CN108404822A - A kind of graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel and preparation method thereof - Google Patents
A kind of graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel and preparation method thereof Download PDFInfo
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Abstract
A method of graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel are prepared, aeroge preparing technical field is belonged to.Graphene and ultra-thin manganese dioxide nano-plates hybridized hydrogel is prepared first with hydrothermal method in the present invention, is then conveniently prepared for graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel by vacuum freeze drying process.Aeroge prepared by the present invention combines the excellent electric conductivity of graphene, the multiple advantage of the light porous feature of aeroge and the outstanding chemical property of ultra-thin manganese dioxide nano-plates, has the advantages that easy to operate, mild condition, of low cost and technique are easy to amplification.Aeroge presents microcosmic three-dimensional porous structure, the average pore size of hole is 25~50 μm, the average length of hole wall skeleton structure is 15~30 μm, and average diameter is 4.5~8.0 μm, will be with important application prospects in fields such as capacitor, catalysis, biosensor, lithium ion batteries.
Description
Technical field
The invention belongs to aeroge preparing technical fields, and in particular to one kind is received with graphene oxide and ultra-thin manganese dioxide
Rice piece is raw material, and the side of graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel is prepared by hydro-thermal reaction and freeze-drying
Method.The hybrid aerogel of preparation can be widely applied to the fields such as battery, sensing, catalysis.
Background technology
Aeroge is a kind of the light porous of the structure-controllable for mutually being coalesced by colloidal particle or high-polymer molecular and being constituted
Property solid-state material.Microcosmos network structure has abundant hole, provides big specific surface area, before it has wide application
Scape has been used for acoustic impedance coupling material, catalyst or catalyst carrier, adsorbent, filtering material, high temperature insulating material and height
Performance cell material, has attracted the research interest of more and more scholars in the recent period.
Manganese dioxide is as transition metal oxide, there are variable oxidation state, have it is resourceful, cheap,
The features such as environmental-friendly and operating voltage window is wider, chemical property is good is exactly the favorite in electrode material field all the time,
This is the most important purposes of manganese dioxide.In addition, manganese dioxide has ion exchange and Molecular Adsorption performance, in molecular sieve and urge
The fields such as agent material also show wide foreground, have received widespread attention in recent years.It is well known that the crystalline substance of nano-particle
The factors such as type, size, pattern and dimension affect the performances such as optics, electricity and the magnetics of nano material to some extent.It is existing
Research shows that size, pattern, specific surface area and the pore-size distribution of manganese dioxide particle determine ion diffusion length and
Maximum Contact face between solid electrode/solution interface prepares porous manganese bioxide material to improving its electrochemistry and catalytic
It can be of great significance.The current application study for having manganese dioxide aeroge in ultracapacitor field, but manganese dioxide
The characteristics of poorly conductive, has seriously affected the chemical property of manganese dioxide aeroge, limits manganese dioxide aeroge super
The further development of capacitor area.
Graphene is a kind of new carbon, it is to be closely packed together the two dimension formed by the single layer of carbon atom of plane
Cellular hexaplanar structure is currently known in the world most thin material.Its excellent mechanical performance, the specific surface of superelevation
Product, preferable capacity of heat transmission, high electronic conduction ability make it in super capacitor, sensor, organization bracket, drug conduction and
The fields such as solar cell become the hot spot of research.Being particularly due to graphene has superpower storage and conducts the energy of electronics
Power, Recent study personnel have carried out many trials to its application field in ultracapacitor, but in practical applications, it deposits
It is serious in interlayer polycondensation, effective surface area reduce the problem of.
Graphene and manganese dioxide hybrid aerogel combine the superior electrical conductivity of graphene, aeroge light porous spy
The multiple advantage of point and the outstanding chemical property of manganese dioxide, it would be possible to obtain more excellent performance.It reports at present
The composite construction of three-dimensional grapheme and manganese dioxide usually supports skeleton first with template structure graphene, then grows dioxy
Change manganese nano material, obtains final three-dimensional and imitate aerogel structure.Zhenan Bao etc. are in the solution by the graphene film of peeling
It is coated in three-dimensional porous weaving support construction, subsequent electrochemical deposition manganese dioxide obtains graphene@manganese dioxide three-dimensionals
Compound (Nano Lett.2011,11,2905).Yun Suk Huh etc. have synthesized a kind of three-dimensional using the method for erodent template
Graphene porous structure material, and by electric plating method growth in situ a thin layer manganese dioxide on the surface of graphene, obtain one
The composite construction (Acs Nano 2012,6,4020) of kind graphene@manganese dioxide.Peng Chen etc. are in three-dimensional foam ni substrate
Surface grows graphene, and subsequent Situ Hydrothermal grows manganese dioxide, synthesizes three-dimensional grapheme/manganese dioxide composites (Carbon
2012,50,4865).Yu Shuhong etc. is compound by the commercial sponge graphene of method structure of dipping using commercial sponge as substrate
Structure, further growth in situ manganese dioxide, design are prepared for commercial sponge@graphene@manganese dioxide three on the surface of graphene
Tie up composite construction (Nano Energy 2013,2,505).Xie Erqing etc. passes through the method for dipping using metal foam nickel as template
Nickel foam@graphene porous structures are built, then a kind of three-dimensional grapheme porous structure material is obtained with solvent corrosion nickel foam, most
Afterwards by electric plating method growth in situ manganese dioxide on the surface of graphene, a kind of flexible graphene@manganese dioxide is built
Three dimensional composite structure (ACS Nano 2013,7,174).But three-dimensional grapheme and manganese dioxide prepared by these methods
Composite construction, size and aperture are all limited by mould material, and template preparation process is complicated, and there is also mould materials point
The problem of son residual, limits a large amount of preparations of the composite material of three-dimensional grapheme and manganese dioxide and further applies.
Currently, graphene and the report of manganese dioxide hybrid aerogel are also fewer.Xiaodong Chen etc. pass through hydro-thermal
Reaction constructs the hybrid aerogel of graphene and a variety of nano materials, including spherical MnO2Nano-particle
(Adv.Mater.2014,26,3681).Han Baohang etc. by azepine graphene hydrogel by being immersed in potassium permanganate and sodium sulphate
Mixed solution in, reacted using the carbon in potassium permanganate and azepine graphene and obtain azepine graphene and manganese dioxide
Grain hybrid aerogel (CN105789628A).Manganese dioxide nano-plates have the advantages of large specific surface area, electrochemical performance,
But there is presently no the reports for preparing graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel.Therefore, a kind of at low cost
The graphene of preparation high-purity that is honest and clean, easy to operate, being readily produced amplification and ultra-thin manganese dioxide nano-plates hybrid aerogel
Method is urgently developed.
Invention content
The purpose of the present invention is to provide a kind of sides preparing graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel
Method.Graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel prepared by the present invention combine the excellent electric conductivity of graphene,
The light porous feature of aeroge and the multiple advantage of the outstanding chemical property of ultra-thin manganese dioxide nano-plates.Institute of the present invention
The method of vacuum freeze drying has the advantages that easy to operate, mild condition, of low cost and technique are easy to amplification.
Compared with existing other technologies, the invention has the advantages that：
1. manganese dioxide has two dimension in graphene prepared by the present invention and ultra-thin manganese dioxide nano-plates hybrid aerogel
Laminated structure.
2. graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel prepared by the present invention are by graphene and ultra-thin two
Aeroge skeleton is collectively formed in manganese oxide nanometer sheet, and wherein graphene and the mixing of ultra-thin manganese dioxide nano-plates is more uniform.
3. graphene and manganese dioxide in graphene prepared by the present invention and ultra-thin manganese dioxide nano-plates hybrid aerogel
Ratio can be by preparing graphene and ultra-thin manganese dioxide nano-plates hybridized hydrogel colloidal solution in graphene and two
The ratio of manganese oxide is easily adjusted.
The present invention is from the mixed solution for preparing graphene oxide and ultra-thin manganese dioxide nano-plates, first with hydro-thermal side
Graphene and ultra-thin manganese dioxide nano-plates hybridized hydrogel is prepared in method, is then facilitated by vacuum freeze drying process fast
Prompt is prepared for graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel.
A kind of method preparing graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel of the present invention, step
It is as follows：
1) preparation of manganese dioxide nano-plates：
0.15~3mmol surfactants are dissolved in 30mL deionized waters, 240~267mL is then sequentially added and goes
The septivalency manganese salt solution of ionized water, 1.8~18mL of manganous salt aqueous solution of a concentration of 5~50mM and a concentration of 5~50mM
1.2~12mL；It is heated 2~5 hours at 100~110 DEG C after mixing, auburn manganese dioxide nano is obtained after filtering
Pellet；
2) preparation of ultra-thin manganese dioxide nano-plates colloidal solution：
Manganese dioxide nano-plates precipitation ethyl alcohol and deionized water that step 1) is prepared are rinsed repeatedly and purified,
Then 1.5~25mL deionized waters are added into precipitation, ultrasound obtains the ultra-thin manganese dioxide nano-plates of sepia for 5~10 minutes
Colloidal solution；
3) preparation of graphene oxide aqueous dispersions：
Graphene oxide (Acs Nano 2010,4,4806) is prepared with the Hummer methods of improvement, then purifies simultaneously
It is made into the concentration of needs, ultrasonic disperse forms graphene oxide aqueous dispersions；
4) preparation of graphene and ultra-thin manganese dioxide nano-plates hybridized hydrogel：
The ultra-thin manganese dioxide nano-plates glue that the graphene oxide aqueous dispersions that step 3) obtains are obtained with step 2)
Liquid solution mixes, and then mixed solution is ultrasonically treated to uniform no precipitation, and polytetrafluoroethylene (PTFE) reaction under high pressure is added in mixed liquor
Hydro-thermal reaction is carried out in kettle, obtains the graphene of black and ultra-thin manganese dioxide nano-plates hybridized hydrogel；
5) preparation of graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel：
The hybridized hydrogel that step 4) is prepared is freezed, the sample of freezing is then put into vacuum freeze drying
It is freeze-dried in machine, to which graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel be prepared.
Surfactant described in step 1) be lauryl sodium sulfate, ammonium lauryl sulfate, dodecyl sulphate potassium,
Positive decyl sodium sulphate, sodium tetradecyl sulfate, dodecyl polyoxy ether sulfate, dodecyltriethanolamine sulfate, bay
One kind in sour sodium, two (2- ethylhexyls) Disodium sulfosuccinates, sodium p-octadecyl toluene sulfonate.
Manganous salt described in step 1) is one kind in manganese chloride, manganese sulfate, manganese nitrate, manganese phosphate, manganese acetate.
Septivalency manganese salt described in step 1) is potassium permanganate, sodium permanganate, high manganese lithium, acerdol, zinc permanganate, height
One kind in barium manganate, magnesium permanganate or ammonium permanganate.
The concentration of ultra-thin manganese dioxide nano-plates colloidal solution described in step 2) is 0.5~9mg/mL.
The concentration of graphene oxide aqueous dispersions made from step 3) is 5~20mg/mL.
The mass ratio of graphene oxide and ultra-thin manganese dioxide nano-plates described in step 4) is 1：1~9：1.
The temperature of hydro-thermal reaction described in step 4) is 180~200 DEG C, and the time of reaction is 3~12h.
The temperature of freezing described in step 5) is -20 DEG C~-196 DEG C, and the time is 0.5~24 hour.
The temperature of vacuum freeze drying described in step 5) is -50~-80 DEG C, and the time is 6~48 hours.
The equipment letter of the method use of the present invention for preparing graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel
List, mild condition, chemical reagent used are cheap and easy to get.By preparing graphene and ultra-thin manganese dioxide nano-plates hybridized hydrogel
Colloidal solution in the ratio of graphene and manganese dioxide be easily adjusted.The hybrid aerogel of preparation presents microcosmic
Three-dimensional porous structure, the average pore size of hole is 25~50 μm, and the average length of hole wall skeleton structure is 15~30 μm, average
A diameter of 4.5~8.0 μm.Graphene and ultra-thin manganese dioxide nano-plates aeroge prepared by the present invention is in capacitor, catalysis, life
The fields such as object sensor, lithium ion battery will be with important application prospects.
Description of the drawings
Fig. 1：The graphene for the different shape and volume that embodiment 1 is prepared and ultra-thin manganese dioxide nano-plates hydridization gas
The digital camera photo of gel；
Fig. 2：The graphene oxide (GO) and graphene and ultra-thin manganese dioxide nano-plates hydridization that embodiment 1 is prepared
Aeroge (MnO2/ rGO) Raman spectrograms；
Fig. 3：Graphene that embodiment 1 is prepared and ultra-thin manganese dioxide nano-plates hybrid aerogel are in different times magnifications
Electron scanning micrograph under several, figure (b) are the partial enlarged views of figure (a)；
Fig. 4：The manganese element X of graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel that embodiment 1 is prepared is penetrated
Photoelectron spectra figure；
Fig. 5：The digital camera for the graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel that embodiment 2 is prepared shines
Piece.
Specific implementation mode
More detailed description is done to technical scheme of the present invention with specific embodiment below, but the example is not constituted to this
The limitation of invention.
Wherein, the aqueous dispersions of the graphene oxide in embodiment 1-5 are made by the following method：
1) 1g graphite powders and 13.5mL, 85wt.% concentrated phosphoric acid are added in 120mL, 98wt.% concentrated sulfuric acid.In order to pacify
For the sake of complete, this mixture is placed in the beaker of 1000mL and is tested in draught cupboard；
2) while keeping being vigorously stirred, 6g potassium permanganate is slowly added in above-mentioned suspension, the speed of charging is controlled
Degree is 2mg s-1, charging duration is in 45min or so；
3) it after adding potassium permanganate, by beaker ParafilmTM, is used in combination tweezers to prick two apertures, continues to be vigorously stirred；
4) persistently stir 10min after, by the mixture in 50 DEG C of oil baths heating stirring 12h.With the progress of reaction, mix
The gradual retrogradation of object is closed, and has a small amount of gas to emerge；
5) it after completion of the reaction, is kept stirring, waits for that temperature of reaction system is down to room temperature, 500mL ice cubes are slowly added into
It states in mixture.After ice melting, suspension is in blackish green, lasting stirring；
6) be slowly added to the hydrogen peroxide of 30wt.% becomes manganese sulfate by remaining potassium permanganate and manganese dioxide reduction,
Until being generated without bubble.After the processing of hydrogen peroxide, suspension becomes glassy yellow, pours out supernatant after standing sedimentation；
7) hydrochloric acid of 10vol.% is added into mixture, supernatant is poured out after standing sedimentation, is repeated 3 times；It adds
Supernatant is poured out after standing sedimentation, after being repeated 3 times, graphene oxide is transferred in bag filter, thoroughly by the deionized water of 1L
Analysis makes it be further purified to neutrality；
8) graphene oxide is diluted to a certain concentration, ultrasonic 5h disperses to form graphene oxide water-dispersed
Liquid；
9) above-mentioned graphene oxide aqueous dispersions are transferred in centrifuge tube, 30min are centrifuged under 4000rpm rotating speeds,
Precipitation is removed, graphene oxide aqueous dispersions are obtained.
Embodiment 1
1) preparation of manganese dioxide nano-plates：
3mmol surfactants are dissolved in 30mL deionized waters；Then sequentially add 267mL deionized waters, concentration
For the potassium permanganate solution 1.2mL of the manganese chloride aqueous solution 1.8mL and a concentration of 50mM of 50mM；After mixing at 100 DEG C
Lower heating 3 hours obtains auburn manganese dioxide nano-plates precipitation, quality 13.5mg；
2) preparation of ultra-thin manganese dioxide nano-plates colloidal solution：
Manganese dioxide nano-plates precipitation ethyl alcohol and deionized water that step 1) is prepared are rinsed repeatedly and purified；
Then 4.5mL deionized waters are added into precipitation, the ultra-thin manganese dioxide nano-plates colloid that ultrasound obtains sepia for 5 minutes is molten
Liquid, concentration are 3.0mg mL-1；
3) preparation of graphene oxide aqueous dispersions：
Graphene oxide is prepared with the Hummer methods of improvement, then purifying obtains graphene oxide aqueous dispersions
(11.0mg mL-1)；
4) preparation of graphene and ultra-thin manganese dioxide nano-plates hybridized hydrogel：
Graphene oxide aqueous dispersions (0.82mL, the 11.0mg mL that step 3) is obtained-1) obtained with step 2)
Ultra-thin manganese dioxide nano-plates colloidal solution (1mL, 3.0mg mL-1) mixing, graphene oxide and manganese dioxide after mixing
Mass ratio is 3:1, then 1.18mL deionized waters are added into mixed solution, then mixed solution is ultrasonically treated to uniform nothing and is sunk
It forms sediment, mixed liquor is added in polytetrafluoroethylene (PTFE) autoclave, hydro-thermal reaction is carried out in 180 DEG C 6 hours, obtain the stone of black
Black alkene and ultra-thin manganese dioxide nano-plates hybridized hydrogel；
5) preparation of graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel：
The hybridized hydrogel that step 4) is prepared is freezed for 24 hours in -20 DEG C of refrigerators, is then put into the sample of freezing
10h is dried in vacuum freeze drier under the conditions of -50 DEG C, it is miscellaneous to which graphene and ultra-thin manganese dioxide nano-plates be prepared
Change aeroge, product quality 11.8mg.
Attached drawing 1 is different shape prepared in the present embodiment, the graphene of volume and ultra-thin manganese dioxide nano-plates are miscellaneous
Change the digital camera photo of aeroge.As shown, (a) figure is that volume is prepared by mold of 5mL sample bottles as 58.9mm3
Pie graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel, (b) figure is that body is prepared using 10mL sample bottles as mold
Product is 35.3mm3Cylindric graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel, (c) figure is using 20mL sample bottles as mould
It is 28.2mm that volume, which is prepared, in tool3Discoid graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel, (d) figure is different
The size comparison of shape, the graphene of volume and ultra-thin manganese dioxide nano-plates hybrid aerogel schemes.
Attached drawing 2 is preparation-obtained graphene oxide (GO) and graphene and ultra-thin manganese dioxide nano in the present embodiment
Piece hybrid aerogel (MnO2/ rGO) Raman spectrograms.Characteristic peak (the D band of graphene oxide and graphene as shown in the figure
With G band) it is all high-visible, and peak value ratio (ID/IG) by 0.84 1.05 are increased to, illustrate that graphene oxide has been reduced
As graphene.
Attached drawing 3 is that preparation-obtained graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel are swept in the present embodiment
Retouch electron micrograph.Three-dimensional porous structure is all presented in prodigious range as shown in the figure, the average pore size of hole is 30 μ
The average length of m, hole wall skeleton structure are 20 μm, and average diameter is 5.0 μm.Figure b is the partial enlarged view of figure a.
Attached drawing 4 is preparation-obtained graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel manganese member in the present embodiment
The x-ray photoelectron spectroscopy figure of element.As shown, two characteristic peaks are located at 642.1eV and 653.8eV, and combining can phase
Poor 11.7eV illustrates that manganese element exists in aeroge in the form of manganese dioxide.
Embodiment 2 (ratio)
Such as each step operation of embodiment 1, the difference is that by graphene oxide aqueous dispersions in the step 4) of embodiment 1
(0.82mL, 11.0mg mL-1) and ultra-thin manganese dioxide nano-plates colloidal solution (1mL, 3.0 mg mL-1) mixing, stone after mixing
The mass ratio of black olefinic oxide and manganese dioxide is 3:1, then 1.18mL deionized waters are added into mixed solution；And embodiment 2
The volume of the ultra-thin manganese dioxide nano-plates colloidal solution of middle addition is 0.5mL, makes graphene oxide and titanium dioxide after mixing
The mass ratio of manganese is 6:1, then 1.68mL deionized waters are added into mixed solution, then mixed solution is ultrasonically treated to uniform
Without precipitation；Graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel are further prepared using identical method.What is prepared is miscellaneous
Change aeroge and present microcosmic three-dimensional porous structure, the average pore size of hole is 35 μm, the average length of hole wall skeleton structure
It it is 22 μm, average diameter is 4.5 μm.
Embodiment 3 (total concentration)
Such as each step operation of embodiment 1, gone the difference is that 4.5mL will be added into precipitation in the step 2) of embodiment 1
Ionized water, ultrasound obtain the ultra-thin manganese dioxide nano-plates colloidal solution of sepia for 5 minutes, and concentration is 3.0mg mL-1；And implement
2.25mL deionized waters are added in example 3 into precipitation, the ultra-thin manganese dioxide nano-plates colloid that ultrasound obtains sepia for 8 minutes is molten
Liquid, concentration are 6.0mg mL-1；And by graphene oxide aqueous dispersions (0.82mL, 11.0mg in the step 4) of embodiment 1
mL-1) and ultra-thin manganese dioxide nano-plates colloidal solution (1mL, 3.0mg mL-1) mixing, graphene oxide and dioxy after mixing
The mass ratio for changing manganese is 3:1, then 1.18mL deionized waters are added into mixed solution；And the graphene oxygen being added in embodiment 3
The volume of compound aqueous dispersions is 1.64mL, and the concentration of the ultra-thin manganese dioxide nano-plates colloidal solution of addition is 6.0mg mL-1, volume is 1mL, and the mass ratio of graphene oxide and manganese dioxide is 6 after making mixing:1, then be added into mixed solution
Mixed solution is then ultrasonically treated to uniform no precipitation by 0.36mL deionized waters；Stone is further prepared using identical method
Black alkene and ultra-thin manganese dioxide nano-plates hybrid aerogel.The hybrid aerogel of preparation presents microcosmic three-dimensional porous knot
The average pore size of structure, hole is 50 μm, and the average length of hole wall skeleton structure is 30 μm, and average diameter is 8.0 μm.
Embodiment 4 (temperature)
Such as each step operation of embodiment 1, the difference is that polytetrafluoroethylene (PTFE) is added in mixed liquor in the step 4) of embodiment 1
In autoclave, hydro-thermal reaction 6h is carried out in 180 DEG C, obtains the graphene of black and ultra-thin manganese dioxide nano-plates hydridization
Hydrogel；And the temperature of hydro-thermal reaction is 200 DEG C, hydro-thermal reaction 6h in embodiment 4, obtains the graphene of black and ultra-thin dioxy
Change manganese nanometer sheet hybridized hydrogel；Graphene and ultra-thin manganese dioxide nano-plates hydridization gas are further prepared using identical method
Gel.The hybrid aerogel of preparation presents microcosmic three-dimensional porous structure, and the average pore size of hole is 25 μm, hole wall skeleton
The average length of structure is 15 μm, and average diameter is 6.0 μm.
Embodiment 5 (time)
Such as each step operation of embodiment 1, the difference is that polytetrafluoroethylene (PTFE) is added in mixed liquor in the step 4) of embodiment 1
In autoclave, hydro-thermal reaction 6h is carried out in 180 DEG C, obtains the graphene of black and ultra-thin manganese dioxide nano-plates hydridization
Hydrogel；And the temperature of hydro-thermal reaction is 180 DEG C, hydro-thermal reaction 3h in embodiment 4, obtains the graphene of black and ultra-thin dioxy
Change manganese nanometer sheet hybridized hydrogel；Graphene and ultra-thin manganese dioxide nano-plates hydridization gas are further prepared using identical method
Gel.The hybrid aerogel of preparation presents microcosmic three-dimensional porous structure, and the average pore size of hole is 30 μm, hole wall skeleton
The average length of structure is 20 μm, and average diameter is 5.0 μm.
It should be understood that the above-mentioned description for preferred embodiment is more detailed, can not therefore be considered to this
The limitation of invention patent protection range, those skilled in the art under the inspiration of the present invention, are not departing from power of the present invention
Profit requires under protected ambit, can also make the various deformations such as replacement, simple combination, of the invention is claimed model
Enclosing should be determined by the appended claims.
(the mass ratio 1 of embodiment 6:1)
Such as each step operation of embodiment 1, gone the difference is that 4.5mL will be added into precipitation in the step 2) of embodiment 1
Ionized water, ultrasound obtain the ultra-thin manganese dioxide nano-plates colloidal solution of sepia for 5 minutes, and concentration is 3.0mg mL-1；And implement
2.25mL deionized waters are added in example 3 into precipitation, the ultra-thin manganese dioxide nano-plates colloid that ultrasound obtains sepia for 8 minutes is molten
Liquid, concentration are 6.0mg mL-1；And by graphene oxide aqueous dispersions (0.82mL, 11.0mg in the step 4) of embodiment 1
mL-1) and ultra-thin manganese dioxide nano-plates colloidal solution (1mL, 3.0mg mL-1) mixing, graphene oxide and dioxy after mixing
The mass ratio for changing manganese is 3:1, then 1.18mL deionized waters are added into mixed solution；And the ultra-thin dioxy being added in embodiment 6
The concentration for changing manganese nanometer sheet colloidal solution is 6.0mg mL-1, volume is 1.5mL, makes graphene oxide and titanium dioxide after mixing
The mass ratio of manganese is 1:1, then 1.68mL deionized waters are added into mixed solution, then mixed solution is ultrasonically treated to uniform
Without precipitation；Graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel are further prepared using identical method.What is prepared is miscellaneous
Change aeroge and present microcosmic three-dimensional porous structure, the average pore size of hole is 25 μm, the average length of hole wall skeleton structure
It it is 18 μm, average diameter is 4.5 μm.
Embodiment 7
Such as each step operation of embodiment 1, the difference is that adding at 100 DEG C after mixing in the step 1) of embodiment 1
Heat 3 hours obtains auburn manganese dioxide nano-plates precipitation；And heating 3 is small at 110 DEG C after mixing in embodiment 7
When, obtain auburn manganese dioxide nano-plates precipitation；Graphene and ultra-thin titanium dioxide are further prepared using identical method
Manganese nanometer sheet hybrid aerogel.The hybrid aerogel of preparation presents microcosmic three-dimensional porous structure, and the average pore size of hole is
30 μm, the average length of hole wall skeleton structure is 20 μm, and average diameter is 5.0 μm.
Claims (7)
1. a kind of method preparing graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel, its step are as follows：
1) preparation of manganese dioxide nano-plates：
0.15~3mmol surfactants are dissolved in 30mL deionized waters, 240~267mL deionizations are then sequentially added
The septivalency manganese salt solution 1.2 of water, 1.8~18mL of manganous salt aqueous solution of a concentration of 5~50mM and a concentration of 5~50mM~
12mL；It is heated 2~5 hours at 100~110 DEG C after mixing, it is heavy that auburn manganese dioxide nano-plates is obtained after filtering
It forms sediment；
2) preparation of ultra-thin manganese dioxide nano-plates colloidal solution：
Manganese dioxide nano-plates precipitation ethyl alcohol and deionized water that step 1) is prepared are rinsed repeatedly and purified, then
1.5~25mL deionized waters are added into precipitation, ultrasound obtains the ultra-thin manganese dioxide nano-plates colloid of sepia for 5~10 minutes
Solution；
3) preparation of graphene oxide aqueous dispersions：
Graphene oxide is prepared with the Hummer methods of improvement, then purifying and ultrasonic disperse formation graphene oxide water
Dispersion liquid；
4) preparation of graphene and ultra-thin manganese dioxide nano-plates hybridized hydrogel：
The ultra-thin manganese dioxide nano-plates colloid that graphene oxide aqueous dispersions that step 3) obtains and step 2) are obtained is molten
Liquid mixes, and then mixed solution is ultrasonically treated to uniform no precipitation, and mixed liquor is added in polytetrafluoroethylene (PTFE) autoclave
Hydro-thermal reaction is carried out, the graphene of black and ultra-thin manganese dioxide nano-plates hybridized hydrogel are obtained；
5) preparation of graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel：
The hybridized hydrogel that step 4) is prepared is freezed, then the sample of freezing is put into vacuum freeze drier
Freeze-drying, to which reduced graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel be prepared.
2. a kind of method preparing graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel as described in claim 1,
It is characterized in that：Surfactant described in step 1) is lauryl sodium sulfate, ammonium lauryl sulfate, dodecyl sulphate
Potassium, positive decyl sodium sulphate, sodium tetradecyl sulfate, dodecyl polyoxy ether sulfate, dodecyltriethanolamine sulfate, the moon
One kind in sodium metasilicate, two (2- ethylhexyls) Disodium sulfosuccinates, sodium p-octadecyl toluene sulfonate；Manganous salt is chlorination
One kind in manganese, manganese sulfate, manganese nitrate, manganese phosphate, manganese acetate；Septivalency manganese salt be potassium permanganate, sodium permanganate, high manganese lithium,
One kind in acerdol, zinc permanganate, barium permanganate, magnesium permanganate or ammonium permanganate.
3. a kind of method preparing graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel as described in claim 1,
It is characterized in that：The concentration of ultra-thin manganese dioxide nano-plates colloidal solution described in step 2) is 0.5~9mg/mL.
4. a kind of method preparing graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel as described in claim 1,
It is characterized in that：The concentration of graphene oxide aqueous dispersions made from step 3) is 5~20mg/mL.
5. a kind of method preparing graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel as described in claim 1,
It is characterized in that：The mass ratio of graphene oxide and ultra-thin manganese dioxide nano-plates described in step 4) is 1：1~9：1；Hydro-thermal
The temperature of reaction is 180~200 DEG C, and the time of reaction is 3~12h.
6. a kind of method preparing graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel as described in claim 1,
It is characterized in that：The temperature of freezing described in step 5) is -20 DEG C~-196 DEG C, and the time is 0.5~24 hour；Vacuum freeze drying
Temperature be -50~-80 DEG C, the time be 6~48 hours.
7. a kind of graphene and ultra-thin manganese dioxide nano-plates hybrid aerogel, it is characterised in that：It is by claim 1~6 times
Method described in what one is prepared.
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| CN111540868A (en) * | 2020-01-21 | 2020-08-14 | 武汉船用电力推进装置研究所（中国船舶重工集团公司第七一二研究所） | Preparation method and application of two-dimensional manganese dioxide modified polypropylene diaphragm |
| CN111686679A (en) * | 2020-06-01 | 2020-09-22 | 山西大学 | Preparation method and application of manganese dioxide aerogel material |
| CN111718498A (en) * | 2020-06-16 | 2020-09-29 | 西北工业大学 | Preparation method and use method of inorganic hybrid self-repairing hydrogel |
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