, potassium aluminate, lithium titanate, sodium titanate, potassium titanate, lithium titanate, vanadic acid sodium, potassium vanadate, bismuthic acid lithium, sodium bismuthate, bismuthic acid potassium, high manganese lithium, potassium permanganate, sodium permanganate, lithium manganate, potassium manganate, sodium manganate, potassium bichromate, sodium dichromate 99, lithium chromate, potassiumchromate, Sodium chromate, lithium zirconate, sodium zirconate, potassium zirconium, ferrate-lithium, Na2Fe04, potassium ferrate, zincic acid lithium, sodium zincate, potassium zincate, Lithium niobium trioxide, sodium columbate, potassium niobate, cobalt acid lithium, cobalt acid sodium, cobalt acid potassium, lithium nickelate, nickel acid sodium, nickel acid potassium, silicomolybdic acid, silicotungstic acid, silicon vanadic acid, ammonium molybdate, ammonium tungstate, ammonium vanadate, mangaic acid ammonium, ammonium dichromate, ammonium chromate, nickel acid ammonium, phospho-wolframic acid, phospho-molybdic acid and phosphorus vanadic acid.The black solid quality obtained is about 48-60mg.
embodiment 2.74
Porous graphene sample is prepared according to the method for embodiment 2.1, unlike, in step (2), nitrogen protection condition becomes vacuum condition (being less than 10Pa).
embodiment 3metal hydroxides is used to prepare porous graphene (route one) for etching agent
embodiment 3.1
(1) mixture of graphene oxide and cerous hydroxide is prepared
The cerous hydroxide suspension (0.1mol/L, 50mL) obtained by Preparative Example 3.1 is added drop-wise in the ultrapure water solution (4mg/mL, 50mL) of graphene oxide, ultrasonic 30 minutes (power 80W), stirs 12 hours.By the homogeneous mixture solution liquid nitrogen bath that obtains by after freezing for mixing solutions 15 minutes, freeze drier is used to carry out drying (48 hours, temperature is-50 DEG C, and pressure is 7.5Pa).
(2) porous graphene is prepared
The Graphene obtain step (1) and the mixture of cerous hydroxide are as presoma (200mg), and be placed in tube furnace, under the condition of nitrogen protection, be warming up to 650 DEG C, temperature rise rate is 10 DEG C/min, are incubated 120 minutes, naturally cool to room temperature.
By the black solid obtained, be dispersed in (0.5mol/L, 50mL) in dilute hydrochloric acid, stir 3 days, collecting by filtration, use milli-Q water three times, once, 60 DEG C of dryings 12 hours, the black solid quality obtained is 52mg to alcohol flushing.The SEM(Hitachi S-4800 scanning electronic microscope of the porous graphene sample prepared, HIT) photo is as shown in Figure 3.
embodiment 3.2-3.5
Porous graphene sample is prepared according to the method for embodiment 3.1, unlike, the temperature that step (2) high temperature processing step uses is respectively 900 DEG C, 450 DEG C, 300 DEG C and 1000 DEG C, obtains black solid and is respectively 35mg, 52mg, 54mg and 33mg.
embodiment 3.6-3.9
Porous graphene sample is prepared according to the method for embodiment 3.1, unlike, the time of step (2) pyroprocessing is respectively 5 minutes, 60 minutes, 200 minutes and 300 minutes, obtains black solid and is respectively 52mg, 49mg, 38mg and 33mg.
embodiment 3.10-3.14
Porous graphene sample is prepared according to the method for embodiment 3.1, unlike, the concentration of the graphene oxide ultrapure water solution that step (1) uses is respectively 2mg/mL, 6mg/mL, 8mg/mL, 10mg/mL and 20mg/mL.Obtain black solid and be respectively 35mg, 62mg, 78mg, 89mg and 118mg.
embodiment 3.15-3.38
Porous graphene sample is prepared according to the method for embodiment 3.1, unlike, the metal hydroxides that step (1) uses is different, is respectively the metal hydroxides nano granule suspension that Preparative Example 3.2-3.25 prepares.The black solid quality obtained is respectively 45,47,46,45,49,47,49,53,55,49,50,51,47,54,46,51,53,49,46,47,50,51,47 and 53mg.
embodiment 3.39
Porous graphene sample is prepared according to the method for embodiment 3.1, unlike, in step (2), nitrogen protection condition becomes vacuum condition (being less than 10Pa).
embodiment 4metal oxide is used to prepare porous graphene (route one) for etching agent
embodiment 4.1
(1) Graphene that ferroferric oxide nano granules is modified is prepared
The graphene oxide ultrapure water strength of solution obtained by Preparative Example 1 is adjusted to 8mg/mL, by iron acetylacetonate dissolves at N, in dinethylformamide (DMF), strength of solution is 0.1mol/L, is that 1:1 carries out mixing (being respectively 50mL) by two kinds of solution with volume ratio.Stir after 4 hours, getting 30mL, to load volume be the autoclave of 50mL, and 200 DEG C of heating 24 hours, obtain black solid, collecting by filtration, with milli-Q water once, washing with alcohol three times, 60 DEG C of dryings 12 hours.
(2) porous graphene is prepared
The Graphene that ferroferric oxide nano granules step (1) obtained is modified, as presoma (200mg), is placed in tube furnace, under the condition of nitrogen protection; be warming up to 650 DEG C; temperature rise rate is 10 DEG C/min, is incubated 120 minutes, naturally cools to room temperature.
By the black solid obtained, be dispersed in (0.5mol/L, 50mL) in dilute hydrochloric acid, stir 3 days, collecting by filtration, use milli-Q water three times, once, 60 DEG C of dryings 12 hours, the black solid powder obtained is porous graphene sample to alcohol flushing.
embodiment 4.2-4.4
Porous graphene sample is prepared according to the method for embodiment 4.1, unlike, the concentration of the DMF solution of the ferric acetyl acetonade of step (1) is respectively 0.5mol/L, 1mol/L and 10mol/L.Obtain black solid and be respectively 63mg, 54mg and 44mg.
embodiment 4.5-4.7
Porous graphene sample is prepared according to the method for embodiment 4.1, unlike, the temperature that step (2) high temperature processing step uses is respectively 300 DEG C, 450 DEG C and 1000 DEG C, obtains black solid and is respectively 54mg, 52mg and 33mg.
embodiment 4.8-4.10
Porous graphene sample is prepared according to the method for embodiment 4.1, unlike, the time of step (2) pyroprocessing is respectively 5 minutes, 60 minutes and 300 minutes, obtains black solid and is respectively 52mg, 49mg and 33mg.
embodiment 4.11-4.14
Porous graphene sample is prepared according to the method for embodiment 4.1, unlike, the concentration of the graphene oxide ultrapure water solution that step (1) uses is respectively 4mg/mL, 10mg/mL, 16mg/mL and 20mg/mL.Obtain black solid and be respectively 38mg, 45mg, 58mg and 98mg.
embodiment 4.15-4.22
Porous graphene sample is prepared according to the method for embodiment 4.1, unlike, the metal precursor that step (1) uses is different, and namely metal complexes is aluminium acetylacetonate, vanadium acetylacetonate, acetylacetonate nickel, methyl ethyl diketone zirconium, acetylacetone cobalt, zinc acetylacetonate, acetylacetone copper, chromium acetylacetonate respectively.The black solid quality obtained is about 45-55mg.
embodiment 4.23
Porous graphene sample is prepared according to the method for embodiment 4.1, unlike, in step (2), nitrogen protection condition becomes vacuum condition (being less than 10Pa).
embodiment 5metal oxide is used to prepare porous graphene (route two) for etching agent
embodiment 5.1
(1) mixture of graphene oxide and Z 250 is prepared
The ferroferric oxide nano granules (100mg) obtained by Preparative Example 4.1 is dispersed in ultrapure water (25mL), after ultrasonic 30 minutes (power 80W), join the ultrapure water solution (4mg/mL of graphene oxide, 25mL), the mass ratio of graphene oxide and ferroferric oxide nano granules is 1:1, ultrasonic 1 hour (power 80W), then stirs 12 hours.By the homogeneous mixture solution liquid nitrogen bath that obtains by after freezing for mixing solutions 15 minutes, freeze drier is used to carry out drying (48 hours, temperature is-50 DEG C, and pressure is 7.5Pa).
(2) porous graphene is prepared
The Graphene that ferroferric oxide nano granules step (1) obtained is modified, as presoma (200mg), is placed in tube furnace, under the condition of nitrogen protection; be warming up to 650 DEG C; temperature rise rate is 10 DEG C/min, is incubated 120 minutes, naturally cools to room temperature.
By the black solid obtained, be dispersed in (0.5mol/L, 50mL) in dilute hydrochloric acid, stir 3 days, collecting by filtration, use milli-Q water three times, once, 60 DEG C of dryings 12 hours, the quality of the black solid powder obtained is 56mg to alcohol flushing.
embodiment 5.2-5.4
Porous graphene sample is prepared according to the method for embodiment 5.1, unlike, the temperature that step (2) high temperature processing step uses is respectively 300 DEG C, 450 DEG C and 1000 DEG C, obtains black solid and is respectively 58mg, 54mg and 35mg.
embodiment 5.5-5.7
Porous graphene sample is prepared according to the method for embodiment 5.1, unlike, the time of step (2) pyroprocessing is respectively 5 minutes, 60 minutes and 300 minutes, obtains black solid and is respectively 56mg, 52mg and 36mg.
embodiment 5.8-5.11
Porous graphene sample is prepared according to the method for embodiment 5.1, unlike, the concentration of the graphene oxide ultrapure water solution that step (2) uses is respectively 2mg/mL, 8mg/mL, 16mg/mL and 20mg/mL.Obtain black solid and be respectively 36mg, 76mg, 98mg and 112mg.
embodiment 5.12-5.22
Porous graphene sample is prepared according to the method for embodiment 5.1, unlike, metal oxide nanoparticles is different, is namely respectively the metal oxide that Preparative Example 4.2-4.12 prepares.The black solid quality obtained is 45-55mg.
embodiment 5.23
Porous graphene sample is prepared according to the method for embodiment 5.1, unlike, in step (2), nitrogen protection condition becomes vacuum condition (being less than 10Pa).
comparative example 1electron-beam irradiation prepares porous graphene
Prepare Graphene by chemical gaseous phase depositing process, and Graphene is transferred to (this step reference: Li, X. on copper mesh; Cai, W.; An, J.; Kim, S.; Nah, J.; Yang, D.; Piner, R.; Velamakanni, A.; Jung, I.; Tutuc, E.; Banerjee, S.K.; Colombo, L.; Ruoff, R.S.Large-Area Synthesis of High-Qualityand Uniform Graphene Films on Copper Foils.Science2009,324,1312-1314.).By the method for electron beam evaporation plating, at graphenic surface depositing Pd nanoparticle.Copper mesh transfer is entered electron microscopic sample cabin (UltraSTEM100 aberration correction scanning transmission electron microscope), under vacuum (5 × 10
-9torr), by electron beam irradiation Graphene (60keV), there is defect structure in graphenic surface, namely prepares porous graphene sample (Zan, R.; Ramasse, Q.M.; Bangert, U.; Novoselov, K.S.Graphene Reknits Its Holes.Nano Lett.2012,12 (8), 3936-3940.).The method is that the porous graphene output prepared is extremely low, in " sheet " in the enterprising line operate processing of monolithic graphite alkene.
comparative example 2helium ion bombardment prepares porous graphene
Prepare Graphene by mechanically peel method and transfer to SiO
2(this step reference: Novoselov, K. in substrate; Geim, A.; Morozov, S.; Jiang, D.; Zhang, Y.; Dubonos, S.; Grigorieva, I.; Firsov, A.Electric Field Effect in Atomically Thin Carbon Films.Science2004,306,666-669.).Graphene sample is placed in helium ion microscope sample chamber (Zeiss ORION system), sample chamber (Evactron plasma cleaner, 12W, (work in 15 minutes in 10 hours is cleaned with air plasma before test, have a rest 45 minutes, circulate 10 times)).Use helium ion pair Graphene to bombard, voltage is 30kV, can prepare porous graphene (Bell, D.C.; Lemme, M.C.; Stern, L.A.; Williams, J.R.; Marcus, C.M.PrecisionCutting and Patterning of Graphene with Helium Ions.Nanotechnology2009,20 (45), 455301.).The method is that the porous graphene output prepared is extremely low, in " sheet " in the enterprising line operate processing of monolithic graphite alkene.
(2) porous graphene film is prepared
embodiment 6 carbon-thermal reduction prepares porous graphene film
embodiment 6.1
The ultrapure water solution (1mol/mL, 0.1mL) of ammonium molybdate is covered on graphene film that Preparative Example 5.2 obtains, 40 DEG C of standing and drying.Film sample is placed in tube furnace, under the condition of nitrogen protection, is warming up to 400 DEG C, temperature rise rate is 10 DEG C/min, is incubated 30 minutes, naturally cools to room temperature.By the black thin film obtained, be immersed in (0.5mol/L, 20mL) in dilute hydrochloric acid, use ultrapure water three times, alcohol flushing once, 60 DEG C of dryings 12 hours.What obtain is porous graphene film.Photo as shown in Figure 4.
embodiment 6.2-6.5
Porous graphene film sample is prepared according to the method for embodiment 6.1, unlike, the ultrapure water strength of solution of ammonium molybdate is respectively 0.01mol/L, 2mol/L, 5mol/L and 10mol/L.
embodiment 6.6-6.10
Porous graphene film sample is prepared according to the method for embodiment 6.1, unlike, the temperature of high temperature processing step is respectively 300 DEG C, 350 DEG C, 500 DEG C, 650 DEG C and 1000 DEG C.
embodiment 6.11-6.15
Porous graphene film sample is prepared according to the method for embodiment 6.1, unlike, the time of high temperature processing step is respectively 5 minutes, 30 minutes, 60 minutes, 120 minutes and 300 minutes.
embodiment 6.16-6.76
Porous graphene sample is prepared according to the method for embodiment 6.1, unlike, the oxometallate used is potassium molybdate respectively, lithium tungstate, sodium wolframate, potassium wolframate, lithium stannate, sodium stannate, potassium stannate, lithium aluminate, sodium aluminate, potassium aluminate, lithium titanate, sodium titanate, potassium titanate, lithium titanate, vanadic acid sodium, potassium vanadate, bismuthic acid lithium, sodium bismuthate, bismuthic acid potassium, high manganese lithium, potassium permanganate, sodium permanganate, lithium manganate, potassium manganate, sodium manganate, potassium bichromate, sodium dichromate 99, lithium chromate, potassiumchromate, Sodium chromate, lithium zirconate, sodium zirconate, potassium zirconium, ferrate-lithium, Na2Fe04, potassium ferrate, zincic acid lithium, sodium zincate, potassium zincate, Lithium niobium trioxide, sodium columbate, potassium niobate, cobalt acid lithium, cobalt acid sodium, cobalt acid potassium, lithium nickelate, nickel acid sodium, nickel acid potassium, silicomolybdic acid, silicotungstic acid, silicon vanadic acid, ammonium molybdate, ammonium tungstate, ammonium vanadate, mangaic acid ammonium, ammonium dichromate, ammonium chromate, nickel acid ammonium, phospho-wolframic acid, phospho-molybdic acid and phosphorus vanadic acid.
embodiment 6.77-80
Prepare porous graphene film sample according to the method for embodiment 6.1, the graphene film sample unlike, use is respectively graphene film sample prepared by Preparative Example 5.3-5.6.
embodiment 6.81-106
Prepare porous graphene film sample according to the method for embodiment 6.1, the etching agent unlike, use Wei the cerous hydroxide suspension that be prepared by Preparative Example 3.1-3.26 by ammonium molybdate variation, and suspension concentration is dilution for 0.1mol/L.
embodiment 6.107-114
Porous graphene film sample is prepared according to the method for embodiment 6.1, unlike, the etching agent of use becomes from ammonium molybdate the ferroferric oxide nano granules prepared by Preparative Example 4.1-4.8 respectively.Ferroferric oxide nano granules ultrapure water strength of solution is 0.1mol/L.
embodiment 6.115
Porous graphene sample is prepared according to the method for embodiment 6.1, unlike, nitrogen protection condition becomes vacuum condition (being less than 10Pa).
embodiment 7 electron beam auxiliary law prepares porous graphene film
embodiment 7.1
The ultrapure water solution (1mol/mL, 0.1mL) of ammonium molybdate is covered on graphene film that Preparative Example 5.2 obtains, 40 DEG C of standing and drying.Film sample is placed in vacuum condition, uses electron beam to carry out radiation (electron-beam voltage is 6KV) 5 minutes.By the black thin film obtained, be immersed in (0.5mol/L, 20mL) in dilute hydrochloric acid, use ultrapure water three times, alcohol flushing once, 60 DEG C of dryings 12 hours.What obtain is porous graphene film.The SEM(Hitachi S-4800 scanning electronic microscope of the porous graphene film sample of preparation, HIT) photo is as shown in Figure 5.
embodiment 7.2-7.5
Porous graphene film sample is prepared according to the method for embodiment 7.1, unlike, the ultrapure water strength of solution of ammonium molybdate is respectively 0.01mol/L, 2mol/L, 5mol/L and 10mol/L.
embodiment 7.6-7.9
Porous graphene film sample is prepared according to the method for embodiment 7.1, unlike, electron-beam voltage is respectively 1KV, 10KV, 15KV and 20KV.
embodiment 7.10-7.12
Porous graphene film sample is prepared according to the method for embodiment 7.1, unlike, the electron beam irradiation time is respectively 0.5 minute, 3 minutes 10 minutes.
embodiment 7.13-1.73
Porous graphene sample is prepared according to the method for embodiment 7.1, unlike, the oxometallate used is Sodium orthomolybdate respectively, potassium molybdate, lithium tungstate, sodium wolframate, potassium wolframate, lithium stannate, sodium stannate, potassium stannate, lithium aluminate, sodium aluminate, potassium aluminate, lithium titanate, sodium titanate, potassium titanate, lithium titanate, vanadic acid sodium, potassium vanadate, bismuthic acid lithium, sodium bismuthate, bismuthic acid potassium, high manganese lithium, potassium permanganate, sodium permanganate, lithium manganate, potassium manganate, sodium manganate, potassium bichromate, sodium dichromate 99, lithium chromate, potassiumchromate, Sodium chromate, lithium zirconate, sodium zirconate, potassium zirconium, ferrate-lithium, Na2Fe04, potassium ferrate, zincic acid lithium, sodium zincate, potassium zincate, Lithium niobium trioxide, sodium columbate, potassium niobate, cobalt acid lithium, cobalt acid sodium, cobalt acid potassium, lithium nickelate, nickel acid sodium, nickel acid potassium, silicomolybdic acid, silicotungstic acid, silicon vanadic acid, ammonium molybdate, ammonium tungstate, ammonium vanadate, mangaic acid ammonium, ammonium dichromate, ammonium chromate or nickel acid ammonium, phospho-wolframic acid, phospho-molybdic acid and phosphorus vanadic acid.
embodiment 7.74-7.77
Porous graphene film sample is prepared according to the method for embodiment 7.1, unlike, the graphene film sample of use is respectively and is prepared by Preparative Example 5.3-5.6.
embodiment 7.78-7.99
Prepare porous graphene film sample according to the method for embodiment 7.1, the etching agent unlike, use Wei the cerous hydroxide suspension that be obtained by Preparative Example 3.1-3.22 by ammonium molybdate variation, and suspension concentration is dilution for 0.1mol/L.
embodiment 7.100-7.107
Porous graphene film sample is prepared according to the method for embodiment 7.1, unlike, the etching agent of use becomes from ammonium molybdate the ferroferric oxide nano granules prepared by Preparative Example 4.1-4.8.Ferroferric oxide nano granules ultrapure water strength of solution is 0.1mol/L.
As can be seen from the above embodiments, adopt the technical scheme of the application all successfully can prepare porous graphene or porous graphene film, and the present invention can realize the relatively large preparation of porous graphene.Compared with the preparation method of the porous graphene reported before, present method has the following advantages:
(1) output is high.Porous graphene output prepared by present method affects by charging capacity, and improve the charging capacity of precursor, output can reach a gram level, and the pore size on porous graphene surface and hole density can be regulated and controled by the ratio of etching agent Graphene in adjustment precursor.Prepare the method for porous graphene in comparative example mainly for the processing that monolithic graphite alkene or graphene film carry out, study in its surperficial pore-creating, output is very low, usually in " sheet ".
(2) equipment is simple.The present invention only needs to use tube furnace (<2000 unit), vacuum pump (<1 ten thousand yuan), just can complete the preparation of porous graphene or graphene film.Need in comparative example to use scanning transmission electron microscope and these large-scale equipment of helium ion microscope, equipment price very high (usually tens to millions of unit not etc.).Meanwhile, the method in comparative example also has very high requirement for the vacuum tightness of sample chamber, degree of cleaning.
As can be seen from Fig. 4 and Fig. 5, the porous ink alkene film that embodiment 6.1 prepares, the etching agent of use is oxometallate, and carry out pore-creating by thermal treatment, aperture is about 100nm, and hole is closeer, can also observe the fold of Graphene in SEM photo.Fig. 5 is the porous graphene film using electron beam lithography method to prepare, and by using electron beam to provide energy, etching agent also in the pore-creating of graphene film surface etch, can compare thermal reduction method, its aperture and hole density all less.
Therefore, the invention provides a kind of lower-cost method preparing porous graphene in a large number, porous graphene is had to the meaning of outbalance in the applied research of material science.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (10)
1. a preparation method for porous graphene, is characterized in that, the method comprises, and Graphene and/or graphene oxide is mixed with etching agent, obtains mixture; Under anaerobic, carbon-thermal reduction is carried out to mixture, and carry out acid treatment to remove unreacted and reacted etching agent; Described etching agent is one or more in oxometallate, metal hydroxides and metal oxide.
2. method according to claim 1, wherein, the mass ratio of described Graphene and/or graphene oxide and etching agent is 0.1-10:1, is preferably 0.5-2:1.
3. method according to claim 1, wherein,
Described oxometallate is Sodium orthomolybdate, potassium molybdate, lithium tungstate, sodium wolframate, potassium wolframate, lithium stannate, sodium stannate, potassium stannate, lithium aluminate, sodium aluminate, potassium aluminate, lithium titanate, sodium titanate, potassium titanate, lithium titanate, vanadic acid sodium, potassium vanadate, bismuthic acid lithium, sodium bismuthate, bismuthic acid potassium, high manganese lithium, potassium permanganate, sodium permanganate, lithium manganate, potassium manganate, sodium manganate, potassium bichromate, sodium dichromate 99, lithium chromate, potassiumchromate, Sodium chromate, lithium zirconate, sodium zirconate, potassium zirconium, ferrate-lithium, Na2Fe04, potassium ferrate, zincic acid lithium, sodium zincate, potassium zincate, Lithium niobium trioxide, sodium columbate, potassium niobate, cobalt acid lithium, cobalt acid sodium, cobalt acid potassium, lithium nickelate, nickel acid sodium, nickel acid potassium, silicomolybdic acid, silicotungstic acid, silicon vanadic acid, ammonium molybdate, ammonium tungstate, ammonium vanadate, mangaic acid ammonium, ammonium dichromate, ammonium chromate, nickel acid ammonium, phospho-wolframic acid, one or more in phospho-molybdic acid and phosphorus vanadic acid,
Described metal hydroxides is one or more the oxyhydroxide in the IIth A, III A, I B, II B, IV B, V B, VI B, VIII race and lanthanide series metal; Preferably, described metal hydroxides is the oxyhydroxide of one or more metals in magnesium, aluminium, copper, zinc, cadmium, titanium, zirconium, vanadium, niobium, molybdenum, iron, cobalt, nickel, ruthenium and lanthanum;
Described metal oxide is one or more the oxide compound in the IIIth A, I B, II B, IV B, V B and VIII race's metal; Preferably, described metal oxide is the oxide compound of one or more metals in aluminium, copper, zinc, chromium, zirconium, vanadium and iron, cobalt and nickel.
4. according to the method in claim 1-3 described in any one, wherein, described etching agent is one or more in sodium aluminate, Sodium orthomolybdate and sodium wolframate.
5. method according to claim 1, wherein, described carbon-thermal reduction condition comprises: temperature is 300-1000 DEG C, and the time is 5-300 minute.
6. the preparation method of a porous graphene film, it is characterized in that, the method comprises, and is dispersed in by etching agent on Graphene and/or graphene oxide film, carry out carbon-thermal reduction under anaerobic, and carry out acid treatment to remove unreacted or reacted etching agent; Described etching agent is one or more in oxometallate, metal hydroxides and metal oxide.
7. method according to claim 6, wherein, the mass ratio of described Graphene and/or graphene oxide and etching agent is 0.1-10:1, is preferably 0.5-2:1.
8. method according to claim 6, wherein,
Described oxometallate is Sodium orthomolybdate, potassium molybdate, lithium tungstate, sodium wolframate, potassium wolframate, lithium stannate, sodium stannate, potassium stannate, lithium aluminate, sodium aluminate, potassium aluminate, lithium titanate, sodium titanate, potassium titanate, lithium titanate, vanadic acid sodium, potassium vanadate, bismuthic acid lithium, sodium bismuthate, bismuthic acid potassium, high manganese lithium, potassium permanganate, sodium permanganate, lithium manganate, potassium manganate, sodium manganate, potassium bichromate, sodium dichromate 99, lithium chromate, potassiumchromate, Sodium chromate, lithium zirconate, sodium zirconate, potassium zirconium, ferrate-lithium, Na2Fe04, potassium ferrate, zincic acid lithium, sodium zincate, potassium zincate, Lithium niobium trioxide, sodium columbate, potassium niobate, cobalt acid lithium, cobalt acid sodium, cobalt acid potassium, lithium nickelate, nickel acid sodium, nickel acid potassium, silicomolybdic acid, silicotungstic acid, silicon vanadic acid, ammonium molybdate, ammonium tungstate, ammonium vanadate, mangaic acid ammonium, ammonium dichromate, ammonium chromate, nickel acid ammonium, phospho-wolframic acid, one or more in phospho-molybdic acid and phosphorus vanadic acid,
Described metal hydroxides is one or more the oxyhydroxide in the IIth A, III A, I B, II B, IV B, V B, VI B, VIII race and lanthanide series metal; Preferably, described metal hydroxides is the oxyhydroxide of one or more metals in magnesium, aluminium, copper, zinc, cadmium, titanium, zirconium, vanadium, niobium, molybdenum, iron, cobalt, nickel, ruthenium and lanthanum;
Described metal oxide is one or more the oxide compound in the IIIth A, I B, II B, IV B, V B and VIII race's metal; Preferably, described metal oxide is the oxide compound of one or more metals in aluminium, copper, zinc, chromium, zirconium, vanadium and iron, cobalt and nickel.
9. according to the method in claim 6-8 described in any one, wherein, described etching agent is one or more in sodium aluminate, Sodium orthomolybdate and sodium wolframate.
10. method according to claim 6, wherein, described carbon-thermal reduction condition comprises: temperature is 300-1000 DEG C, and the time is 5-300 minute.
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102867650A (en) * | 2012-09-03 | 2013-01-09 | 中国科学院大连化学物理研究所 | High-magnification supercapacitor composite electrode material and preparation method thereof |
-
2013
- 2013-11-18 CN CN201310581279.2A patent/CN104649253A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102867650A (en) * | 2012-09-03 | 2013-01-09 | 中国科学院大连化学物理研究所 | High-magnification supercapacitor composite electrode material and preparation method thereof |
Non-Patent Citations (4)
| Title |
|---|
| JUN YAN ET AL.: "Fast and reversible surface redox reaction of graphene-MnO2 composites as supercapacitor electrodes", 《CARBON》, vol. 48, 25 June 2010 (2010-06-25) * |
| LI LI ZHANG ET AL.: "Highly Conductive and Porous Activated Reduced Graphene Oxide Films for High-Power Supercapacitors", 《NANO LETTERS》, vol. 12, 28 February 2012 (2012-02-28) * |
| THANGAVELU PALANISELVAM ET AL.: "An efficient oxygen reduction electrocatalyst from graphene by simultaneously generating pores and nitrogen doped active sites", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 22, 24 September 2012 (2012-09-24), XP055136917, DOI: doi:10.1039/c2jm35128e * |
| YANWU ZHU ET AL.: "Carbon-Based Supercapacitors Produced by Activation of Graphene", 《SCIENCE》, vol. 332, 24 June 2011 (2011-06-24), XP055158805, DOI: doi:10.1126/science.1200770 * |
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