CN105253879A - High-porosity functional graphene material as well as preparation method and applications thereof - Google Patents
High-porosity functional graphene material as well as preparation method and applications thereof Download PDFInfo
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Abstract
The invention relates to a high-porosity functional graphene material as well as a preparation method and applications thereof. The high-porosity functional graphene material is of a three-dimensional porous network structure formed by taking a two-dimensional graphene sheet layer as a basic building unit. The preparation method is implemented through carrying out activation reaction on carbon dioxide and graphene aerogel or graphene/metal hybrid aerogel by using a one-step method. The applications include that the material is applied to the aspects of adsorbents for organic vapor adsorption, adsorbents for gas adsorption, electrodes of super capacitors, lithium-ion batteries, or catalysis. The method disclosed by the invention is convenient and simple, and extremely suitable for carrying out large-scale production industrially. The functional graphene material prepared according to the invention is of a hierarchical porous structure, and has super-large specific surface area and pore volume, high organic vapor adsorption capacity, excellent electrochemical properties and good cycling stability, therefore, the material can be applied to the fields of environment and energy and the like.
Description
Technical field
The present invention relates to Graphene porous material and its production and use, particularly a kind of functional graphene material and its production and use of high porosity.
Background technology
In the past few decades, scientific research personnel has prepared a large amount of cellular solids, such as porous silica, zeolite, metal organic frame and micropore organic polymer etc.But in these solid adsorbent, many people think that nanoporous carbon is most potential porous material, because it has high-specific surface area, excellent chemical stability and the characteristic such as cheap and easy to get.
Since two thousand four, by sp
2the single-layer graphene that carbon atom is formed is considered to significantly nano material.It not only has the chemical stability of high specific conductivity, good mechanical property and excellence, but also has the specific surface area of superelevation.Although the theoretical specific surface area of single-layer graphene can reach 2630m
2g
-1, but the specific surface area of the grapheme material usually obtained is far below this numerical value.These grapheme materials compared with low specific surface area mainly because the strong tendency of assembling of its sheet interlayer causes.Therefore, the grapheme material preparing high porosity has great importance.The porous material constructed by Graphene has several obvious advantage than other porous carbon materials.The chemical stability of the first Graphene excellence and thermostability enable constructed porous material stand exacting terms.The second, the high mechanical strength of graphene sheet layer can improve the stability of prepared porous material, thus hinders subsiding of vesicular structure.3rd, construct porous material duct be convenient to the rapid diffusion of electrolytic solution, meanwhile, the conductive capability of Graphene excellence can make it as the collector of quick transmitted load.4th, containing a large amount of oxygen-containing functional group Graphene derivative, such as, the graphene oxide of graphene oxide and chemical reduction, can combine from different organic or inorganic species as base material, this can provide a suitable chance to construct graphene-based porous material.The characteristic of above-mentioned excellence can make graphene-based porous material have extraordinary application prospect in fields such as organic steam absorption, gas adsorption, electrochemical capacitor, lithium ion battery and catalysis.At present, many methods have been used to prepare graphene-based porous material, such as crosslinking, chemical activation method, local reduction way and template-mediated method.
Aerogel is the cellular solid that a class has three-dimensional net structure, and they have the physics-chem characteristic of many excellences, such as high-specific surface area, large pore volume and low density etc.After aerosil reported first, the dissimilar aerogel with higher porosity is also developed in succession.The carbonaceous aerogel be made up of nano-carbon material shows in fields such as electrode materials, absorption and catalysis and applies widely.Graphene aerogel material also result in great concern in recent years.It has high-specific surface area, large pore volume, excellent conductivity, the preferably advantage such as mechanical property and low density.
Carbonic acid gas a kind ofly conventional utilizes high-temperature activation method to prepare the activator of porous carbon materials.But, up to the present, also not about the report of carbon dioxide activation legal system for the functional graphene material of high porosity passing through graphene aerogel.
Summary of the invention
In order to solve problems of the prior art, functional graphene material that the object of the present invention is to provide a kind of high porosity and its production and use.Functional graphene material of the present invention not only has the characteristic of Graphene porous material, and shows excellent organic steam absorption and chemical property.
For reaching above-mentioned purpose, the present invention adopts following technical scheme:
A functional graphene material for high porosity, it is the three-dimensional porous network structure formed by construction unit based on two-dimensional graphene lamella.Because Graphene has the conductivity of high-specific surface area and excellence, thus make the functional graphene material of this high porosity really can be applied to organic steam absorption and ultracapacitor field.
As preferably, the specific surface area of described functional graphene material is 500-2300m
2g
– 1, pore volume is 0.5-5.5cm
3g
– 1; Further preferably, specific surface area is 690-2080m
2g
– 1, pore volume is 1.2-5.4cm
3g
– 1;
Preferably, the aperture of described functional graphene material is 0.2nm-20 μm, and porosity is 85%-99%; Further preferably, aperture is 0.5nm-1 μm, and porosity is 90%-95%;
Preferably, the specific conductivity of described functional graphene material is 10
– 4-10
2scm
– 1; Further preferably, specific conductivity is 10
– 2-10
1scm
– 1.
The present invention also provides the preparation method of the functional graphene material of above-mentioned high porosity, and the method comprises carbonic acid gas and graphene aerogel or Graphene/metal hybrid aerogel generation priming reaction, and single stage method obtains the functional graphene material of high porosity.
Preferably, described priming reaction temperature is 650-1000 DEG C, more preferably 750-950 DEG C;
Preferably, the described priming reaction time is 1-20h, more preferably 1-4h;
Preferably, described priming reaction temperature rise rate is 1-50 DEG C of min
-1, more preferably 1-10 DEG C of min
-1;
Preferably, described priming reaction rate of temperature fall is 1-50 DEG C of min
-1;
Preferably, the preparation method of the functional graphene material of above-mentioned high porosity, the method comprise first by graphene aerogel or Graphene/metal hybrid aerogel in an inert atmosphere with 1-50 DEG C of min
-1temperature rise rate rise to 650-1000 DEG C, then inert atmosphere is switched to carbon dioxide, priming reaction 1-20h in carbon dioxide atmosphere, then with 1-50 DEG C of min
-1rate of temperature fall be down to room temperature (general 15-25 DEG C);
Preferably, described inert atmosphere is argon gas or nitrogen;
Preferably, described priming reaction carries out in tube furnace, more preferably carries out in high temperature process furnances; Be placed in the tube furnace/high temperature process furnances being connected with carbon dioxide by graphene aerogel or Graphene/metal hybrid aerogel and carry out priming reaction.
The preparation method of the functional graphene material of above-mentioned high porosity, wherein, preferably, the preparation method of described graphene aerogel or Graphene/metal hybrid aerogel comprises the following steps:
(1) graphite oxide ultrasonic disperse in water is formed graphene oxide aqueous dispersions;
Or in described graphene oxide aqueous dispersions, add inorganics further, after stirring, obtain uniform graphene oxide/inorganics aqueous dispersions; Described inorganics comprises one or more in the soluble inorganic matter of platiniferous, gold or palladium etc.;
(2) step (1) gained graphene oxide aqueous dispersions or graphene oxide/inorganics aqueous dispersions are carried out hydro-thermal reaction, obtain even immobilising Graphene hydrogel or Graphene/metal hybrid hydrogel;
(3) wash, obtain Graphene hydrogel or Graphene/metal hybrid hydrogel;
(4) dry, obtain described graphene aerogel or Graphene/metal hybrid aerogel.
The preparation method of above-mentioned graphene aerogel or Graphene/metal hybrid aerogel, wherein:
Described in step (1), graphite oxide or graphene oxide can be prepared by art methods.
Such as, the preparation method of graphite oxide disclosed in Chinese Patent Application No. CN201210053921.5 or graphene oxide.
Or, described graphene oxide can be prepared through oxidising process by block graphite material, such as: the natural flaky graphite starting material vitriol oil and potassium permanganate oxidation peeled off and obtain the graphene oxide aqueous solution with better dispersiveness, this is the good method of one preparing graphene oxide at present in a large number.Graphene oxide surface containing oxygen-containing functional groups such as more carboxyl, epoxy group(ing) and hydroxyls, thus make it have good wetting ability, and can utilize these oxygen-containing functional groups to graphene oxide carry out modification and further functionalization obtain its derivative (GeimAK, NovoselovKS.NatureMater.2007,6:183-191; Zu, SZ, HanBH.J.Phys.Chem.C2009,113:13651-13657 etc.).
Preferably, described graphene oxide has oxygen-containing functional group, described oxygen-containing functional group comprises carboxyl.Certainly, described oxygen-containing functional group can also comprise one or more in epoxy group(ing), hydroxyl and aldehyde radical.
Further preferably, in described graphene oxide, the content of carboxyl is 10-30wt%;
Preferably, in described graphene oxide, the weight percentage of oxygen-containing functional group is 10%-50%, more preferably 20%-40%, and such as, in described graphene oxide, the weight percentage of oxygen-containing functional group is 30%.
Preferably, power ultrasonic described in step (1) is 10-600W, and ultrasonic frequency is 20-200KHz;
Preferably, in graphene oxide aqueous dispersions described in step (1), the concentration of graphene oxide is 1-10mgmL
– 1;
Preferably, described in step (1), the mass ratio of graphene oxide and described inorganics is 1:1-100:1;
Preferably, inorganics described in step (1) is one or more in six hydration Platinic chlorides, tetra chlorauric acid, Palladous chloride;
Preferably, in described graphene oxide/inorganics aqueous dispersions, the concentration of six hydration Platinic chlorides, tetra chlorauric acid or Palladous chloride is 0.1-20mgmL
– 1;
Preferably, described in step (2), the temperature of hydro-thermal reaction is 100-200 DEG C;
Preferably, Graphene/metal hybrid hydrogel described in step (2) is one or more in Graphene/golden hybridized hydrogel, graphene/platinum hybridized hydrogel, Graphene/palladium hybridized hydrogel, Graphene/golden platinum hybrid hydrogel;
Preferably, hydro-thermal reaction described in step (2) comprises puts into hydrothermal reaction kettle by described graphene oxide aqueous dispersions or graphene oxide/inorganics aqueous dispersions, is then carried out in an oven by described hydrothermal reaction kettle; Further preferably, described hydrothermal reaction kettle is autoclave;
Preferably, described in step (2), the temperature of hydro-thermal reaction is 100-200 DEG C, and the time of hydro-thermal reaction is 2-24h;
Preferably, washing described in step (3) uses water or the trimethyl carbinol to carry out;
Preferably, Graphene hydrogel or the Graphene metal hybrid hydrogel of inorganics is not remained after washing;
Preferably, described in step (4), drying means is lyophilize; Further preferably, described cryodesiccated temperature is-20 DEG C-liquid nitrogen temperature, and the cryodesiccated time is 2-48h; Vacuum tightness is 5-800Pa;
Preferably, described Graphene/metal hybrid aerogel is one or more in Graphene/golden hybrid aerogel, graphene/platinum hybrid aerogel, Graphene/palladium hybrid aerogel, Graphene/golden platinum hybrid aerogel etc.
The present invention also comprises the functional graphene material of high porosity obtained as stated above.
Contriver experimental studies have found that through a large amount of: graphene aerogel or Graphene/metal hybrid aerogel are placed on and are connected with in the high temperature process furnances of carbon dioxide, utilize carbonic acid gas and graphene aerogel or Graphene/metal hybrid aerogel generation chemical reaction, single stage method can obtain the functional graphene material of high porosity.This reaction method for preparing is simple, and the functional graphene material of preparation has higher organic steam absorption and ultracapacitor performance.
High porosity, by a kind of easy carbon dioxide activation method, is incorporated in Graphene porous material by the present invention.Because Graphene has the conductivity of bigger serface and excellence, thus make this functional graphene material really can be applied to organic steam absorption and ultracapacitor field.Method technique of the present invention is simple, is suitable for scale operation.
The present invention also provides the purposes of the functional graphene material of above-mentioned high porosity, described purposes comprise the functional graphene materials application of described high porosity is adsorbed at organic steam sorbent material, the sorbent material of gas adsorption, the electrode of ultracapacitor, in lithium ion battery or catalysis etc.; Be preferably used as the sorbent material of organic steam absorption and the electrode of ultracapacitor.
Preferably, during sorbent material as organic steam, adsorbate is toluene and methyl alcohol, and adsorptive capacity is 100-4000mgg
– 1;
Preferably, during electrode as ultracapacitor, current density is 0.1-10Ag
– 1time, electrochemical capacitor is 50-200Fg
– 1.
Compared with other technology existing, tool of the present invention has the following advantages:
The functional graphene material of high porosity of the present invention combines the double dominant of the excellent specific property of Graphene and the light porous of aerogel, have extra specific surface area, large pore volume, classification three-dimensional network vesicular structure, very high organic steam adsorptive capacity the chemical property of excellence and good cyclical stability, in environment and energy storage field, show excellent performance.
In addition, the functional graphene material of this high porosity also can at lithium ion battery, electromagnetic shielding, electron device, catalysis, solar cell, biosensor, high temperature insulating protection, molecular device, adsorb and the field such as to be separated and to be widely used.
In addition, the preparation method of this functional graphene material is simple and convenient, has the feature of the low and applicable scale operation of cost; Further, use carbonic acid gas to activate graphene aerogel or Graphene/metal hybrid aerogel as activator, the functional graphene material of high porosity can be obtained.
Accompanying drawing explanation
Fig. 1 is the digital photograph of graphene aerogel prepared in embodiment 3;
Fig. 2 is the electron scanning micrograph of the functional graphene material of high porosity prepared in embodiment 3;
Fig. 3 is the transmission electron microscope photo of the functional graphene material of high porosity prepared in embodiment 3;
Fig. 4 is the nitrogen adsorption desorption graphic representation of the functional graphene material of graphene aerogel prepared in embodiment 3 and high porosity;
Fig. 5 is the X-ray diffractometer spectrogram of the functional graphene material of graphene aerogel prepared in embodiment 3 and high porosity;
Fig. 6 be the functional graphene material of high porosity prepared in embodiment 3 under 298K to the adsorption isothermal line of toluene, methyl alcohol and water vapour;
Fig. 7 is that the functional graphene material of high porosity prepared in embodiment 3 is at 1.0molL
-1cyclic voltammetry curve in tetraethylammonium tetrafluoroborate/acetonitrile electrolytic solution;
Fig. 8 is the ratio capacitance of functional graphene material and the relation curve of discharge current density of high porosity prepared in embodiment 3.
Embodiment
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment only understands the present invention for helping, and should not be considered as concrete restriction of the present invention.
Wherein, the graphene oxide aqueous dispersions in embodiment 1-16 prepares by the following method:
(1) measure the 150mL vitriol oil, 4g graphite (median size is about 20 μm) and 3g SODIUMNITRATE are joined in the above-mentioned vitriol oil; Said mixture to be placed in the beaker of 2000mL and to cool with ice-water bath; While keeping vigorous stirring, 18g potassium permanganate is joined in said mixture lentamente;
(2) after potassium permanganate adds, ice-water bath is withdrawn, then this mixture is at room temperature kept 5 days;
(3) react after five days, the distilled water of 300mL is joined in said mixture at leisure;
(4) adding by 500mL concentration is wherein the hydrogen peroxide of 3wt%; After the process of hydrogen peroxide, mixture becomes glassy yellow from brown;
(5) add the hydrochloric acid of 5wt% wherein, after standing sedimentation, supernatant liquor is poured out, repeat 4 times; Add the distilled water of 3L again, after standing sedimentation, supernatant liquor is poured out, centrifugal after repeating 3 times, obtain graphite oxide; By this graphite oxide dialysis at least one week, it is made to be further purified;
(6) graphite oxide of above-mentioned preparation is made into the concentration of needs, last ultrasonic disperse forms graphene oxide aqueous dispersions; Described ultrasonic power is 200W, and ultrasonic frequency is 40KHz.
Embodiment 1
By graphene oxide aqueous dispersions (18mL, concentration 5mgmL
– 1) be placed on containing in teflon-lined stainless steel cauldron, at 180 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the Graphene hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure Graphene hydrogel.After this Graphene hydrogel lyophilize, graphene aerogel can be obtained.
The graphene aerogel obtained is placed on after in quartz boat, transfers them in tube furnace; By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 750 DEG C.When tube furnace temperature reaches 750 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 2h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 2
By (18mL, concentration 5mgmL in graphene oxide aqueous dispersions
– 1) be placed on containing in teflon-lined stainless steel cauldron, at 180 hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the Graphene hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure Graphene hydrogel.After this Graphene hydrogel lyophilize, graphene aerogel can be obtained.
The graphene aerogel obtained is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 850 DEG C.When tube furnace temperature reaches 850 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 2h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 3
By (18mL, concentration 5mgmL in graphene oxide aqueous dispersions
– 1) be placed on containing in teflon-lined stainless steel cauldron, at 180 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the Graphene hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure Graphene hydrogel.After this Graphene hydrogel lyophilize, graphene aerogel can be obtained.
The graphene aerogel obtained is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 950 DEG C.When tube furnace temperature reaches 950 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 2h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 4
By tetra chlorauric acid (0.5mL, concentration 10mgmL
– 1) join (20mL, concentration 2mgmL in graphene oxide aqueous dispersions
– 1), then this mixture is placed on containing in teflon-lined stainless steel cauldron, at 180 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the Graphene/golden hybridized hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure Graphene/golden hybridized hydrogel.After this Graphene/golden hybridized hydrogel lyophilize, Graphene/golden hybrid aerogel can be obtained.
The Graphene obtained/golden hybrid aerogel is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 750 DEG C.When tube furnace temperature reaches 750 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 2h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 5
By tetra chlorauric acid (0.5mL, concentration 10mgmL
– 1) join (20mL, concentration 2mgmL in graphene oxide aqueous dispersions
– 1), then this mixture is placed on containing in teflon-lined stainless steel cauldron, at 180 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the Graphene/golden hybridized hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure Graphene/golden hybridized hydrogel.After this Graphene/golden hybridized hydrogel lyophilize, Graphene/golden hybrid aerogel can be obtained.
The Graphene obtained/golden hybrid aerogel is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 850 DEG C.When tube furnace temperature reaches 850 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 2h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 6
By tetra chlorauric acid (0.5mL, concentration 10mgmL
– 1) join (20mL, concentration 2mgmL in graphene oxide aqueous dispersions
– 1), then this mixture is placed on containing in teflon-lined stainless steel cauldron, at 180 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the Graphene/golden hybridized hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure Graphene/golden hybridized hydrogel.After this Graphene/golden hybridized hydrogel lyophilize, Graphene/golden hybrid aerogel can be obtained.
The Graphene obtained/golden hybrid aerogel is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 950 DEG C.When tube furnace temperature reaches 950 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 2h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 7
By six hydration Platinic chloride (0.5mL, concentration 10mgmL
– 1) join (20mL, concentration 2mgmL in graphene oxide aqueous dispersions
– 1), then this mixture is placed on containing in teflon-lined stainless steel cauldron, at 180 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the graphene/platinum hybridized hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure graphene/platinum hybridized hydrogel.After this graphene/platinum hybridized hydrogel lyophilize, graphene/platinum hybrid aerogel can be obtained.
The graphene/platinum hybrid aerogel obtained is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 750 DEG C.When tube furnace temperature reaches 750 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 2h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 8
By six hydration Platinic chloride (0.5mL, concentration 10mgmL
– 1) join (20mL, concentration 2mgmL in graphene oxide aqueous dispersions
– 1), then this mixture is placed on containing in teflon-lined stainless steel cauldron, at 180 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the graphene/platinum hybridized hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure graphene/platinum hybridized hydrogel.After this graphene/platinum hybridized hydrogel lyophilize, graphene/platinum hybrid aerogel can be obtained.
The graphene/platinum hybrid aerogel obtained is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 850 DEG C.When tube furnace temperature reaches 850 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 2h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 9
By six hydration Platinic chloride (0.5mL, concentration 10mgmL
– 1) join (20mL, concentration 2mgmL in graphene oxide aqueous dispersions
– 1), then this mixture is placed on containing in teflon-lined stainless steel cauldron, at 180 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the graphene/platinum hybridized hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure graphene/platinum hybridized hydrogel.After this graphene/platinum hybridized hydrogel lyophilize, graphene/platinum hybrid aerogel can be obtained.
The graphene/platinum hybrid aerogel obtained is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 950 DEG C.When tube furnace temperature reaches 950 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 2h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 10
By Palladous chloride (0.5mL, concentration 10mgmL
– 1) join (20mL, concentration 2mgmL in graphene oxide aqueous dispersions
– 1), then this mixture is placed on containing in teflon-lined stainless steel cauldron, at 180 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the Graphene/palladium hybridized hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure Graphene/palladium hybridized hydrogel.After this Graphene/palladium hybridized hydrogel lyophilize, Graphene/palladium hybrid aerogel can be obtained.
The Graphene obtained/palladium hybrid aerogel is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 750 DEG C.When tube furnace temperature reaches 750 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 2h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 11
By Palladous chloride (0.5mL, concentration 10mgmL
– 1) join (20mL, concentration 2mgmL in graphene oxide aqueous dispersions
– 1), then this mixture is placed on containing in teflon-lined stainless steel cauldron, at 180 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the Graphene/palladium hybridized hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure Graphene/palladium hybridized hydrogel.After this Graphene/palladium hybridized hydrogel lyophilize, Graphene/palladium hybrid aerogel can be obtained.
The Graphene obtained/palladium hybrid aerogel is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 850 DEG C.When tube furnace temperature reaches 850 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 2h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 12
By Palladous chloride (0.5mL, concentration 10mgmL
– 1) join (20mL, concentration 2mgmL in graphene oxide aqueous dispersions
– 1), then this mixture is placed on containing in teflon-lined stainless steel cauldron, at 180 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the Graphene/palladium hybridized hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure Graphene/palladium hybridized hydrogel.After this Graphene/palladium hybridized hydrogel lyophilize, Graphene/palladium hybrid aerogel can be obtained.
The Graphene obtained/palladium hybrid aerogel is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 950 DEG C.When tube furnace temperature reaches 950 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 2h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 13
By (18mL, concentration 2mgmL in graphene oxide aqueous dispersions
– 1) be placed on containing in teflon-lined stainless steel cauldron, at 120 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the Graphene hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure Graphene hydrogel.After this Graphene hydrogel lyophilize, graphene aerogel can be obtained.
The graphene aerogel obtained is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 950 DEG C.When tube furnace temperature reaches 950 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 1h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 14
By (18mL, concentration 5mgmL in graphene oxide aqueous dispersions
– 1) be placed on containing in teflon-lined stainless steel cauldron, at 150 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the Graphene hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure Graphene hydrogel.After this Graphene hydrogel lyophilize, graphene aerogel can be obtained.
The graphene aerogel obtained is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 5 DEG C of min
-1temperature rise rate rise to 950 DEG C.When tube furnace temperature reaches 950 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 1h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 15
By tetra chlorauric acid (0.5mL, concentration 10mgmL
– 1) join (20mL, concentration 2mgmL in graphene oxide aqueous dispersions
– 1), then this mixture is placed on containing in teflon-lined stainless steel cauldron, at 120 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the Graphene/golden hybridized hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure Graphene/golden hybridized hydrogel.After this black alkene of stone/golden hybridized hydrogel lyophilize, Graphene/golden hybrid aerogel can be obtained.
The Graphene obtained/golden hybrid aerogel is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 850 DEG C.When tube furnace temperature reaches 850 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 1h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Embodiment 16
By Palladous chloride (1mL, concentration 20mgmL
– 1) join (20mL, concentration 4mgmL in graphene oxide aqueous dispersions
– 1), then this mixture is placed on containing in teflon-lined stainless steel cauldron, at 120 DEG C of hydro-thermal reaction 12h.Question response terminates, and after temperature of reaction system is down to room temperature, said mixture forms the Graphene/palladium hybridized hydrogel of black.By a large amount of water displacement of above-mentioned hydrogel, obtain pure Graphene/palladium hybridized hydrogel.After this Graphene/palladium hybridized hydrogel lyophilize, Graphene/palladium hybrid aerogel can be obtained.
The Graphene obtained/palladium hybrid aerogel is placed on after in quartz boat, transfers them in tube furnace.By tube furnace temperature in nitrogen atmosphere with 10 DEG C of min
-1temperature rise rate rise to 950 DEG C.When tube furnace temperature reaches 950 DEG C, nitrogen gas is switched to carbon dioxide, in carbon dioxide atmosphere, activates 3h.Then with 10 DEG C of min
-1rate of temperature fall be down to room temperature, obtain the functional graphene material of high porosity.
Experimental example 1
Carry out related experiment to the functional graphene material of the obtained graphene aerogel of embodiment 3 and high porosity respectively, result is as follows:
The digital photograph of the graphene aerogel of Fig. 1 prepared by embodiment 3, as can be seen from the figure this graphene aerogel is the block materials of ater.The electron scanning micrograph of the functional graphene material of the high porosity of Fig. 2 prepared by embodiment 3, as can be seen from Figure 2 prepared functional graphene material has three-dimensional porous network structure.Fig. 3 is the transmission electron microscope photo of the functional graphene material of high porosity prepared in embodiment 3, graphene sheet layer has many folds as can see from Figure 3.
Fig. 4 is that (in figure, X-coordinate RelativePressure represents relative pressure for the nitrogen adsorption desorption graphic representation of the functional graphene material of graphene aerogel prepared in embodiment 3 and high porosity, ordinate zou AbsorbedVolume represents adsorptive capacity, CGA950-2h represents the functional graphene material of graphene aerogel at 950 DEG C of high porosities obtained after carbon dioxide activation 2h, GA represents graphene aerogel), as can be seen from Figure 4, prepared graphene aerogel and functional graphene material all have meso-hole structure, its specific surface area is respectively 690 and 2080m
2g
– 1.Fig. 5 is that (X-coordinate represents angle of diffraction for the X-ray diffractometer spectrogram of graphene aerogel prepared in embodiment 3 and functional graphene material, ordinate zou represents intensity, CGA950-2h represents the functional graphene material of graphene aerogel at 950 DEG C of high porosities obtained after carbon dioxide activation 2h, GA represents graphene aerogel, GO represents graphene oxide), can find out that the porous material of preparation has occurred a broad peak at about 24 ° of (interlamellar spacing is about 0.37nm) places.
Fig. 6 is that to the adsorption isothermal line of toluene, methyl alcohol and water vapour, (X-coordinate represents relative pressure under 298K for the functional graphene material of high porosity prepared in embodiment 3, ordinate zou represents adsorptive capacity, Toluene represents toluene, Methanol represents methyl alcohol, Water represents water), as can be seen from Figure 6 prepared functional graphene material has good organic steam absorption property, and it is respectively 2800 and 1360mgg to the adsorptive capacity of toluene and methyl alcohol
-1.
Fig. 7 is that functional graphene material prepared in embodiment 3 is at 1.0molL
-1cyclic voltammetry curve (X-coordinate represents current potential, and ordinate zou represents electric current) in tetraethylammonium tetrafluoroborate/acetonitrile electrolytic solution, as can be seen from Figure 7, all cyclic voltammetry curves all show accurate rectangular shape.When scanning speed is increased to 100mVs
-1time, the cyclic voltammetry curve of functional graphene material still keeps accurate rectangular shape.Fig. 8 is that (X-coordinate represents current density for the relation curve of the ratio capacitance of functional graphene material prepared in embodiment 3 and discharge current density, ordinate zou represents ratio capacitance), as can be seen from Figure 8 prepared functional graphene material has good high rate performance, even if when current density is increased to 10Ag
-1time, the electrochemical capacitor of functional graphene material still can reach 80Fg
-1.
Applicant states, the present invention illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, namely do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, to equivalence replacement and the interpolation of ancillary component, the concrete way choice etc. of each raw material of product of the present invention, all drops within protection scope of the present invention and open scope.
Claims (10)
1. a functional graphene material for high porosity, is characterized in that, it is the three-dimensional porous network structure formed by construction unit based on two-dimensional graphene lamella.
2. the functional graphene material of high porosity according to claim 1, is characterized in that, the specific surface area of described functional graphene material is 500-2300m
2g
– 1, pore volume is 0.5-5.5cm
3g
– 1; Preferably, specific surface area is 690-2080m
2g
– 1, pore volume is 1.2-5.4cm
3g
– 1;
Preferably, the aperture of described functional graphene material is 0.2nm-20 μm, and porosity is 85%-99%; Further preferably, aperture is 0.5nm-1 μm, and porosity is 90%-95%;
Preferably, the specific conductivity of described functional graphene material is 10
– 4-10
2scm
– 1; Further preferably, specific conductivity is 10
– 2-10
1scm
– 1.
3. the preparation method of functional graphene material described in claim 1 or 2, it is characterized in that, the method comprises carbonic acid gas and graphene aerogel or Graphene/metal hybrid aerogel generation priming reaction, and single stage method obtains the functional graphene material of high porosity;
Preferably, described priming reaction temperature is 650-1000 DEG C, more preferably 750-950 DEG C;
Preferably, the described priming reaction time is 1-20h, more preferably 1-4h;
Preferably, described priming reaction temperature rise rate is 1-50 DEG C of min
-1, more preferably 1-10 DEG C of min
-1;
Preferably, described priming reaction rate of temperature fall is 1-50 DEG C of min
-1.
4. preparation method according to claim 3, is characterized in that, the method comprise first by graphene aerogel or Graphene/metal hybrid aerogel in an inert atmosphere with 1-50 DEG C of min
-1temperature rise rate rise to 650-1000 DEG C, then inert atmosphere is switched to carbon dioxide, priming reaction 1-20h in carbon dioxide atmosphere, then with 1-50 DEG C of min
-1rate of temperature fall be down to room temperature;
Preferably, described inert atmosphere is argon gas or nitrogen;
Preferably, described priming reaction carries out in tube furnace, more preferably carries out in high temperature process furnances.
5. the preparation method according to claim 3 or 4, is characterized in that, the preparation method of described graphene aerogel or Graphene/metal hybrid aerogel comprises the following steps:
(1) graphite oxide ultrasonic disperse in water is formed graphene oxide aqueous dispersions;
Or in described graphene oxide aqueous dispersions, add inorganics further, after stirring, obtain uniform graphene oxide/inorganics aqueous dispersions; Described inorganics comprises one or more in the soluble inorganic matter of platiniferous, gold or palladium;
(2) step (1) gained graphene oxide aqueous dispersions or graphene oxide/inorganics aqueous dispersions are carried out hydro-thermal reaction, obtain even immobilising Graphene hydrogel or Graphene/metal hybrid hydrogel;
(3) wash, obtain Graphene hydrogel or Graphene/metal hybrid hydrogel;
(4) dry, obtain described graphene aerogel or Graphene/metal hybrid aerogel.
6. preparation method according to claim 5, is characterized in that, in preparation method's step (1) of described graphene aerogel or Graphene/metal hybrid aerogel,
Described graphene oxide has oxygen-containing functional group, and described oxygen-containing functional group comprises carboxyl; Preferably, described oxygen-containing functional group also comprises one or more in epoxy group(ing), hydroxyl and aldehyde radical;
Preferably, in described graphene oxide, the content of carboxyl is 10-30wt%;
Preferably, in described graphene oxide, the weight percentage of oxygen-containing functional group is 10%-50%, more preferably 20%-40%;
Preferably, described ultrasonic power is 10-600W, and ultrasonic frequency is 20-200KHz;
Preferably, in described graphene oxide aqueous dispersions, the concentration of graphene oxide is 1-10mgmL
– 1;
Preferably, the mass ratio of described graphene oxide and described inorganics is 1:1-100:1;
Preferably, described inorganics is one or more in six hydration Platinic chlorides, tetra chlorauric acid, Palladous chloride;
Preferably, in described graphene oxide/inorganics aqueous dispersions, the concentration of six hydration Platinic chlorides, tetra chlorauric acid or Palladous chloride is 0.1-20mgmL
– 1.
7. the preparation method according to claim 5 or 6, is characterized in that, in preparation method's step (2) of described graphene aerogel or Graphene/metal hybrid aerogel,
The temperature of described hydro-thermal reaction is 100-200 DEG C;
Preferably, described Graphene/metal hybrid hydrogel is one or more in Graphene/golden hybridized hydrogel, graphene/platinum hybridized hydrogel, Graphene/palladium hybridized hydrogel, Graphene/golden platinum hybrid hydrogel;
Preferably, described hydro-thermal reaction comprises puts into hydrothermal reaction kettle by described graphene oxide aqueous dispersions or graphene oxide/inorganics aqueous dispersions, is then carried out in an oven by described hydrothermal reaction kettle; Further preferably, described hydrothermal reaction kettle is autoclave;
Preferably, the temperature of described hydro-thermal reaction is 100-200 DEG C, and the time of hydro-thermal reaction is 2-24h.
8. the preparation method according to any one of claim 5-7, is characterized in that, in preparation method's step (3) of described graphene aerogel or Graphene/metal hybrid aerogel,
Described washing uses water or the trimethyl carbinol to carry out;
Preferably, Graphene hydrogel or the Graphene/metal hybrid hydrogel of inorganics is not remained after washing.
9. the preparation method according to any one of claim 5-8, is characterized in that, in preparation method's step (4) of described graphene aerogel or Graphene/metal hybrid aerogel,
Described drying means is lyophilize; Preferably, described cryodesiccated temperature is-20 DEG C-liquid nitrogen temperature, and the cryodesiccated time is 2-48h; Vacuum tightness is 5-800Pa;
Preferably, described Graphene/metal hybrid aerogel is one or more in Graphene/golden hybrid aerogel, graphene/platinum hybrid aerogel, Graphene/palladium hybrid aerogel, Graphene/golden platinum hybrid aerogel.
10. the purposes of the functional graphene material of high porosity described in claim 1 or 2, or the purposes of the functional graphene material of the high porosity that described in any one of claim 3-9 prepared by method, described purposes comprise the functional graphene materials application of described high porosity is adsorbed at organic steam sorbent material, the sorbent material of gas adsorption, the electrode of ultracapacitor, in lithium ion battery or catalysis;
Preferably, during sorbent material as organic steam, adsorbate is toluene and methyl alcohol, and adsorptive capacity is 100-4000mgg
– 1;
Preferably, during electrode as ultracapacitor, current density is 0.1-10Ag
– 1time, electrochemical capacitor is 50-200Fg
– 1.
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