CN102941042B - A kind of Graphene/metal oxide hybrid aeroge, preparation method and application thereof - Google Patents

A kind of Graphene/metal oxide hybrid aeroge, preparation method and application thereof Download PDF

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CN102941042B
CN102941042B CN201210413356.9A CN201210413356A CN102941042B CN 102941042 B CN102941042 B CN 102941042B CN 201210413356 A CN201210413356 A CN 201210413356A CN 102941042 B CN102941042 B CN 102941042B
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graphene
hybrid
metal oxide
hybrid aerogel
aeroge
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CN102941042A (en
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张学同
陈亮
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北京理工大学
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02CCAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00Capture or disposal of greenhouse gases
    • Y02C20/40Capture or disposal of greenhouse gases of CO2
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10Energy storage using batteries
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/13Energy storage using capacitors

Abstract

The present invention relates to a kind of Graphene/metal oxide hybrid aeroge, preparation method and application thereof, belong to fields of nano material application.Described hybrid aerogel is made up of Graphene network and metal oxide network, and two networks are wound hybrid aerogel mutually, and wherein metal oxide network is also crystalline state.The preparation of described hybrid aerogel comprises prepares graphene oxide organic solution, and add soluble metallic salt and epoxides wherein, obtain even immobilising hydridization wet gel, drying and charing obtain described Graphene/metal oxide hybrid aeroge.Described hybrid aerogel can be used as energy storage material, electromagnetic shielding material, the catalytic carrier of biology enzyme and CO 2sorbing material, have a wide range of applications.

Description

A kind of Graphene/metal oxide hybrid aeroge, preparation method and application thereof
Technical field
The present invention relates to a kind of Graphene/metal oxide hybrid aeroge, preparation method and application thereof, belong to fields of nano material application.
Background technology
Graphene is the thinnest in the world at present is also the hardest nano material.But also there is the physical and chemical performance of many excellences.The thermal conductivity factor of such as Graphene is up to 5300W/mK, and higher than CNT and diamond, under normal temperature, its electron mobility is more than 15000cm 2/ Vs, also than CNT or silicon wafer height, and resistivity only about 10 -6Ω cm, than copper or silver lower, be the material that at present in the world resistivity is minimum.Perfect Graphene has desirable two dimensional crystal structure, can be regarded as the graphite flake layer that one deck is stripped, each carbon atom is connected by very strong σ key and other three carbon atoms, and these very strong C-C keys cause graphene sheet layer to have excellent structural rigidity.Carbon atom has four valence electrons, each like this carbon atom contributes the pi-electron of a non-Cheng Jian, these pi-electrons become vertical direction can form π track with plane, pi-electron can move freely in crystal, give the electric conductivity that Graphene is good, and give the physicochemical properties of the many excellences of Graphene, the graphene-based material of different performance can be constructed with it.If application number is 201110207639.3, 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 add iron ion in Graphene, after high-order oxidation, obtain the composite of Graphene and tri-iron tetroxide.But described composite is pulverous amorphous state, does not have excellent internal structure.
In energy and material, state-of-the-art electrode material for super capacitor is RuO 2but, because its price is very expensive and easily cause environmental pollution, limit its application.Transition group metallic oxide is the magnetic metal oxide of tool especially, can be widely used in Magnetic Isolation, magnetic diagnosis and electromagnetic shielding field and receive 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, there is high specific capacity and environmentally safe, be considered to most suitable RuO 2alternative materials.But nearly all metal oxide is all the insulator of electricity, their application made 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, along with the high speed development of biocatalysis technology, the requirement of people to living things catalysis agent carrier is also more and more higher, and method the most conventional is at present exactly that enzyme or cell are fixed in the matrix of porous, such as, in porous silica, mesoporous activated carbon and high molecular polymer.But enzyme or cell are in use difficult to separate from reaction system, cause recycle very inconvenient.The ever more important so Magnetic Isolation also just seems in this process.
As a kind of porous material of novelty.Aeroge has high porosity (80% ~ 98%), the specific area (20 ~ 2000m of superelevation 2/ g), performance that continuous print porous etc. is excellent, 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, the novel functional material with different purposes can be obtained.
Summary of the invention
The object of this invention is to provide a kind of Graphene/metal oxide hybrid aeroge, preparation method and application, described hybrid aerogel has crystallization dual network structure, performance is more excellent compared with traditional aeroge, can be widely used in the electrode material of energy storage device, enzyme immobilizatio, electromagnetic shielding and gas absorption field.
For achieving the above object, technical scheme of the present invention is as follows:
A kind of Graphene/metal oxide hybrid aeroge, described hybrid aerogel is made up of the Graphene crystal conduction network of two dimension and the metal oxide network of crystallization, and two networks are mutually wound gel skeleton and form hybrid aerogel.
Described hybrid aerogel has crystallization dual network, and its structure is defined as: if remove arbitrarily a network (Graphene network or metal oxide network), aeroge still can keep its block structure.
The aperture of preferred described hybrid aerogel is 1nm ~ 20 μm, and porosity is 88% ~ 98%, and density is 0.03 ~ 0.80g/cm 3, specific area is 20 ~ 2000m 2/ g, conductance is 10 -5~ 10 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;
A preparation method for Graphene/metal oxide hybrid aeroge, described method step is as follows:
(1) graphene oxide solution is prepared;
Wherein, graphene oxide solution adopts the conventional method in field of preparation of graphene, prepare in water system environment, if application number is 201010263656.4, 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 ethanol replacement graphene oxide solution, centrifugation is precipitated thing, is disperseed in organic solvent by the sediment obtained, 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, dispersion obtains uniform suspension 1; Described soluble metallic salt is not containing the crystallization water or the crystallization water containing different number;
Preferred described soluble metallic salt is selected from containing 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, dispersion obtains uniform suspension 2; Suspension 2 is left standstill 2 ~ 48h at 20 DEG C ~ 80 DEG C, obtains 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 being caught by the hydrogen ion in water, the hydroxyl stayed is combined with metal ion, and form metal hydroxides, 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 step (4), dispersing mode is ultrasonic disperse or emulsion dispersion, and described emulsification carries out on high speed shear dispersion machine.
(5) hydridization wet gel is carried out drying, obtain amorphous hybrid aerogel.
In preferred steps (5), described dry run is freeze drying, be specially and add ethanol or acetone in hydridization wet gel, ethanol or acetone are poured out, after repeating 4 ~ 8 times after soaking 5 ~ 10h, water is added in hydridization wet gel, water is poured out, after repeating 2 ~ 4 times, by freezing at-5 DEG C ~-50 DEG C for hydridization wet gel >=30min after soaking 5 ~ 10h, then at 10 DEG C ~ 100 DEG C dry 30min ~ 48h, amorphous hybrid aerogel is obtained; Freezing and dry run is all carried out under the vacuum of 1 ~ 1000Pa.
Described freeze drying process by the restriction of freeze drying equipment, can any business or non-commercial freeze drying equipment in complete.Hydridization wet gel also first can adopt liquid nitrogen frozen, then proceeds to vacuum drying in freeze-dryer; Also can direct freeze drying in freeze-dryer.Freezing mode can adopt directed freezing (controlling freezing direction), and non-directional also can be adopted freezing.
In preferred steps (5), described dry run is that supercritical fluid mode is dry, be specially and add ethanol or acetone in hydridization wet gel, 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 hybrid aerogel.
Described supercritical drying process by the restriction of supercritical drying equipment, can any business or non-commercial supercritical drying equipment in complete the supercritical drying of hydridization alcohol (or ketone) gel, to obtain hybrid aerogel.
(6) hybrid aerogel is carbonized under inert gas shielding, obtain crystallization dual network Graphene/metal oxide hybrid aeroge of the present invention;
Described carbonization temperature is 260 ~ 800 DEG C, and inert gas is argon gas or nitrogen, and heating rate is 1 ~ 50 DEG C/min, and carbonization time is 1 ~ 48h, and rate of temperature fall is 1 ~ 50 DEG C/min.Described charing can be carried out in high temperature carbonization furnace.
A kind of application of Graphene/metal oxide hybrid aeroge, described application is using the electrode material of described hybrid aerogel as ultracapacitor, the ultracapacitor specific capacity obtained is 100 ~ 1000F/g, internal resistance≤0.2 Ω, leakage current≤1mA, circulate after 10000 times, ratio capacitance remains on more than 90% of initial capacitance.
An application for Graphene/metal oxide hybrid aeroge, described application is using the negative material of described hybrid aerogel as lithium ion battery, and the initial discharge capacity of described negative material is 1000 ~ 3200mAhg -1, and have good high rate performance and recycle performance, circulate after 10000 times, capability retention is more than 85%.
An application for Graphene/metal oxide hybrid aeroge, described application is using described hybrid aerogel as electromagnetic shielding material, is within the scope of 10KHz ~ 10GHz in frequency, and its shield effectiveness is 5 ~ 90dB.
A kind of application of Graphene/metal oxide hybrid aeroge, described application is using the catalytic carrier of described hybrid aerogel 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 the catalytic activity of 99%, and can recycle more than 10 times.
An application for Graphene/metal oxide hybrid aeroge, described application is as CO using described hybrid aerogel 2sorbing material, under normal temperature, adsorbance is 2.5 ~ 20mmolg -1.
In addition some Graphene/metal oxide hybrid aeroge also has electrochromic property, can be used for the design of molecular device.
Beneficial effect
1. the invention provides a kind of Graphene/metal oxide hybrid aeroge, described hybrid aerogel has crystallization dual network structure, combines the ultralight porosity characteristic of the physical and chemical performance of Graphene excellence, the functional characteristics of metal oxide and aeroge.
2. the invention provides the preparation method of described hybrid aerogel, wherein in step (2), by graphene oxide dispersion in organic solvent, be conducive to follow-up Hydrolysis Reactions of Metal-ions and polymerisation.
3. the invention provides the preparation method of described hybrid aerogel, wherein in step (4), in metal ion water solution preocess, epoxides is as a kind of proton agent for capturing, after being caught by hydrogen ion in water, the hydroxyl stayed is combined with metal ion, forms metal hydroxides, after leaving standstill, metal hydroxides polymerization forms network, obtains even immobilising hydridization wet gel.Water in reaction can be provided by the slaine with the crystallization water.
4. the invention provides the preparation method of described hybrid aerogel, wherein in step (5), after freeze drying or supercritical drying, formation be graphene oxide and unbodied metal oxide hybrid aeroge; In high temperature carbonization process in step (6), graphene oxide thermal reduction becomes the Graphene crystal of two dimension, and unbodied metal oxide generation crystal transfer, becomes the metal oxide of crystallization simultaneously.The metal oxide of described crystallization can form three-dimensional network, different from unbodied metal oxide.
5. hybrid aerogel provided by the invention, biology sensor, electrochromic device, energy storage (lithium ion battery and ultracapacitor etc.), catalyst carrier, adsorb be separated, molecular device, hydrogen storage material, electromagnetic shielding, the fields such as life science have a wide range of applications.
Accompanying drawing explanation
Fig. 1 is Graphene/Fe that embodiment 1 obtains 2o 3the SEM figure of hybrid aerogel and digital photograph;
Fig. 2 is Graphene/Co that embodiment 4 obtains 3o 4the SEM figure of hybrid aerogel and digital photograph;
Fig. 3 is SEM figure and the digital photograph of Graphene/NiO hybrid aerogel that embodiment 5 obtains;
Fig. 4 is Graphene/Fe that embodiment 1 ~ 3 obtains 2o 3nitrogen adsorption/the desorption curve of hybrid aerogel;
Fig. 5 is Graphene/Fe that embodiment 1 ~ 3 obtains 2o 3the I-V curve of hybrid aerogel;
Fig. 6 is Graphene/Fe that embodiment 1 ~ 3 obtains 2o 3the B-H loop of hybrid aerogel;
Fig. 7 is Graphene/Fe that embodiment 3 obtains 2o 3the digital photograph of the single graphene aerogel that hybrid aerogel obtains through high-temperature calcination and acid etch process and di-iron trioxide aeroge, and the SEM photo of correspondence;
Fig. 8 is the cyclic voltammetry curve of the hybrid aerogel electrode that embodiment 3 obtains;
Fig. 9 is the constant current charge-discharge curve of the hybrid aerogel electrode that embodiment 3 obtains.
Figure 10 is that the hybrid aerogel that obtains of embodiment 3 is to the curve of adsorption kinetics of glycuronidase.
Figure 11 is the catalytic activity curve of the immobilized enzyme of hybrid aerogel that embodiment 3 obtains and resolvase.
Figure 12 is that the immobilized enzyme of hybrid aerogel that embodiment 3 obtains recycles performance.
Detailed description of the invention
Below by embodiment, the invention will be further described.
Wherein, the graphene oxide organic solution in embodiment 1 ~ 7 prepares by the following method:
(1) be that the sulfuric acid of 98wt% adds in 100mL flask by 25mL concentration, be heated to 90 DEG C, under stirring condition, slowly add 5g potassium peroxydisulfate and 5g phosphorus pentoxide successively.Then be cooled to 80 DEG C, add 5g graphite powder, stirring reaction 4.5 hours, the distilled water adding 1L leaves standstill 12h, obtains pre-oxidation graphite.
(2) after carrying out filtering and washing with 2L distilled water to the pre-oxidation graphite obtained, by pre-oxidation graphite dry 12h at 50 DEG C.
(3) getting 230mL concentration is the flask that the sulfuric acid of 98wt% is placed in 1L, and be cooled with an ice bath 20min, then slowly adds dried pre-oxidation graphite and 30g potassium permanganate successively, magnetic agitation 20min; After flask is reacted 2h in 35 DEG C of water-baths, slowly add 460mL distilled water, then add the distilled water diluting of 1.4L, after stirring reaction 2h, add the hydrogen peroxide of 25mL30wt%, now the color of reactant liquor becomes khaki;
(4) in reactant liquor, add the hydrochloric acid of 5wt%, after standing sedimentation, supernatant is poured out, repeat 3 times; Add 2L distilled water again, after standing sedimentation, supernatant is poured out, centrifugal after repeating 2 times, obtain graphene oxide, described graphene oxide is made into the graphene oxide solution needing concentration.
(5) a certain amount of graphene oxide solution is got, add the hydrochloric acid that concentration is 35wt%, to producing obvious sediment after standing sedimentation, then add that a large amount of absolute ethyl alcohol carries out washing, centrifugal, collecting precipitation thing, after repeating 3 ~ 5 times, the sediment obtained is scattered in organic solvent, ultrasonic disperse forms the graphene oxide organic solution of high concentration, then with organic solvent of the same race, obtained graphene oxide organic solution is mixed with required concentration, the graphene oxide concentration of organic solution scope finally obtained is 1 ~ 12mg/mL.
Embodiment 1
1) get the graphene oxide organic solution that 5mL concentration is 1mg/mL, add 0.04gFeCl 36H 2o, ultrasonic disperse is until form uniform suspension 1.Wherein organic solvent is ethanol.
2) in suspension 1, add the epoxychloropropane of 784 μ L, then ultrasonic disperse is until form uniform suspension 2, then at 20 DEG C, leaves standstill 48h, obtains even immobilising hydridization wet gel.Wherein epoxychloropropane and Fe 3+mol ratio be 10:1.
3) in hydridization wet gel, add ethanol, after soaking 10h, ethanol is poured out, after repeating 5 times, obtain alcogel, the supercritical CO produced with SFT company of the U.S. 2the dry 24h of drying instrument, supercritical CO 2dry critical-temperature is 31.05 DEG C, and critical pressure is 7.38Pa, obtains graphene oxide/FeOx hybrid aerogel.
4) the hybrid aerogel charing 20h in the high temperature carbonization furnace (production of Tianjin Zhong Huan company) of argon shield will obtained, carbonization temperature is 260 DEG C, and heating rate is 2 DEG C/min, and rate of temperature fall is 2 DEG C/min.Obtain the Graphene/Fe of crystallization dual network structure 2o 3hybrid aerogel, wherein Graphene and Fe 2o 3theoretical Mass than for 1:5.
As required, in the Graphene/metal oxide hybrid aeroge of gained, the mass ratio of Graphene and metal oxide can be controlled within the scope of 1:100 ~ 100:1.Following examples are identical.
Embodiment 2
1) get the graphene oxide organic solution that 5mL concentration is 6mg/mL, add 0.40gFe (NO 3) 39H 2o, ultrasonic disperse is until form uniform suspension 1.Wherein organic solvent is DMF.
2) in suspension 1, add the expoxy propane of 784 μ L, then ultrasonic disperse is until form uniform suspension 2, then at 50 DEG C, leaves standstill 24h, obtains even immobilising hydridization wet gel.Its oxypropylene and Fe 3+mol ratio be 10:1.
3) in hydridization wet gel, add acetone, after soaking 5h, ethanol is poured out, after repeating 8 times, obtain alcogel, the supercritical CO produced with SFT company of the U.S. 2the dry 3h of drying instrument, supercritical CO 2dry critical-temperature is 31.05 DEG C, and critical pressure is 7.38Pa, obtains graphene oxide/FeOx hybrid aerogel.
4) the hybrid aerogel charing 48h in the high temperature carbonization furnace (production of Tianjin Zhong Huan company) of argon shield will obtained, carbonization temperature is 260 DEG C, and heating rate is 10 DEG C/min, and rate of temperature fall is 10 DEG C/min.Obtain the Graphene/Fe of crystallization dual network structure 2o 3hybrid aerogel, wherein Graphene and Fe 2o 3theoretical Mass than for 1:2.5.
Embodiment 3
1) get the graphene oxide organic solution that 5mL concentration is 12mg/mL, add 1.20gFe 2(SO4) 3, ultrasonic disperse is until form uniform suspension 1.Wherein organic solvent is isopropyl alcohol.
2) in suspension 1, add the expoxy propane of 3920 μ L, then ultrasonic disperse is until form uniform suspension 2, then at 80 DEG C, leaves standstill 2h, obtains even immobilising hydridization wet gel.Its oxypropylene and Fe 3+mol ratio be 50:1.
3) in hydridization wet gel, ethanol is added, after soaking 10h, ethanol is poured out, after repeating 4 times, water is added in hydridization wet gel, water is poured out, after repeating 2 times, by freezing at-25 DEG C for hydridization wet gel >=30min after soaking 10h, then at 70 DEG C of dry 30min, amorphous graphene oxide/FeOx hybrid aerogel is obtained; Freezing and dry run is all carried out under the vacuum of 10Pa.
4) the hybrid aerogel charing 1h in the high temperature carbonization furnace (production of Tianjin Zhong Huan company) of argon shield will obtained, carbonization temperature is 800 DEG C, and heating rate is 50 DEG C/min, and rate of temperature fall is 50 DEG C/min.Obtain the Graphene/Fe of crystallization dual network structure 2o 3hybrid aerogel, wherein Graphene and Fe 2o 3theoretical Mass than for 1:1.
Embodiment 4
1) get the graphene oxide organic solution that 5mL concentration is 12mg/mL, add 0.238gCoCl 26H 2o, ultrasonic disperse is until form uniform suspension 1.Wherein organic solvent is methyl alcohol.
2) in suspension 1, add the epoxychloropropane of 261 μ L, then ultrasonic disperse is until form uniform suspension 2, then at 35 DEG C, leaves standstill 10h, obtains even immobilising hydridization wet gel.Wherein epoxychloropropane and Co 2+mol ratio be 3:1.
3) in hydridization wet gel, add ethanol, after soaking 10h, ethanol is poured out, after repeating 5 times, obtain alcogel, the supercritical CO produced with SFT company of the U.S. 2the dry 24h of drying instrument, supercritical CO 2dry critical-temperature is 31.05 DEG C, and critical pressure is 7.38Pa, obtains graphene oxide/CoOx hybrid aerogel.
4) hybrid aerogel obtained is placed in high temperature carbonization furnace (production of Tianjin Zhong Huan company) the charing 6h of argon shield, carbonization temperature is 500 DEG C, and heating rate is 5 DEG C/min, and rate of temperature fall is 5 DEG C/min.Obtain the Graphene/Co of crystallization dual network structure 3o 4hybrid aerogel.Wherein Graphene and Co 3o 4theoretical Mass than for 1:1.
Embodiment 5
1) get the graphene oxide organic solution that 5mL concentration is 6mg/mL, add 0.48gNiCl 26H 2o, ultrasonic disperse is until form uniform suspension 1.Wherein organic solvent is oxolane.
2) in suspension 1, add the epoxychloropropane of 784 μ L, then ultrasonic disperse is until form uniform suspension 2, then at 35 DEG C, leaves standstill 10h, can obtain even immobilising hydridization wet gel.Wherein epoxychloropropane and Ni 2+mol ratio be 10:1.
3) in hydridization wet gel, acetone is added, after soaking 5h, ethanol is poured out, after repeating 4 times, water is added in hydridization ketone gel, water is poured out, after repeating 4 times, by freezing at-5 DEG C for hydridization wet gel >=30min after soaking 5h, then at 30 DEG C of dry 48h, amorphous graphene oxide/NiOx hybrid aerogel is obtained; Freezing and dry run is all carried out under the vacuum of 10Pa.
4) hybrid aerogel obtained is carbonized 12h as in the high temperature carbonization furnace (production of Tianjin Zhong Huan company) of argon shield, carbonization temperature is 500 DEG C, and heating rate is 1 DEG C/min, and rate of temperature fall is 1 DEG C/min.Obtain the Graphene/NiO hybrid aerogel of crystallization dual network structure.Wherein Graphene and the Theoretical Mass of NiO are than being 1:1.
Embodiment 6
1) get the graphene oxide organic solution that 5mL concentration is 6mg/mL, add 0.34gZrCl 46H 2o, ultrasonic disperse is until form uniform suspension 1.Wherein organic solvent is 1-METHYLPYRROLIDONE.
2) in suspension 1, add the expoxy propane of 784 μ L, then ultrasonic disperse is until form uniform suspension 2, then at 20 DEG C, leaves standstill 48h, can obtain even immobilising hydridization wet gel.Its oxypropylene and Zr 4+mol ratio be 10:1.
3) in hydridization wet gel, add ethanol, after soaking 10h, ethanol is poured out, after repeating 5 times, obtain alcogel, the supercritical CO produced with SFT company of the U.S. 2the dry 24h of drying instrument, supercritical CO 2dry critical-temperature is 31.05 DEG C, and critical pressure is 7.38Pa, obtains graphene oxide/ZrOx hybrid aerogel.
4) hybrid aerogel obtained is carbonized 12h as in the high temperature carbonization furnace (production of Tianjin Zhong Huan company) of argon shield, carbonization temperature is 600 DEG C, and heating rate is 5 DEG C/min, and rate of temperature fall is 5 DEG C/min.Obtain the Graphene/zirconia hybrid aerogel of crystallization dual network structure.Wherein Graphene and ZrO 2theoretical Mass than for 1:1.
Embodiment 7
1) get the graphene oxide organic solution that 5mL concentration is 6mg/mL, add 0.19gTiCl 4, 0.108gH 2o, ultrasonic disperse is until form uniform suspension 1.Wherein organic solvent is DMF.
2) in the suspension 1 obtained, add the expoxy propane of 784 μ L, then ultrasonic disperse is until form uniform suspension 2, then at 35 DEG C, leaves standstill 10h, can obtain even immobilising hydridization wet gel.Its oxypropylene and Ti 4+mol ratio be 10:1.
3) in hydridization wet gel, add ethanol, after soaking 10h, ethanol is poured out, after repeating 5 times, obtain alcogel, the supercritical CO produced with SFT company of the U.S. 2the dry 24h of drying instrument, supercritical CO 2dry critical-temperature is 31.05 DEG C, and critical pressure is 7.38Pa, obtains graphene oxide/TiOx hybrid aerogel.
4) hybrid aerogel obtained is carbonized 8h as in the high temperature carbonization furnace (production of Tianjin Zhong Huan company) of argon shield, carbonization temperature is 400 DEG C, and heating rate is 3 DEG C/min, and rate of temperature fall is 3 DEG C/min.Obtain the Graphene/titania hybrid aeroge of crystallization dual network structure.Wherein Graphene and TiO 2theoretical Mass than for 1:1.
Test the hybrid aerogel that embodiment 1 ~ 7 obtains, result is as follows:
Fig. 1 is Graphene/Fe that embodiment 1 obtains 2o 3eSEM (SEM) figure of hybrid aerogel and digital photograph, Fig. 2 is Graphene/Co that embodiment 4 obtains 3o 4the SEM figure of hybrid aerogel and digital photograph, Fig. 3 is SEM figure and the digital photograph of Graphene/NiO hybrid aerogel that embodiment 5 obtains.As can be seen from Fig. 1, Fig. 2 and Fig. 3, described hybrid aerogel is a kind of three-dimensional porous structure, and when metal oxide negligible amounts, metal oxide is that graininess is dispersed in graphenic surface; When metal oxide quantity is more, metal oxide can be coated by graphenic surface, forms crystallization dual network structure.
Fig. 4 is Graphene/Fe that embodiment 1 ~ 3 obtains 2o 3nitrogen adsorption/the desorption curve of hybrid aerogel, 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 hybrid aerogel is meso-hole structure, and the specific area of embodiment 1,2,3 is respectively 271m 2/ g, 287m 2/ g, 414m 2/ g, aperture is respectively 10nm, 25nm, 37nm, and the density recording hybrid aerogel by mass/volume is respectively 60 ± 5gcm -3, 40 ± 5gcm -3, 30 ± 5gcm -3; The hybrid aerogel aperture that embodiment 4 ~ 7 obtains is 1nm ~ 20 μm, and density is 0.03 ~ 0.8gcm -3, specific area is 20 ~ 2000m 2g -1.
Fig. 5 is Graphene/Fe that embodiment 1 ~ 3 obtains 2o 3the I-V curve of hybrid aerogel, curve a, b, c be corresponding embodiment 1,2,3 respectively, and wherein abscissa is voltage, and ordinate is electric current, and illustrate that described hybrid aerogel is three-dimensional conductive hybrid aerogel, the conductance of embodiment 1 ~ 3 correspondence is respectively 4.97 × 10 -3, 4.63 × 10 -2, 5.23 × 10 -2sm -1.The hybrid aerogel electrical conductivity that embodiment 4 ~ 7 obtains is 10 -5~ 10 2sm -1.
Fig. 6 is Graphene/Fe that embodiment 1 ~ 3 obtains 2o 3the B-H loop of hybrid aerogel, curve a, b, c be corresponding embodiment 1,2,3 respectively, and wherein abscissa is the magnetic field intensity applied, and ordinate is saturation magnetization.Hybrid aerogel described in explanation has good magnetic, the saturation magnetization of embodiment 1 ~ 3 correspondence is respectively 23,53,54emug -1.
Be 1 μm with Mold Making thickness, diameter is the blocky graphite alkene/Fe of 11.5cm 2o 3hybrid aerogel, then HPE7401A EMC analysis instrument is connected with the vertical flange coaxial test device of DN15115 type of Southeast China University's development, capability of electromagnetic shielding test is carried out to hybrid aerogel, test result shows that described hybrid aerogel is within the scope of frequency 100kHz ~ 1.5GHz, and shield effectiveness is about 5 ~ 90dB.There is good capability of electromagnetic shielding.
Embodiment 8.
Graphene/Fe that embodiment 3 is obtained 2o 3hybrid aerogel is calcined in the Muffle furnace communicated with air, and 500 DEG C of calcining 8h, it is 3 DEG C/min that heating rate controls, and it is 3 DEG C/min that rate of temperature fall controls, and removes Graphene network, can obtain single di-iron trioxide aeroge.
Graphene/Fe that embodiment 3 is obtained 2o 3after hybrid aerogel etches 12h with 1MHCl, again change 1MHCl etching, after repeating 4 ~ 8 times, remove di-iron trioxide network, carry out second time supercritical drying, namely obtain single graphene aerogel.
On Fig. 7, row is the digital photograph of the graphene aerogel be made up of two-dimensional graphene crystal and the SEM photo of correspondence of gained, and lower row is the digital photograph of the di-iron trioxide aeroge of the crystallization of gained and the SEM photo of correspondence.As can be seen from the figure, graphene aerogel is ater, and 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 hybrid aerogel prepared has dual network structure.And the three-dimensional porous property of single aeroge that SEM picture also demonstrates removing of network and obtains.
Embodiment 9
Graphene/Fe that embodiment 3 is obtained 2o 3after hybrid aerogel grinds with mortar, according to aeroge: acetylene black: the mass ratio of PTFE (binding agent)=87:10:3, be mixed with mixture to grind in mortar, until form homogeneous high viscosity solution, then with tablet press machine, mixture is pressed in Ni film, is placed in 120 DEG C of dryings 6 hours, is then assembled into two electrode systems, using Ni film as working electrode, Pt electrode is as to electrode.Electrolyte is the KOH solution of 6moL/L.All electro-chemical tests (test such as cyclic voltammetric and constant current charge-discharge) all carry out in CHI660D (Shanghai Chen Hua company becomes to produce) electrochemical workstation.Fig. 8 is the cyclic voltammetry curve of hybrid aerogel electrode, and wherein transverse axis is voltage, and the longitudinal axis is capacity, sweeps speed for 2mV/s; Fig. 9 is the constant current charge-discharge curve of hybrid aerogel electrode, and wherein transverse axis is the time, and the longitudinal axis is voltage.406F/g is approximately by the ratio capacitance calculating hybrid aerogel.
Embodiment 10
By the 5mg of embodiment 3 Graphene/Fe 2o 3hybrid aerogel adds containing 2gL -1(50mM in the Tris-HCl buffer solution of glycuronidase (β-glucuronidase), pH=7.3) ceaselessly shake, in ice bath (4 DEG C), hatching is after 60 minutes, survey the absorbance of solution with UV-Vis spectrum, then obtain the adsorbance of hybrid aerogel to glycuronidase.Figure 10 is the curve of adsorption kinetics of hybrid aerogel to glycuronidase, and wherein transverse axis is the time, and the longitudinal axis is adsorbance, can find out, the maximal absorptive capacity of hybrid aerogel to glycuronidase is about 2.45mg/mg.Then the enzyme after immobilization is used for catalysis glycyrrhizic acid and is converted into enoxolone, reaction equation is as follows:
Find that the catalytic activity of the enzyme after immobilization and resolvase is suitable.Figure 11 is the catalytic activity correction data figure of immobilized enzyme and resolvase.And there is magnetic due to hybrid aerogel, can Magnetic Isolation be carried out, so the enzyme after hybrid aerogel immobilization can be reused.Figure 12 is immobilised enzymes and recycles performance block diagram, and wherein abscissa is cycle-index, and ordinate is conversion ratio.Shown glycuronidase conversion ratio when using first is 99.50%, is 34.8% at the 7th circulation time conversion ratio.
In sum, these are only preferred embodiment of the present invention, be not intended to limit protection scope of the present invention.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.

Claims (8)

1. a Graphene/metal oxide hybrid aeroge, it is characterized in that: described hybrid aerogel is made up of the Graphene crystal conduction network of two dimension and the metal oxide network of crystallization, two networks are mutually wound around and form gel skeleton formation hybrid aerogel, and 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 or CeO 2; Wherein, following steps are adopted to prepare hybrid aerogel:
(1) graphene oxide solution is prepared;
(2) with the water in ethanol replacement graphene oxide solution, centrifugation is precipitated thing, is disperseed in organic solvent by the sediment obtained, obtains graphene oxide organic solution;
(3) in graphene oxide organic solution, add soluble metallic salt, dispersion obtains uniform suspension 1;
(4) in suspension 1, add epoxides, dispersion obtains uniform suspension 2; Suspension 2 is left standstill 2 ~ 48h at 20 DEG C ~ 80 DEG C, obtains even immobilising hydridization wet gel;
(5) hydridization wet gel is carried out drying, obtain amorphous hybrid aerogel;
(6) hybrid aerogel is carbonized under inert gas shielding, obtain described Graphene/metal oxide hybrid aeroge.
2. a kind of Graphene/metal oxide hybrid aeroge according to claim 1, is characterized in that: the aperture of described hybrid aerogel is 1nm ~ 20 μm, and porosity is 88% ~ 98%, and density is 0.03 ~ 0.80g/cm 3, specific area is 20 ~ 2000m 2/ g, conductance is 10 -5~ 10 2s/m.
3. a kind of Graphene/metal oxide hybrid aeroge as claimed in claim 1, it is characterized in that: in step (2), described organic solvent is selected from ethanol, dimethyl formamide, isopropyl alcohol, methyl alcohol, oxolane or 1-METHYLPYRROLIDONE; After obtaining graphene oxide organic solution, the concentration of graphene oxide is formulated as 1 ~ 12mg/mL.
4. a kind of Graphene/metal oxide hybrid aeroge as claimed in claim 1, 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.
5. a kind of Graphene/metal oxide hybrid aeroge as claimed in claim 1, is characterized in that: in step (5), and dry run is that freeze drying or supercritical fluid mode are dry;
Wherein freeze drying, be specially and add ethanol or acetone in hydridization wet gel, after soaking 5 ~ 10h, ethanol or acetone are poured out, after repeating 4 ~ 8 times, then add water in hydridization wet gel, after soaking 5 ~ 10h, water is poured out, after repeating 2 ~ 4 times, by freezing at-5 DEG C ~-50 DEG C for hydridization wet gel >=30min, then at 10 DEG C ~ 100 DEG C dry 30min ~ 48h, obtain amorphous hybrid aerogel; Freezing and dry run is all carried out under the vacuum of 1 ~ 1000Pa;
Supercritical fluid mode is dry, is specially and adds ethanol or acetone in hydridization wet gel, pours 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 hybrid aerogel.
6. a kind of Graphene/metal oxide hybrid aeroge as claimed in claim 1, it is characterized in that: in step (6), the temperature of described charing is 260 ~ 800 DEG C, inert gas is argon gas or nitrogen, heating rate is 1 ~ 50 DEG C/min, carbonization time is 1 ~ 48h, and rate of temperature fall is 1 ~ 50 DEG C/min; Described charing is carried out in high temperature carbonization furnace.
7. an application for Graphene/metal oxide hybrid aeroge as claimed in claim 1, described application be using described hybrid aerogel as energy storage material, comprise the electrode material of ultracapacitor and the negative material of lithium ion battery.
8. an application for Graphene/metal oxide hybrid aeroge as claimed in claim 1, described application is as the catalytic carrier of electromagnetic shielding material, biology enzyme or CO using described hybrid aerogel 2sorbing material.
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