CN102941042A - Graphene/metal oxide hybrid aerogel, preparation method and applications thereof - Google Patents
Graphene/metal oxide hybrid aerogel, preparation method and applications thereof Download PDFInfo
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- CN102941042A CN102941042A CN2012104133569A CN201210413356A CN102941042A CN 102941042 A CN102941042 A CN 102941042A CN 2012104133569 A CN2012104133569 A CN 2012104133569A CN 201210413356 A CN201210413356 A CN 201210413356A CN 102941042 A CN102941042 A CN 102941042A
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- hydridization
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- metal oxide
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Images
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/13—Energy storage using capacitors
Abstract
The present invention relates a graphene/metal oxide hybrid aerogel, a preparation method and applications thereof, and belongs to the field of nanometer material applications. The hybrid aerogel comprises a graphene network and a metal oxide network, wherein the two networks are mutually wound to form a hybrid aerogel, and the metal oxide network is further a crystalline state. The hybrid aerogel preparation comprises: preparing a graphene oxide organic solution, adding a soluble metal salt and an epoxide to obtain a uniform non-flowing hybrid wet gel, and carrying out drying and charring to obtain the graphene/metal oxide hybrid aerogel. The hybrid aerogel can be used as an energy storage material, an electromagnetic shielding material, a biological enzyme catalysis carrier and a CO2 absorption material, and has wide applications.
Description
Technical field
The present invention relates to a kind of Graphene/metal oxide hydridization aeroge, preparation method and application thereof, belong to fields of nano material application.
Background technology
Graphene be at present the thinnest in the world also be the hardest nano material.But also the physical and chemical performance with many excellences.For example the thermal conductivity factor of Graphene is higher than CNT and diamond up to 5300W/mK, and its electron mobility surpasses 15000cm under the normal temperature
2/ Vs, also ratio nano carbon pipe or silicon wafer height, and resistivity only approximately 10
-6Ω cm, lower than copper or silver, be the present material of resistivity minimum in the world.Perfectly Graphene has desirable two dimensional crystal structure, can be regarded as the graphite flake layer that one deck is stripped from, each carbon atom is connected by three carbon atoms of very strong σ key and other, and these very strong C-C keys cause graphene sheet layer to have excellent structural rigidity.Carbon atom has four valence electrons, each carbon atom is contributed the not pi-electron of Cheng Jian like this, these pi-electrons become vertical direction can form the π track with the plane, pi-electron can move freely in crystal, give Graphene good electric conductivity, and give the physicochemical properties of the many excellences of Graphene, can construct with it the graphene-based material of different performance.Be 201110207639.3 such as application number, denomination of invention is the application for a patent for invention of " the electromagnetic Graphene of absorbing high-frequency and ferriferrous oxide composite material and method for making ", be in Graphene, to add iron ion, obtain the composite of Graphene and tri-iron tetroxide after the high-order oxidation.But described composite is pulverous amorphous state, does not have good internal structure.
In energy and material, state-of-the-art electrode material for super capacitor is RuO
2, but because its price is very expensive and easily cause environmental pollution, limited its application.Transition group metallic oxide is the magnetic metal oxide of tool especially, can be widely used in the diagnosis of Magnetic Isolation, magnetic and electromagnetic shielding field and receives much concern.In addition magnetic metal oxide Fe
2O
3, NiO, Co
3O
4Also be a kind of very important electrode material, they are cheap, have high specific capacity and environmentally safe, are considered to only RuO
2Substitution material.But nearly all metal oxide all is the insulator of electricity, their application that makes is very limited, in order to address this problem, people add the electric conductivity that conductive filler (such as graphite, CNT and Graphene etc.) improves composite usually in metal oxide materials.On the other hand, high speed development along with biocatalysis technology, people are also more and more higher to the requirement of living things catalysis agent carrier, and the most conventional method is exactly that enzyme or cell are fixed in the matrix of porous at present, for example in porous silica, mesoporous activated carbon and the high molecular polymer.But enzyme or cell in use are difficult to separate from reaction system, cause recycle very inconvenient.The ever more important so Magnetic Isolation also just seems in this process.
Porous material as a kind of novelty.Aeroge has the specific area (20 ~ 2000m of high porosity (80% ~ 98%), superelevation
2/ g), the excellent performance such as continuous porous, can be used as hydrogen storage material and living things catalysis agent carrier.Therefore, magnetic, the energy, dielectric material and graphene aerogel are carried out functionalization, can obtain having the novel functional material of different purposes.
Summary of the invention
The purpose of this invention is to provide a kind of Graphene/metal oxide hydridization aeroge, preparation method and application, described hydridization aeroge has crystallization dual network structure, to compare performance more excellent with traditional aeroge, can be widely used in the electrode material of energy storage device, immobilization, electromagnetic shielding and the gas absorption field of enzyme.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of Graphene/metal oxide hydridization aeroge, described hydridization aeroge is comprised of the Graphene crystal conduction network of two dimension and the metal oxide network of crystallization, and two networks mutually twine and form gel skeleton formation hydridization aeroge.
Described hydridization aeroge has the crystallization dual network, and its organization definition is: if remove arbitrarily a network (Graphene network or metal oxide network), aeroge still can keep its block structure.
The aperture of preferred described hydridization aeroge is 1nm ~ 20 μ m, and porosity is 88% ~ 98%, and density is 0.03 ~ 0.80g/cm
3, specific area is 20 ~ 2000m
2/ g, conductance is 10
-510
2S/m.
Preferred described metal oxide is Fe
2O
3, Co
3O
4, NiO, ZrO
2, SnO
2, TiO
2, V
2O
5, La
2O
3, Cr
2O
3, Al
2O
3, ZnO, CeO
2
The preparation method of a kind of Graphene/metal oxide hydridization aeroge, described method step is as follows:
(1) preparation graphene oxide solution;
Wherein, graphene oxide solution adopts the conventional method in the Graphene preparation field, preparing in the water system environment, is 201010263656.4 such as application number, and denomination of invention is the preparation method of graphene oxide solution in " a kind of graphene aerogel and preparation method thereof ";
(2) with the water in the ethanol substitutionary oxydation graphene solution, centrifugation is precipitated thing, and the sediment that obtains is dispersed in the organic solvent, obtains graphene oxide organic solution;
Preferred described organic solvent is selected from ethanol, dimethyl formamide (DMF), isopropyl alcohol, methyl alcohol, oxolane or N methyl pyrrolidone.
After preferably obtaining graphene oxide organic solution, the concentration of graphene oxide is formulated as 1 ~ 12mg/mL.
(3) in graphene oxide organic solution, add soluble metallic salt, disperse to obtain uniform suspension 1; Described soluble metallic salt does not contain the crystallization water or contains the crystallization water of different numbers;
Preferred described soluble metallic salt is selected from and contains Fe
3+, Co
2+, Ni
2+, Zr
4+, Sn
4+, Ti
4+, V
5+, La
3+, Cr
3+, Al
3+, Zn
2+, Ce
4+Sulfate, nitrate, phosphate or chloride.
(4) in suspension 1, add epoxides, disperse to obtain uniform suspension 2; Suspension 2 is left standstill 2 ~ 48h under 20 ° of C ~ 80 ° C, obtain even immobilising hydridization wet gel.
Preferred described epoxides is selected from expoxy propane, epoxychloropropane or epoxy bromopropane.
Described epoxides is as a kind of proton agent for capturing, and after the seizure of the hydrogen ion in the water, the hydroxyl that stays is combined with metal ion, forms metal hydroxides, and the addition of epoxides is as the criterion metal ion all can be converted into metal hydroxides; The mol ratio of preferred epoxide and metal ion is 3:1 ~ 50:1.
In preferred steps (3) and the step (4), dispersing mode is ultrasonic dispersion or emulsion dispersion, and described emulsification is to carry out at the high speed shear dispersion machine.
(5) the hydridization wet gel is carried out drying, obtain amorphous hydridization aeroge.
In the preferred steps (5), described dry run is freeze drying, be specially and add ethanol or acetone in the hydridization wet gel, ethanol or acetone are poured out after soaking 5 ~ 10h, repeat 4 ~ 8 times after, in the hydridization wet gel, add entry, after soaking 5 ~ 10h water is poured out, repeat 2 ~ 4 times after, with hydridization wet gel freezing 〉=30min under-5 ° of C ~-50 ° C, then the dry 30min ~ 48h of ° C 10 ° of C ~ 100 obtains amorphous hydridization aeroge; Freezing and dry run is all carried out under the vacuum of 1 ~ 1000Pa.
Described freeze drying process is not subjected to the restriction of freeze drying equipment, can finish in freeze drying equipment any commerce or non-commercial.The hydridization wet gel also can adopt first liquid nitrogen frozen, then changes vacuum drying in the freeze-dryer over to; Also can directly freeze drying in freeze-dryer.Freezing mode can adopt directed freezing (controlling freezing direction), also can adopt non-directional freezing.
In the preferred steps (5), described dry run is that the supercritical fluid mode is dry, be specially in the hydridization wet gel and add ethanol or acetone, pour out after soaking 5 ~ 10h, repeat 4 ~ 8 times, obtain hydridization alcogel or hydridization ketone gel, then with Supercritical Ethanol or supercritical carbon dioxide drying 〉=2h, obtain amorphous hydridization aeroge.
Described supercritical drying drying process is not subjected to the restriction of supercritical drying equipment, can finish the supercritical drying of hydridization alcohol (or ketone) gel in supercritical drying equipment any commerce or non-commercial, to obtain the hydridization aeroge.
(6) the hydridization aeroge is carried out charing under inert gas shielding, obtain crystallization dual network Graphene of the present invention/metal oxide hydridization aeroge;
Described carbonization temperature is 260 ~ 800 ° of C, and inert gas is argon gas or nitrogen, and heating rate is 1 ~ 50 ° of C/min, and carbonization time is 1 ~ 48h, and rate of temperature fall is 1 ~ 50 ° of C/min.Described charing can be carried out in the high temperature carbonization stove.
The application of a kind of Graphene/metal oxide hydridization aeroge, described application is with the electrode material of described hydridization aeroge as ultracapacitor, the ultracapacitor specific capacity that obtains is 100 ~ 1000F/g, internal resistance≤0.2 Ω, leakage current≤1mA, circulate after 10000 times, remain on more than 90% of initial capacitance than electric capacity.
The application of a kind of Graphene/metal oxide hydridization aeroge, described application are that the first discharge capacity of described negative material is 1000 ~ 3200mAhg with the negative material of described hydridization aeroge as lithium ion battery
-1, and have good high rate performance and recycle performance, circulate after 10000 times, capability retention is more than 85%.
The application of a kind of Graphene/metal oxide hydridization aeroge, described application be with described hydridization aeroge as electromagnetic shielding material, in frequency was 10KHz ~ 10GHz scope, its shield effectiveness was 5 ~ 90dB.
The application of a kind of Graphene/metal oxide hydridization aeroge, described application is with the catalytic carrier of described hydridization aeroge as biology enzyme, the enzyme adsorbance of described catalytic carrier is 1 ~ 24mg/mg, and do not change the activity of enzyme, the later enzyme of immobilization still has 99% catalytic activity, and can be recycling more than 10 times.
The application of a kind of Graphene/metal oxide hydridization aeroge, described application are as CO with described hydridization aeroge
2Sorbing material, adsorbance is 2.5 ~ 20mmol g under the normal temperature
-1
Some Graphene/metal oxide hydridization aeroge also has electrochromic property in addition, can be used for the design of molecular device.
Beneficial effect
1. the invention provides a kind of Graphene/metal oxide hydridization aeroge, described hydridization aeroge has crystallization dual network structure, combines the physical and chemical performance of Graphene excellence, the functional characteristics of metal oxide and the ultralight porosity characteristic of aeroge.
2. the invention provides the preparation method of described hydridization aeroge, wherein in step (2), graphene oxide is dispersed in the organic solvent, be conducive to follow-up Hydrolysis Reactions of Metal-ions and polymerisation.
3. the invention provides the preparation method of described hydridization aeroge, wherein in step (4), in the Hydrolysis Reactions of Metal-ions process, epoxides is as a kind of proton agent for capturing, after the seizure of the hydrogen ion in the water, the hydroxyl that stays is combined with metal ion, forms metal hydroxides, leave standstill rear metal hydroxides polymerization and form network, obtain even immobilising hydridization wet gel.Water in the reaction can be provided by the slaine with the crystallization water.
4. the invention provides the preparation method of described hydridization aeroge, wherein in step (5), behind freeze drying or supercritical drying, formation be graphene oxide and unbodied metal oxide hydridization aeroge; In the high temperature carbonization process in step (6), the graphene oxide thermal reduction becomes the Graphene crystal of two dimension, and unbodied metal oxide generation crystal transfer simultaneously becomes the metal oxide of crystallization.The metal oxide of described crystallization can consist of three-dimensional network, and is different from unbodied metal oxide.
5. hydridization aeroge provided by the invention, biology sensor, electrochromic device, energy storage (lithium ion battery and ultracapacitor etc.), catalyst carrier, adsorb with separate, molecular device, hydrogen storage material, electromagnetic shielding, the fields such as life science have widely to be used.
Description of drawings
Fig. 1 is Graphene/Fe that embodiment 1 obtains
2O
3SEM figure and the digital photograph of hydridization aeroge;
Fig. 2 is Graphene/Fe that embodiment 4 obtains
2O
3SEM figure and the digital photograph of hydridization aeroge;
Fig. 3 is SEM figure and the digital photograph of the Graphene that obtains of embodiment 5/NiO hydridization aeroge;
Fig. 4 is Graphene/Fe that embodiment 1 ~ 3 obtains
2O
3The nitrogen adsorption of hydridization aeroge/desorption curve;
Fig. 5 is Graphene/Fe that embodiment 1 ~ 3 obtains
2O
3The I-V curve of hydridization aeroge;
Fig. 6 is Graphene/Fe that embodiment 1 ~ 3 obtains
2O
3The B-H loop of hydridization aeroge;
Fig. 7 is Graphene/Fe that embodiment 3 obtains
2O
3The hydridization aeroge is processed through high-temperature calcination and acid etch and the single graphene aerogel that obtains and the digital photograph of di-iron trioxide aeroge, and corresponding SEM photo;
Fig. 8 is the cyclic voltammetry curve of the hydridization silica aerogel electrode that obtains of embodiment 3;
Fig. 9 is the constant current charge-discharge curve of the hydridization silica aerogel electrode that obtains of embodiment 3.
Figure 10 is that the hydridization aeroge that obtains of embodiment 3 is to the curve of adsorption kinetics of glycuronidase.
Figure 11 is the immobilized enzyme of hydridization aeroge that obtains of embodiment 3 and the catalytic activity curve of resolvase.
Figure 12 is that the immobilized enzyme of hydridization aeroge that embodiment 3 obtains recycles performance.
The specific embodiment
Below by embodiment, the invention will be further described.
Wherein, the graphene oxide organic solution among the embodiment 1 ~ 9 prepares by the following method:
(1) is in the sulfuric acid adding 100mL flask of 98wt% with 25mL concentration, is heated to 90 ° of C, slowly add successively 5g potassium peroxydisulfate and 5g phosphorus pentoxide under the stirring condition.Then be cooled to 80 ° of C, add the 5g graphite powder, stirring reaction 4.5 hours, the distilled water that adds 1L leaves standstill 12h, obtains pre-oxidation graphite.
(2) with 2L distilled water the pre-oxidation graphite that obtains is carried out filtering and washing after, with pre-oxidation graphite dry 12h under 50 ° of C.
(3) getting 230mL concentration is the flask that the sulfuric acid of 98wt% places 1L, cools off 20min with ice bath, then slowly adds successively dried pre-oxidation graphite and 30g potassium permanganate, magnetic agitation 20min; Flask reacted 2h in 35 ° of C water-baths after, slowly add 460mL distilled water, add the distilled water diluting of 1.4L again, behind the stirring reaction 2h, add the hydrogen peroxide of 25mL 30wt%, this moment, the color of reactant liquor became khaki;
(4) add the hydrochloric acid of 5wt% in the reactant liquor, behind the standing sedimentation supernatant is poured out, repeat 3 times; Add again 2L distilled water, behind the standing sedimentation supernatant is poured out, centrifugal after repeating 2 times, obtain graphene oxide, described graphene oxide is made into needs the graphene oxide of concentration solution.
(5) get a certain amount of graphene oxide solution, adding concentration is the hydrochloric acid of 35wt%, behind the standing sedimentation to producing obvious sediment, then add that a large amount of absolute ethyl alcohols wash, centrifugal, collecting precipitation thing, after repeating 3 ~ 5 times, the sediment that obtains is scattered in the organic solvent, ultrasonic dispersion forms the graphene oxide organic solution of high concentration, then with organic solvent of the same race resulting graphene oxide organic solution is mixed with required concentration, the graphene oxide concentration of organic solution scope that obtains at last is 1 ~ 12mg/mL.
1) gets the graphene oxide organic solution that 5mL concentration is 1mg/mL, add 0.04gFeCl
36H
2O, ultrasonic dispersion is until form uniform suspension 1.Wherein organic solvent is ethanol.
2) add the epoxychloropropane of 784 μ L in the suspension 1, then then ultrasonic dispersion leaves standstill 48h until form uniform suspension 2 under 20 ° of C, obtains even immobilising hydridization wet gel.Wherein epoxychloropropane and Fe
3+Mol ratio be 10:1.
3) in the hydridization wet gel, add ethanol, ethanol poured out after soaking 10h, repeats 5 times after, obtain alcogel, with the supercritical CO of U.S. SFT company production
2The dry 24h of drying instrument, supercritical CO
2Dry critical-temperature is 31.05 ° of C, and critical pressure is 7.38Pa, obtains graphene oxide/FeOx hydridization aeroge.
4) with the hydridization aeroge charing 20h in the high temperature carbonization stove (ring company produces in the Tianjin) of argon shield that obtains, carbonization temperature is 260 ° of C, and heating rate is 2 ° of C/min, and rate of temperature fall is 2 ° of C/min.Obtain the Graphene/Fe of crystallization dual network structure
2O
3Hydridization aeroge, wherein Graphene and Fe
2O
3Theoretical Mass than for 1:5.
As required, in the Graphene of gained/metal oxide hydridization aeroge, the mass ratio of Graphene and metal oxide can be controlled in 1:100 ~ 100:1 scope.Following examples are identical.
1) gets the graphene oxide organic solution that 5mL concentration is 6mg/mL, add 0.40gFe (NO
3)
39H
2O, ultrasonic dispersion is until form uniform suspension 1.Wherein organic solvent is DMF.
2) add the expoxy propane of 784 μ L in the suspension 1, then then ultrasonic dispersion leaves standstill 24h until form uniform suspension 2 under 50 ° of C, obtains even immobilising hydridization wet gel.Wherein expoxy propane and Fe
3+Mol ratio be 10:1.
3) in the hydridization wet gel, add acetone, ethanol poured out after soaking 5h, repeats 8 times after, obtain alcogel, with the supercritical CO of U.S. SFT company production
2The dry 3h of drying instrument, supercritical CO
2Dry critical-temperature is 31.05 ° of C, and critical pressure is 7.38Pa, obtains graphene oxide/FeOx hydridization aeroge.
4) with the hydridization aeroge charing 48h in the high temperature carbonization stove (ring company produces in the Tianjin) of argon shield that obtains, carbonization temperature is 260 ° of C, and heating rate is 10 ° of C/min, and rate of temperature fall is 10 ° of C/min.Obtain the Graphene/Fe of crystallization dual network structure
2O
3Hydridization aeroge, wherein Graphene and Fe
2O
3Theoretical Mass than for 1:2.5.
1) gets the graphene oxide organic solution that 5mL concentration is 12mg/mL, add 1.20gFe
2(SO4)
3, ultrasonic dispersion is until form uniform suspension 1.Wherein organic solvent is isopropyl alcohol.
2) add the expoxy propane of 3920 μ L in the suspension 1, then then ultrasonic dispersion leaves standstill 2h until form uniform suspension 2 under 80 ° of C, obtains even immobilising hydridization wet gel.Wherein expoxy propane and Fe
3+Mol ratio be 50:1.
3) in the hydridization wet gel, add ethanol, after soaking 10h ethanol is poured out, after repeating 4 times, in the hydridization wet gel, add entry, after soaking 10h water is poured out, repeat 2 times after, with hydridization wet gel freezing 〉=30min under-25 ° of C, then at the dry 30min of 70 ° of C, obtain amorphous graphene oxide/FeOx hydridization aeroge; Freezing and dry run is all carried out under the vacuum of 10Pa.
4) with the hydridization aeroge charing 1h in the high temperature carbonization stove (ring company produces in the Tianjin) of argon shield that obtains, carbonization temperature is 800 ° of C, and heating rate is 50 ° of C/min, and rate of temperature fall is 50 ° of C/min.Obtain the Graphene/Fe of crystallization dual network structure
2O
3Hydridization aeroge, wherein Graphene and Fe
2O
3Theoretical Mass than for 1:1.
1) gets the graphene oxide organic solution that 5mL concentration is 12mg/mL, add 0.238gCoCl
26H
2O, ultrasonic dispersion is until form uniform suspension 1.Wherein organic solvent is methyl alcohol.
2) add the epoxychloropropane of 261 μ L in the suspension 1, then then ultrasonic dispersion leaves standstill 10h until form uniform suspension 2 under 35 ° of C, obtains even immobilising hydridization wet gel.Wherein epoxychloropropane and Co
2+Mol ratio be 3:1.
3) in the hydridization wet gel, add ethanol, ethanol poured out after soaking 10h, repeats 5 times after, obtain alcogel, with the supercritical CO of U.S. SFT company production
2The dry 24h of drying instrument, supercritical CO
2Dry critical-temperature is 31.05 ° of C, and critical pressure is 7.38Pa, obtains graphene oxide/CoOx hydridization aeroge.
4) the hydridization aeroge that obtains is placed high temperature carbonization stove (production of Tianjin ring company) the charing 6h of argon shield, carbonization temperature is 500 ° of C, and heating rate is 5 ° of C/min, and rate of temperature fall is 5 ° of C/min.Obtain the Graphene/Co of crystallization dual network structure
3O
4The hydridization aeroge.Wherein Graphene and Co
3O
4Theoretical Mass than for 1:1.
1) gets the graphene oxide organic solution that 5mL concentration is 6mg/mL, add 0.48gNiCl
26H
2O, ultrasonic dispersion is until form uniform suspension 1.Wherein organic solvent is oxolane.
2) add the epoxychloropropane of 784 μ L in the suspension 1, then then ultrasonic dispersion leaves standstill 10h until form uniform suspension 2 under 35 ° of C, can obtain even immobilising hydridization wet gel.Wherein epoxychloropropane and Ni
2+Mol ratio be 10:1.
3) in the hydridization wet gel, add acetone, after soaking 5h ethanol is poured out, after repeating 4 times, in hydridization ketone gel, add entry, after soaking 5h water is poured out, repeat 4 times after, with hydridization wet gel freezing 〉=30min under-5 ° of C, then at the dry 48h of 30 ° of C, obtain amorphous graphene oxide/NiOx hydridization aeroge; Freezing and dry run is all carried out under the vacuum of 10Pa.
4) with the hydridization aeroge that obtains as for charing 12h in the high temperature carbonization stove (ring company produces in the Tianjin) of argon shield, carbonization temperature is 500 ° of C, heating rate is 1 ° of C/min, rate of temperature fall is 1 ° of C/min.Obtain the Graphene of crystallization dual network structure/NiO hydridization aeroge.Wherein Graphene is 1:1 with the Theoretical Mass ratio of NiO.
Embodiment 6
1) gets the graphene oxide organic solution that 5mL concentration is 6mg/mL, add 0.34gZrCl
46H
2O, ultrasonic dispersion is until form uniform suspension 1.Wherein organic solvent is 1-METHYLPYRROLIDONE.
2) add the expoxy propane of 784 μ L in the suspension 1, then then ultrasonic dispersion leaves standstill 48h until form uniform suspension 2 under 20 ° of C, can obtain even immobilising hydridization wet gel.Wherein expoxy propane and Zr
4+Mol ratio be 10:1.
3) in the hydridization wet gel, add ethanol, ethanol poured out after soaking 10h, repeats 5 times after, obtain alcogel, with the supercritical CO of U.S. SFT company production
2The dry 24h of drying instrument, supercritical CO
2Dry critical-temperature is 31.05 ° of C, and critical pressure is 7.38Pa, obtains graphene oxide/ZrOx hydridization aeroge.
4) with the hydridization aeroge that obtains as for charing 12h in the high temperature carbonization stove (ring company produces in the Tianjin) of argon shield, carbonization temperature is 600 ° of C, heating rate is 5 ° of C/min, rate of temperature fall is 5 ° of C/min.Obtain the Graphene of crystallization dual network structure/zirconia hydridization aeroge.Wherein Graphene and ZrO
2Theoretical Mass than for 1:1.
1) gets the graphene oxide organic solution that 5mL concentration is 6mg/mL, add 0.19g TiCl
4, 0.108g H
2O, ultrasonic dispersion is until form uniform suspension 1.Wherein organic solvent is DMF.
2) add the expoxy propane of 784 μ L in the suspension 1 that obtains, then then ultrasonic dispersion leaves standstill 10h until form uniform suspension 2 under 35 ° of C, can obtain even immobilising hydridization wet gel.Wherein expoxy propane and Ti
4+Mol ratio be 10:1.
3) in the hydridization wet gel, add ethanol, ethanol poured out after soaking 10h, repeats 5 times after, obtain alcogel, with the supercritical CO of U.S. SFT company production
2The dry 24h of drying instrument, supercritical CO
2Dry critical-temperature is 31.05 ° of C, and critical pressure is 7.38Pa, obtains graphene oxide/TiOx hydridization aeroge.
4) with the hydridization aeroge that obtains as for charing 8h in the high temperature carbonization stove (ring company produces in the Tianjin) of argon shield, carbonization temperature is 400 ° of C, heating rate is 3 ° of C/min, rate of temperature fall is 3 ° of C/min.Obtain the Graphene of crystallization dual network structure/titania hybrid aeroge.Wherein Graphene and TiO
2Theoretical Mass than for 1:1.
The hydridization aeroge that embodiment 1 ~ 7 obtains is tested, and the result is as follows:
Fig. 1 is Graphene/Fe that embodiment 1 obtains
2O
3The ESEM of hydridization aeroge (SEM) figure and digital photograph, Fig. 2 is Graphene/Fe that embodiment 4 obtains
2O
3The SEM of hydridization aeroge figure and digital photograph, Fig. 3 are SEM figure and the digital photograph of the Graphene that obtains of embodiment 5/NiO hydridization aeroge.Can find out from Fig. 1, Fig. 2 and Fig. 3, described hydridization aeroge is a kind of three-dimensional porous structure, and when the metal oxide negligible amounts, metal oxide is graininess and is dispersed in the Graphene surface; When metal oxide quantity was more, metal oxide can coat the Graphene surface, forms crystallization dual network structure.
Fig. 4 is Graphene/Fe that embodiment 1 ~ 3 obtains
2O
3The nitrogen adsorption of hydridization aeroge/desorption curve, curve a, b, c be corresponding embodiment 1,2,3 respectively, and wherein transverse axis is test pressure, and the longitudinal axis is adsorbance, illustrates that described hydridization aeroge is meso-hole structure, and embodiment 1,2,3 specific area are respectively 271m
2/ g, 287m
2/ g, 414m
2/ g, the aperture is respectively 10nm, 25nm, 37nm, and the density that records the hydridization aeroge with mass/volume is respectively 60 ± 5g cm
-3, 40 ± 5g cm
-3, 30 ± 5g cm
-3The hydridization aeroge aperture that embodiment 4 ~ 7 obtains is 1nm ~ 20 μ m, and density is 0.03 ~ 0.8g cm
-3, specific area is 20 ~ 2000m
2g
-1
Fig. 5 is Graphene/Fe that embodiment 1 ~ 3 obtains
2O
3The I-V curve of hydridization aeroge, curve a, b, c be corresponding embodiment 1,2,3 respectively, and wherein abscissa is voltage, and ordinate is electric current, illustrates that described hydridization aeroge is three-dimensional conduction hydridization aeroge, and the conductance of embodiment 1 ~ 3 correspondence is respectively 4.97 * 10
-3, 4.63 * 10
-2, 5.23 * 10
-2S m
-1The hydridization aeroge electrical conductivity that embodiment 4 ~ 7 obtains is 10
-5~ 10
2S m
-1
Fig. 6 is Graphene/Fe that embodiment 1 ~ 3 obtains
2O
3The B-H loop of hydridization aeroge, curve a, b, c be corresponding embodiment 1,2,3 respectively, and wherein abscissa is the magnetic field intensity that applies, and ordinate is saturation magnetization.Illustrate that described hydridization aeroge has good magnetic, the saturation magnetization of embodiment 1 ~ 3 correspondence is respectively 23,53,54emu g
-1
Be 1 μ m with Mold Making thickness, diameter is blocky graphite alkene/Fe of 11.5cm
2O
3The hydridization aeroge, then the vertical flange coaxial test device of DN15115 type with Southeast China University's development connects HPE7401A EMC analysis instrument, the hydridization aeroge is carried out the capability of electromagnetic shielding test, test result shows described hydridization aeroge in frequency 100kHz ~ 1.5GHz scope, and shield effectiveness is about 5 ~ 90dB.Has good capability of electromagnetic shielding.
Graphene/Fe that embodiment 3 is obtained
2O
3The hydridization aeroge with Muffle furnace that air communicates in calcine, 500 ° of C calcining 8h, heating rate is controlled to be 3 ° of C/min, rate of temperature fall is controlled to be 3 ° of C/min, removes the Graphene network, can obtain single di-iron trioxide aeroge.
Graphene/Fe that embodiment 3 is obtained
2O
3The hydridization aeroge with 1M HCl etching 12h after, again change 1M HCl etching, repeat 4 ~ 8 times after, remove the di-iron trioxide network, carry out the supercritical drying second time, namely obtain single graphene aerogel.
Row is digital photograph and the corresponding SEM photo of the graphene aerogel that is made of two-dimentional Graphene crystal of gained, the SEM photo of the digital photograph of the di-iron trioxide aeroge of the crystallization that lower row be gained and correspondence on Fig. 7.As can be seen from the figure, graphene aerogel is ater, and the di-iron trioxide aeroge is rufous, when removing Graphene network or di-iron trioxide network, remaining network still can keep the block structure of aeroge, shows that the hydridization aeroge for preparing has the dual network structure.And the SEM picture has also proved the three-dimensional porous property of removing of network and resulting single aeroge.
Graphene/Fe that embodiment 3 is obtained
2O
3After the hydridization aeroge grinds with mortar, according to aeroge: acetylene black: the PTFE(binding agent)=mass ratio of 87:10:3, being mixed with mixture grinds in mortar, until form the high viscosity solution of homogeneous, then with tablet press machine mixture is pressed in the Ni film, placed 120 ° of C dry 6 hours, then be assembled into two electrode systems, as working electrode, the conduct of Pt electrode is to electrode with the Ni film.Electrolyte is the KOH solution of 6moL/L.All electro-chemical tests (tests such as cyclic voltammetric and constant current charge-discharge) all become to produce in CHI660D(Shanghai occasion China company) carry out in the electrochemical workstation.Fig. 8 is the cyclic voltammetry curve of hydridization silica aerogel electrode, and wherein transverse axis is voltage, and the longitudinal axis is capacity, sweeps speed and is 2mV/s; Fig. 9 is the constant current charge-discharge curve of hydridization silica aerogel electrode, and wherein transverse axis is the time, and the longitudinal axis is voltage.Be approximately 406F/g by the ratio electric capacity that calculates the hydridization aeroge.
5mg Graphene/Fe with embodiment 3
2O
3The hydridization aeroge adds and contains 2g L
-1Glycuronidase ((50mM in the Tris-HCl buffer solution of β-glucuronidase), pH=7.3) ceaselessly concussion, hatching was surveyed the absorbance of solution after 60 minutes with UV-Vis spectrum in ice bath (4 ° of C), then obtained the hydridization aeroge to the adsorbance of glycuronidase.Figure 10 be the hydridization aeroge to the curve of adsorption kinetics of glycuronidase, wherein transverse axis is the time, the longitudinal axis is adsorbance, can find out, the hydridization aeroge is about 2.45mg/mg to the maximal absorptive capacity of glycuronidase.Then the enzyme after the immobilization is used for the catalysis glycyrrhizic acid and is converted into enoxolone, reaction equation is as follows:
Enzyme after the discovery immobilization is suitable with the catalytic activity of resolvase.Figure 11 is the catalytic activity correction data figure of immobilized enzyme and resolvase.And because the hydridization aeroge has magnetic, can carry out Magnetic Isolation, so the endonuclease capable after the immobilization of hydridization aeroge is reused.Figure 12 is immobilised enzymes and recycles the performance block diagram, and wherein abscissa is cycle-index, and ordinate is conversion ratio.Shown in glycuronidase conversion ratio when using first be 99.50%, be 34.8% at the 7th circulation time conversion ratio.
In sum, above is preferred embodiment of the present invention only, is not for limiting protection scope of the present invention.Within the spirit and principles in the present invention all, any modification of doing, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. Graphene/metal oxide hydridization aeroge, it is characterized in that: described hydridization aeroge is comprised of the Graphene crystal conduction network of two dimension and the metal oxide network of crystallization, and two networks mutually twine and consist of gel skeleton and consist of the hydridization aeroge.
2. a kind of Graphene according to claim 1/metal oxide hydridization aeroge, it is characterized in that: the aperture of described hydridization aeroge is 1nm ~ 20 μ m, and porosity is 88% ~ 98%, and density is 0.03 ~ 0.80g/cm
3, specific area is 20 ~ 2000m
2/ g, conductance is 10
-510
2S/m.
3. the preparation method of a kind of Graphene as claimed in claim 1/metal oxide hydridization aeroge, it is characterized in that: described method step is as follows:
(1) preparation graphene oxide solution;
(2) with the water in the ethanol substitutionary oxydation graphene solution, centrifugation is precipitated thing, and the sediment that obtains is dispersed in the organic solvent, obtains graphene oxide organic solution;
(3) in graphene oxide organic solution, add soluble metallic salt, disperse to obtain uniform suspension 1;
(4) in suspension 1, add epoxides, disperse to obtain uniform suspension 2; Suspension 2 is left standstill 2 ~ 48h under 20 ° of C ~ 80 ° C, obtain even immobilising hydridization wet gel;
(5) the hydridization wet gel is carried out drying, obtain amorphous hydridization aeroge;
(6) the hydridization aeroge is carried out charing under inert gas shielding, obtain described Graphene/metal oxide hydridization aeroge.
4. the preparation method of a kind of Graphene as claimed in claim 3/metal oxide hydridization aeroge, it is characterized in that: in step (2), described organic solvent is selected from ethanol, dimethyl formamide, isopropyl alcohol, methyl alcohol, oxolane or N methyl pyrrolidone; After obtaining graphene oxide organic solution, the concentration of graphene oxide is formulated as 1 ~ 12mg/mL.
5. the preparation method of a kind of Graphene as claimed in claim 3/metal oxide hydridization aeroge, it is characterized in that: in step (3), described soluble metallic salt is selected from and contains Fe
3+, Co
2+, Ni
2+, Zr
4+, Sn
4+, Ti
4+, V
5+, La
3+, Cr
3+, Al
3+, Zn
2+, Ce
4+Sulfate, nitrate, phosphate or chloride, in the Graphene that obtains/metal oxide hydridization aeroge, described metal oxide is Fe
2O
3, Co
3O
4, NiO, ZrO
2, SnO
2, TiO
2, V
2O
5, La
2O
3, Cr
2O
3, Al
2O
3, ZnO, CeO
2
6. the preparation method of a kind of Graphene as claimed in claim 3/metal oxide hydridization aeroge, it is characterized in that: in step (4), described epoxides is selected from expoxy propane, epoxychloropropane or epoxy bromopropane; The mol ratio of epoxides and metal ion is 3:1 ~ 50:1.
7. the preparation method of a kind of Graphene as claimed in claim 3/metal oxide hydridization aeroge is characterized in that: in the step (5), described dry run is that freeze drying or supercritical fluid mode are dry;
Wherein freeze drying, be specially in the hydridization wet gel and add ethanol or acetone, after soaking 5 ~ 10h ethanol or acetone are poured out, after repeating 4 ~ 8 times, in the hydridization wet gel, add entry again, behind immersion 5 ~ 10h water is poured out, after repeating 2 ~ 4 times, with hybridized hydrogel freezing 〉=30min under-5 ° of C ~-50 ° C, then the dry 30min ~ 48h of ° C 10 ° of C ~ 100 obtains amorphous hydridization aeroge; Freezing and dry run is all carried out under the vacuum of 1 ~ 1000Pa;
The supercritical fluid mode is dry, is specially in the hydridization wet gel to add ethanol or acetone, pours out behind immersion 5 ~ 10h, repeat 4 ~ 8 times, obtain hydridization alcogel or hydridization ketone gel, then with Supercritical Ethanol or supercritical carbon dioxide drying 〉=2h, obtain amorphous hydridization aeroge.
8. the preparation method of a kind of Graphene as claimed in claim 3/metal oxide hydridization aeroge, it is characterized in that: in the step (6), described carbonization temperature is 260 ~ 800 ° of C, inert gas is argon gas or nitrogen, heating rate is 1 ~ 50 ° of C/min, carbonization time is 1 ~ 48h, and rate of temperature fall is 1 ~ 50 ° of C/min.Described charing is carried out in the high temperature carbonization stove.
9. the application of Graphene/metal oxide hydridization aeroge, described application be with described hydridization aeroge as energy storage material, comprise the electrode material of ultracapacitor and the negative material of lithium ion battery.
10. the application of Graphene/metal oxide hydridization aeroge, described application are with catalytic carrier or the CO of described hydridization aeroge as electromagnetic shielding material, biology enzyme
2Sorbing material.
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