CN105906364B - Compressible aeroge of a kind of graphene based on hydrothermal reduction method and preparation method thereof, application - Google Patents
Compressible aeroge of a kind of graphene based on hydrothermal reduction method and preparation method thereof, application Download PDFInfo
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Abstract
The present invention provides compressible aeroge of a kind of graphene based on hydrothermal reduction method and preparation method thereof, application.Using original graphite as raw material, graphene oxide (GO) is prepared using Hummers methods first, then again using graphene oxide as raw material, hydrogel is prepared using high temperature reduction mode hydro-thermal method by the 1 pyrene butyric acid (OPBA) of γ oxos for adding in various concentration, Polymer Solution is impregnated after freeze-drying and obtains compressible aeroge, there is larger application in terms of hydrophilic and oleophilic and electric transducer.The compressibility of preparation, the graphite oxide aerogel of elastomeric state, for development environment friendly, the premium quality product for meeting the top grades such as industrial pipeline, survival capsule, warship bulkhead leather rigors has important directive significance.Step is simple and convenient to operate, is highly practical.
Description
Technical field
The invention belongs to polymeric material field, the compressible airsetting of more particularly to a kind of graphene based on hydrothermal reduction method
Glue and preparation method thereof, application.
Background technology
Graphene (Graphene) is a kind of single layer of carbon atom material, is by sp2The bi-dimensional cellular of hydbridized carbon atoms composition
Shape crystal.This carbon thin slice of one layer of carbon atom thickness " only ", by everybody be considered it is current in the world it is known it is most hard, most have
Toughness, most thin new material.Graphene has very high intensity, since the powerful active force between carbon atom becomes at present
The best material of known mechanical strength.Graphene is also harder than diamond, and the intensity steel more best than in the world is also high by 100
Times.Its unique rock-steady structure makes graphene also have special electric light thermal characteristics, including half-integer quantum hall effect, high ratio
Surface area, spin(-)orbit reciprocation, high-termal conductivity, zero gap semiconductor, high electron/hole mobility and excellent machinery
Performance is considered compound in the quantum devices such as integrated circuit, single-molecule detection device, field-effect transistor, energy storage material, functionality
Material, catalyst carrier etc. have very extensive application prospect.
Graphene is usually removed by graphite surface and obtained, and the method used earliest is that machinery strips off method.And in other techniques
In, it is graphite oxide usually by graphite initial oxidation, then ultrasonic disperse obtains graphene oxide (GO), finally by various reduction
Means obtain redox graphene (RGO).
Graphene is a kind of than more loose substance, is easy to reunite in macromolecule matrix, and graphene is in itself not
Hydrophilic, not oleophylic also limits the compound of graphene and other high-molecular compounds to a certain extent, and especially nanometer is answered
It closes.Thus, Many researchers have carried out the modification of graphene many research, to improve the parent of graphene and macromolecule matrix
And property, it is compound well so as to obtain.
Hydrogel is a kind of special dispersion, be by macromolecule, small molecule aggregation or colloidal particle by physics or
The water-filled threedimensional solid hydrophilic network structural system of chemical crosslinking.As a kind of new soft material, hydrogel is used extensively
In artificial tissue, pharmaceutical carrier, electrode material, sensor and adsorbent etc..Conventional hydrogels are generally by organic polymer
It is crosslinked, but its poor mechanical performance and stability limit their extensive use.Water conservancy in hydrogel is used
Air replaces, then transform hydrogel is aeroge.Carbonaceous hydrogel and aeroge be a major class by the gel of very big concern,
Due to its multifunctionality.The porous structure of three-dimensional network and carbon gel can provide effective diffusion of electrolyte ion and electronics,
So as to cause good application prospect in ultracapacitor.CNT bases aeroge and graphene aerogel keep high electric conductivity, hard
Solid mechanical performance, the advantages of excellent flexibility and high surface area.Importantly, many aeroges is Free Station
It is vertical, without adhesive and easy mass production.These advantages allow them as light and handy flexibly electrode of super capacitor-one
A suitable power supply is used for portable and wearable electronic device.
As a kind of important structural material, porous compressible flexible material is because it is in the energy, life science and environment
The wide application prospects of technical fields such as protection cause researcher and widely pay close attention in recent years.It is however, same in same structure
The performances such as the pore structure of Shi Shixian prosperities, compressive characteristics but not a duck soup.During material porosity is improved, often
It can lead to the brittleness of structure, cause the reduction of mechanical performance.How to select suitable construction unit, nanoscale up regulation its
Performance and to carry out the ultralight high resiliency macrostructure that Controllable assembly realizes that this kind of hole is flourishing and mechanical performance is excellent be a richness
Challenging subject.
Invention content
In order to overcome above-mentioned deficiency, the present invention provide a kind of compressible aeroge of graphene based on hydrothermal reduction method and its
Preparation method, application.The compressibility of preparation, the graphene aerogel of elastomeric state, disclosure satisfy that energy snubber, damping, environmental protection
The rigors of contour performance products.
In the prior art generally using phenolic resin class substances such as resorcinol, formaldehyde as adhesive, the graphite of preparation
Although alkene aeroge has low-density, high-specific surface area, macropore volume, high conductivity, good thermal stability and structure-controllable
The advantages that, but effectively elastic connection can not be formed between graphene level, the compressibility of aeroge, bad mechanical property.For
Overcome the above problem, the present invention is had found on the basis of the theory analysis and large-scale experiment：Using γ-oxo -1- pyrene butyric acid
When OPBA is as adhesive, there is π-π interaction forces, OPBA and high molecular polymer using OPBA and RGO (between phenyl ring)
Hydrogen bond between HMP, the interaction of hydrogen bond between HMP and RGO, three kinds of active forces of formation can assign aeroge it is excellent can
Compressibility and mechanical performance.
To achieve the above object, the present invention adopts the following technical scheme that：
A kind of preparation method of the compressible aeroge of graphene based on hydrothermal reduction method, including：
It is adhesive by raw material, γ-oxo -1- pyrene butyric acid OPBA of graphene oxide-GO, hydro-thermal pyrolysis reduction is made
RGO-OPBA aeroges；
The dip-coating macromolecule polymer solution HMP on RGO-OPBA aeroges removes solvent to get RGO-OPBA-HMP
Aeroge.
Preferably, the mass ratio of the graphene oxide, γ-oxo -1- pyrene butyric acid is：4~16:1~1.2；
Preferably, the high temperature pyrolysis reducing condition is：160~200 DEG C, reaction time 10-18h；
Preferably, the high molecular polymer is PVAC polyvinylalcohol, polyvinyl acetate emulsion PVAC, polyacrylamide PAM
In one or more combinations.
Preferably, the condition of the dip-coating is：By RGO-OPBA aeroges in the height that mass concentration is 0.5~30mg/ml
It is impregnated 5~6 hours in Molecularly Imprinted Polymer Solution H MP solution.
Preferably, the graphene oxide is prepared by the oxidation in the acid of mixing or the system of oxidant, described
Acid or oxidant are preferably selected from H2SO4、HNO3、H2O2、KMnO4、K2Cr2O7。
Preferably, the specific method for removing solvent is supercritical drying, desivac, room temperature and environmental pressure drying
Technology is implemented to form aeroge.
Preferably, the amount for being present in the impurity in the RGO-OPBA-HMP aeroges is less than 5%.
The present invention also provides a kind of preparation method of the compressible aeroge of the graphene preferably based on hydrothermal reduction method,
Including：
The preparation of 1.GO
Using natural flake graphite as raw material, graphite oxide is prepared using Hummers methods.Under ice bath state, 24mL is taken
The concentrated sulfuric acid is placed in 200mL flasks, and adds in 1.0g graphite and 0.8gNaNO thereto3, stir evenly and be slow added into backward
5gKMnO4Powder (adds in) in three times, and solution is warming up to 40 DEG C of reaction 2h after stirring 10min.It is warming up to 70 DEG C of reactions
30min is slowly added to 50mL deionized waters when solution temperature drops to room temperature, and 3mL is added in inwards when temperature is down to 0 DEG C
30% H2O2To terminate reaction, reactant becomes golden yellow, and until bubble-free from brownish black.Centrifugation is carried out to reaction solution to wash
Wash, the ultrasound that the solution containing graphite oxide after washing is carried out to 30min is removed, then centrifuged under the conditions of 1000rpm with
Remove unstripped graphite oxide, then centrifuge under 4500rpm 10min take precipitation be dried in vacuo after up to graphene oxide powder
End.A certain amount of graphene oxide powder is taken to be dispersed in water, ultrasound prepares GO suspension.Then it is placed on KQ3200B types ultrasound
Ultrasound 6h takes out in wave washer.
2. constant volume
The graphite oxide of 3-5ml is taken to be uniformly distributed it in culture dish, weigh, culture dish is put into DHG-9070A types
3h or so in electric heating constant-temperature blowing drying box, takes out culture dish, weighs again later, then places into DHG-9070A type electric heating
In constant temperature blast drying oven, until its gross mass no longer changes, its final mass is weighed, you can calculate the dense of graphite oxide
Degree.
3. the preparation of the compressible aeroge of hydrothermal reduction
Graphite oxide (GO) alkene solution of 2-6mg/ml is configured, is put into reaction kettle after ultrasonic disperse is uniform.With mass ratio
(GO：OPBA=4:1；8:1；10:1；12:1；16:1) ratio adds in a concentration of 1-2mg/ml and is dispersed in absolute ethyl alcohol
γ-oxo -1- pyrenes butyric acid (OPBA).The mixed solution being configured is placed on DF-101S heat collecting type heated at constant temperature magnetic agitations
0.5-1h is stirred at room temperature on device.It is put into after stirring evenly in DHG-9070A type electric heating constant-temperature blowing drying boxes, temperature is adjusted to
180 DEG C, reaction time 12-18h.After reaction, it takes out sample to be cleaned repeatedly with distilled water for several times, freeze-drying obtains RGO-
OPBA aeroges.The Polymer Solution (PVAC polyvinylalcohol) that compound concentration is 0.5,1,3,5,10,30mg/ml, by RGO-
OPBA aeroges immerse, and impregnate 5 hours, and freeze-drying obtains compressible aeroge.
The present invention also provides the RGO-OPBA-HMP aeroges that can be obtained by any aforementioned method.
The present invention also provides a kind of aeroges, have 1-22.54mg/cm3Density.
The present invention also provides with 1-22.54mg/cm3Density aeroge, including listed in any preceding method
The arbitrary characteristics gone out.
The present invention also provides the aeroges that can be obtained by any preceding method.
The present invention also provides the catalyst including any aforementioned RGO-OPBA-HMP aeroges or catalyst carriers, non-
Reflecting plate, electro-chemical device electrode, for solvent, oil, gasoline and the absorber material of liquid absorption, filter, gas absorption
Medium, Water warfare medium.
The design principle of the present invention
The present invention by by between GO lamellas between the decrease of electrostatic repulsion and RGO and OPBA π-π interact reinforcement
Assemble synthesized gel rubber.Aeroge is immersed in the aqueous solution of PVA again, RGO-OPBA-PVA aeroges are obtained by freeze-drying.
In RGO-OPBA-PVA aeroges, OPBA plays the role of critical as a kind of " glue ".Due to existing in aeroge
Three kinds of active forces and make aeroge have compressibility, stable structure.First, OPBA and RGO (between phenyl ring) has π-π phases
Interreaction force；Secondly, there is the interaction force (hydroxyl of the carbonyl of OPBA, hydroxyl group and PVA of hydrogen bond between OPBA and PVA
Group forms hydrogen bond).These types of active force imparts the excellent mechanical performance of the compressible aeroge (Fig. 1 b) of graphene.Outside
Under force compresses, simple graphene aerogel rupture in i.In contrast, hydrothermal reduction RGO-OPBA-PVA in ii (ρ=
22.54mg/cm3), integrity is kept, and can restore to the original state within a very short time in outer force compresses lower structure.
Beneficial effects of the present invention：
(1) present invention prepare compressibility, elastomeric state graphene aerogel, for development environment friendly, meet
The high-grade premium quality product with leather rigors such as industrial pipeline, survival capsule, warship bulkhead has important directive significance.
(2) RGO-OPBA-HMP aeroges of the invention have excellent compressibility, stable structure, high absorption capacity
By force, there is larger application in terms of hydrophilic and oleophilic and electric transducer.
(3) preparation process of the invention is simple, efficient, easy to operate, highly practical.
Description of the drawings
Fig. 1 be hydro-thermal method prepare compressible graphene aerogel prepare schematic diagram and product pictorial diagram.Wherein, a is system
Standby schematic diagram.Bi is that simple RGO aeroges are incompressible.Bii prepares RGO-OPBA-PVA aeroges for high temperature reduction.
Fig. 2 is properties of product test chart.Wherein, a, b are the fluorescence spectra of aeroge, and c is the TGA (thermogravimetric) of OPBA
Figure, d be RGO and OPBA different qualities than hydrogel ultraviolet spectrogram, e is for RGO with OPVA different qualities than hydrogel
Picture.
Fig. 3 is the stress-strain function curve graph of aeroge.Wherein, a is the PVA that RGO-OPBA-PVA aeroges impregnate
The function of concentration and its density.B-e is the strain stress curve of PVA a concentration of 0.5,1,3,5mg/ml.
Fig. 4 is hydrophilic and oleophilic performance figure.
Fig. 5 is pressure drag electric conductivity figure.
Specific embodiment
Feature of present invention and other correlated characteristics are described in further detail by the following examples, in order to the same industry
The understanding of technical staff：
Embodiment 1
The preparation of 1.GO
Using natural flake graphite as raw material, graphite oxide is prepared using Hummers methods.Under ice bath state, 24mL is taken
The concentrated sulfuric acid is placed in 200mL flasks, and adds in 1.0g graphite and 0.8g NaNO thereto3, stir evenly and be slow added into backward
5g KMnO4Powder (adds in) in three times, and solution is warming up to 40 DEG C of reaction 2h after stirring 10min.It is warming up to 70 DEG C of reactions
30min is slowly added to 50mL deionized waters when solution temperature drops to room temperature, and 3mL is added in inwards when temperature is down to 0 DEG C
30% H2O2To terminate reaction, reactant becomes golden yellow, and until bubble-free from brownish black.Centrifugation is carried out to reaction solution to wash
Wash, the ultrasound that the solution containing graphite oxide after washing is carried out to 30min is removed, then centrifuged under the conditions of 1000rpm with
Remove unstripped graphite oxide, then at 3,000 rpm centrifugation 10min take precipitation be dried in vacuo after up to graphene oxide powder
End.A certain amount of graphene oxide powder is taken to be dispersed in water, ultrasound prepares GO suspension.Then it is placed on KQ3200B types ultrasound
Ultrasound 6h takes out in wave washer.
2. constant volume
The graphite oxide of 3-5ml is taken to be uniformly distributed it in culture dish, weigh, culture dish is put into DHG-9070A types
3h or so in electric heating constant-temperature blowing drying box, takes out culture dish later, weighs, and then places into DHG-9070A type electric heating constant temperatures
In air dry oven, until its gross mass no longer changes, its final mass is weighed, you can calculate the concentration of graphite oxide.
3. the preparation of the compressible aeroge of hydrothermal reduction
Graphite oxide (GO) alkene solution of 2-6mg/ml is configured, is put into reaction kettle after ultrasonic disperse is uniform.With mass ratio
(GO：OPBA=4:1 8:1 10:1 12:1 16:1) ratio adds in a concentration of 1-2mg/ml and is dispersed in absolute ethyl alcohol
γ-oxo -1- pyrenes butyric acid (OPBA).The mixed solution being configured is placed on DF-101S heat collecting type heated at constant temperature magnetic agitations
0.5-1h is stirred at room temperature on device.It is put into after stirring evenly in DHG-9070A type electric heating constant-temperature blowing drying boxes, temperature is adjusted to
180 DEG C, reaction time 12-18h.After reaction, it takes out sample to be cleaned repeatedly with distilled water for several times, freeze-drying obtains RGO-
OPBA aeroges.Polymer Solution (PVAC polyvinylalcohol, the polyacrylamide that compound concentration is 0.5,1,3,5,10,30mg/ml
PAM), RGO-OPBA aeroges are immersed, impregnated 5 hours, freeze-drying obtains compressible aeroge.
Discussion of results
What hydro-thermal method prepared compressible graphene aerogel prepares schematic diagram as shown in Figure 1a.Graphene oxide (GO) and
The mixed solution of OPBA handles RGO-OPBA hydrogels by hydrothermal reduction mode, its further freeze-drying process obtains
To RGO-OPBA aeroges.And the reinforcement that π-π interact between the decrease of electrostatic repulsion and RGO and OPBA between GO lamellas
Solution is made to assemble to form gel.Aeroge is immersed in the aqueous solution of PVA again, RGO-OPBA-PVA is obtained by freeze-drying
Aeroge.In RGO-OPBA-PVA aeroges, OPBA plays the role of critical as a kind of " glue ".Due to aeroge
Present in three kinds of active forces and make aeroge have compressibility, stable structure.First, OPBA and RGO (between phenyl ring) has
There are π-π interaction forces；Secondly, have between OPBA and PVA hydrogen bond interaction force (carbonyl of OPBA, carboxylic group with
The hydroxyl group of PVA forms the excellent machinery that hydrogen bond these types active force imparts the compressible aeroge (Fig. 1 b) of graphene
Performance.Under outer force compresses, simple graphene aerogel rupture in i.In contrast, ii high temperatures reduction RGO-OPBA-PVA
(ρ=22.54mg/cm3), integrity is kept, and can restore to the original state within a very short time in outer force compresses lower structure.
What photophysical property (excitation and emission spectra) solution of test OPBA carried out in aqueous solution.Graphene is as glimmering
Optical trapping forces, when graphene and OPBA mix, peak values of the OPBA in 513nm significantly reduces, and almost (Fig. 2 a) is disappeared.
This result is attributed to the pi-pi accumulation interaction between RGO and the phenyl ring of OPBA.By comparing RGO, OPBA, RGO-
OPBA, RGO-OPBA-BSA fluorescence peak (Fig. 2 b), then as can be seen that when RGO is mixed with OPBA, the Fluorescent peal of mixture in
Between RGO and OPBA, because RGO and OPBA is planar structure, so as to further demonstrate the π-π phases between RGO and OPBA
Interaction.As Fig. 2 c carry out the thermogravimetry of OPBA in nitrogen atmosphere.As can be seen from the figure OPBA starts point at 238 degree
Solution, it was demonstrated that its stability is good, and is not decomposed under our reaction temperature.Ultraviolet-visible spectrum is different in Fig. 2 d
Discuss whether OPBA participates in reaction comprehensively under OPBA-RGO mass ratioes.204.5nm (be closed conjugated system (such as aromatic ring), due to
π → π * transition generates strong ultraviolet radiation absorption band, 233,241.5,281 (C=O) and the characteristic absorption that 353nm is OPBA
Peak.Work as RGO：OPBA=8：1, OPBA characteristic absorption peak almost disappears, so we have selected 8：1 reaction ratio.Fig. 2 e are
Different quality than RGO-OPBA hydrogel photos.Wherein, mass ratio RGO-OPBA=8:1 is optimal proportion.
Fig. 3 a are the PVA concentration that RGO-OPBA-PVA aeroges impregnate and the function of its density.As a concentration of 0mg/ml of PVA
When, aeroge density is 12.04mg/ml.With the increase of the concentration of PVA, the density of aeroge is consequently increased.Fig. 3 b-e
It is the strain stress curve of PVA a concentration of 0.5,1,3,5mg/ml.It, should in loading process as C (PVA)=0.5mg/ml
ε≤45% of the range of linearity of force-strain curve.After discharging load, which does not restore shape completely, is restored to initial
75.7% (after 100 cycles) of shape.RGO-OPBA-PVA aeroges (CPVA=1mg/ml) it is able to take high pressure shrinkage strain,
Show there is no serious plastic deformation and intensity as Fig. 3 c. compression verifications are recycled for 100 loading-unloading
In aeroge in ε=65%, thus from RGO lamellas, the interleaving network of OPBA and PAM chains discloses its firm structure.100th
σ-ε the curves of secondary cycle are identical, cycles for the first time, except that in the compression stress slight decrease of ε=65% extremely
Shown in (after 100 cycles) (Fig. 3 e) of 83% original value.Work as CPVAFor 3mg/ml, in ε<30% and 30%<ε<45% it is non-
In the range of the linear elasticity of the range of linearity, recovery rate is 80.5% (after 100 cycles).Work as CPVAFor 5mg/ml, aeroge
45 cycles, ε=55% can only be compressed.Its rate of recovery is 80.5%.And increase with the concentration of PVA, compression performance is more
Difference.
When RGO-OPBA-PVA aeroges is pushed to go to absorb water droplet and oil droplet (Fig. 4 a), it can promptly adsorb the two, water
It drips (rhodamine B dyeing) and oily (soudan III dyeing).The high porosity and wetability of RGO-OPBA-PVA aeroges, make its into
For intake water (surface of dip-coating PVA is hydrophilic) and the advantageous sorbent material of other organic solvents.Fig. 4 b are illustrated
The adsorption capacity of RGO-OPBA-PVA aeroges and water (Q, final weight after fully absorbing with
Percentage after the initial weight of RGO-OPBA-PVA aeroges), it can absorb about 43 times of its weight in 5 seconds
Water.Due to the superior elasticity of RGO-OPBA-PVA aeroges, the liquid of absorption can be by mechanical presses out without destroying
Its porous structure.Therefore, the macropore being adsorbed onto again with liquid in sponge, nanofiber are easily pushed open, so as to obtain
Swelling process.The shape of original and superelevation absorbability (Fig. 4 b, e) are still kept after more than 10 times cycles of this aeroge.According to sight
It examines, sponge can adsorb the up to water of 516mg in being recycled in first time.However, this is after the water of 140mg is retained in sponge extruding
Because since the not every water of interaction between water and sponge can be out recovered (Fig. 4 c) by mechanical presses.
But due to the volatility of dichloromethane, it can almost restore initial mass (Fig. 4 e) completely by squeezing aeroge.It is recycling
In adsorption process, adsorbent and Quality of recovery are stable, it was confirmed that the suction of the excellent cycle of RGO-OPBA-PVA aeroges
The property received and elasticity.In order to characterize the absorption property of aeroge, the adsorption capacity of various organic solvents (for example, hexane etc.) is carried out
Research.Fig. 4 e are to dichloromethane absorption curve 10 periods.Observed high absorption capacity can be attributed to gas
The high porosity and low-density of gel.
Test show 100 cycle (Fig. 5 b) after, it is fixed strain (ε=60%) under electric conductivity the small card of deviation
Its real high electromechanical stability.Such as shown in figure 5d, normalized resistance (Δ R/R0) keep being stable upon compression.It should
Become (ε) and resistivity (R/R0) relationship provide in fig. 5 c.Resistivity (R/R0) linearly reduce, this is and RGO-OPBA-
The mechanical behavior of PVA aeroges is consistent.The density of contact point increases sharply between the large deformation stage, graphene skeleton, causes
The index decreased of resistance.The high load capacity of RGO-OPBA-PVA aeroges and graphene film shows that the strong strain of resistance relies on, this should
It is attributed to the presence of the big graphene sheet layer of the skeleton.And in the device of the resistance against compression in Fig. 5 a, apply with to aeroge
The bright light of pressure LED light enhancing.In LED light voltage is 6V circuit, it is illuminated with airsetting glue connection circuit lamp, and its
Brightness fluctuation is compressing and is discharging aeroge (Fig. 5 e).This phenomenon allows RGO-OPBA-PVA aeroges to apply in pressure
In terms of response sensor.
Embodiment 2
The preparation of 1.GO
Using natural flake graphite as raw material, graphite oxide is prepared using Hummers methods.Under ice bath state, 24mL is taken
The concentrated sulfuric acid is placed in 200mL flasks, and adds in 1.0g graphite and 0.8gNaNO thereto3, stir evenly and be slow added into backward
5gKMnO4Powder (adds in) in three times, and solution is warming up to 40 DEG C of reaction 2h after stirring 10min.It is warming up to 70 DEG C of reactions
30min is slowly added to 50mL deionized waters when solution temperature drops to room temperature, and 3mL is added in inwards when temperature is down to 0 DEG C
30% H2O2To terminate reaction, reactant becomes golden yellow, and until bubble-free from brownish black.Centrifugation is carried out to reaction solution to wash
Wash, the ultrasound that the solution containing graphite oxide after washing is carried out to 30min is removed, then centrifuged under the conditions of 1000rpm with
Remove unstripped graphite oxide, then at 3,000 rpm centrifugation 10min take precipitation be dried in vacuo after up to graphene oxide powder
End.A certain amount of graphene oxide powder is taken to be dispersed in water, ultrasound prepares GO suspension.Then it is placed on KQ3200B types ultrasound
Ultrasound 6h takes out in wave washer.
2. constant volume
The graphite oxide of 3-5ml is taken to be uniformly distributed it in culture dish, weigh, culture dish is put into DHG-9070A types
3h or so in electric heating constant-temperature blowing drying box, takes out culture dish later, weighs, and then places into DHG-9070A type electric heating constant temperatures
In air dry oven, until its gross mass no longer changes, its final mass is weighed, you can calculate the concentration of graphite oxide.
3. the preparation of the compressible aeroge of hydrothermal reduction
Graphite oxide (GO) alkene solution of 2-6mg/ml is configured, is put into reaction kettle after ultrasonic disperse is uniform.With mass ratio
(GO：OPBA=4:1 8:1 10:1 12:1 16:1) ratio adds in a concentration of 1-2mg/ml and is dispersed in absolute ethyl alcohol
γ-oxo -1- pyrenes butyric acid (OPBA).The mixed solution being configured is placed on DF-101S heat collecting type heated at constant temperature magnetic agitations
0.5-1h is stirred at room temperature on device.It is put into after stirring evenly in DHG-9070A type electric heating constant-temperature blowing drying boxes, temperature is adjusted to
160 DEG C, reaction time 10-18h.After reaction, it takes out sample to be cleaned repeatedly with distilled water for several times, freeze-drying obtains RGO-
OPBA aeroges.The Polymer Solution (polyvinyl acetate emulsion PVAC) that compound concentration is 0.5,1,3,5,10,30mg/ml, will
RGO-OPBA aeroges immerse, and impregnate 5 hours, and freeze-drying obtains compressible aeroge.
Embodiment 3
The preparation of 1.GO
Using natural flake graphite as raw material, graphite oxide is prepared using Hummers methods.Under ice bath state, 24mL is taken
The concentrated sulfuric acid is placed in 200mL flasks, and adds in 1.0g graphite and 0.8gNaNO thereto3, stir evenly and be slow added into backward
5gKMnO4Powder (adds in) in three times, and solution is warming up to 40 DEG C of reaction 2h after stirring 10min.It is warming up to 70 DEG C of reactions
30min is slowly added to 50mL deionized waters when solution temperature drops to room temperature, is added in inwards when temperature is down to 0 DEG C
The H of 3mL30%2O2To terminate reaction, reactant becomes golden yellow, and until bubble-free from brownish black.Reaction solution is centrifuged
Washing, the ultrasound that the solution containing graphite oxide after washing is carried out to 30min are removed, are then centrifuged under the conditions of 1000rpm
To remove unstripped graphite oxide, then at 3,000 rpm centrifugation 10min take precipitation be dried in vacuo after up to graphene oxide powder
End.A certain amount of graphene oxide powder is taken to be dispersed in water, ultrasound prepares GO suspension.Then it is placed on KQ3200B types ultrasound
Ultrasound 6h takes out in wave washer.
2. constant volume
The graphite oxide of 3-5ml is taken to be uniformly distributed it in culture dish, weigh, culture dish is put into DHG-9070A types
3h or so in electric heating constant-temperature blowing drying box, takes out culture dish later, weighs, and then places into DHG-9070A type electric heating constant temperatures
In air dry oven, until its gross mass no longer changes, its final mass is weighed, you can calculate the concentration of graphite oxide.
3. the preparation of the compressible aeroge of hydrothermal reduction
Graphite oxide (GO) alkene solution of 2-6mg/ml is configured, is put into reaction kettle after ultrasonic disperse is uniform.With mass ratio
(GO：OPBA=4:18:110:112:116:1) ratio add in γ that a concentration of 1-2mg/ml is dispersed in absolute ethyl alcohol-
Oxo -1- pyrenes butyric acid (OPBA).The mixed solution being configured is placed on DF-101S heat collecting type constant-temperature heating magnetic stirring apparatus upper chambers
Temperature stirring 0.5-1h.It being put into after stirring evenly in DHG-9070A type electric heating constant-temperature blowing drying boxes, temperature is adjusted to 180 DEG C,
Reaction time 12-18h.After reaction, it takes out sample to be cleaned repeatedly with distilled water for several times, freeze-drying obtains RGO-OPBA gas
Gel.Polymer Solution (PVAC polyvinylalcohol, the polyvinyl acetate emulsion that compound concentration is 0.5,1,3,5,10,30mg/ml
The mixture of PVAC, polyacrylamide PAM), RGO-OPBA aeroges are immersed, are impregnated 5 hours, freeze-drying obtains to press
Contracting aeroge.
Finally it should be noted that the foregoing is only a preferred embodiment of the present invention, it is not limited to this hair
It is bright, although the present invention is described in detail referring to the foregoing embodiments, for those skilled in the art, still
It can modify to the technical solution recorded in previous embodiment or equivalent replacement is carried out to which part.It is all in this hair
Within bright spirit and principle, any modification, equivalent replacement, improvement and so on should be included in protection scope of the present invention
Within.Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to the scope of the present invention
Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to
Make the creative labor the various modifications or changes that can be made still within protection scope of the present invention.
Claims (11)
1. a kind of preparation method of the compressible aeroge of graphene based on hydrothermal reduction method, which is characterized in that including：
It is adhesive by raw material, γ-oxo -1- pyrene butyric acid OPBA of graphene oxide GO, RGO- is made in hydro-thermal pyrolysis reduction
OPBA aeroges；
The dip-coating macromolecule polymer solution HMP on RGO-OPBA aeroges removes solvent to get RGO-OPBA-HMP airsettings
Glue；
The high molecular polymer for PVAC polyvinylalcohol, polyvinyl acetate emulsion PVAC, one kind in polyacrylamide PAM or
A variety of combinations.
2. the method as described in claim 1, which is characterized in that the quality of the graphene oxide, γ-oxo -1- pyrene butyric acid
Than for：4~16:1~1.2.
3. the method as described in claim 1, which is characterized in that the hydro-thermal pyrolysis reduction condition is：160 ~ 200 DEG C, reaction
Time 10-18h.
4. the method as described in claim 1, which is characterized in that the condition of the dip-coating is：By RGO-OPBA aeroges in matter
It measures in the PVAC polyvinylalcohol solution of a concentration of 0.5 ~ 30mg/ml and impregnates 5 ~ 6 hours.
5. the method as described in claim 1, which is characterized in that the graphene oxide passes through the acid or oxidant in mixing
Oxidation in system and prepare.
6. method as claimed in claim 5, which is characterized in that the acid or oxidant are selected from H2SO4、HNO3、H2O2、KMnO4、
K2Cr2O7。
7. the method as described in claim 1, which is characterized in that the specific method for removing solvent is supercritical drying, freezes
The technology of dry method, room temperature and environmental pressure drying is implemented to form aeroge.
8. the method as described in claim 1, which is characterized in that be present in the impurity in the RGO-OPBA-HMP aeroges
Amount is less than 5%.
9. the RGO-OPBA-HMP aeroges obtained by the method for any preceding claims.
10. the aeroge of claim 9 has 1-22.54mg/cm3Density.
It is 11. catalyst or catalyst carrier including the RGO-OPBA-HMP aeroges described in claim 9 or 10, non-reflective
Plate, electro-chemical device electrode, the absorber material for liquid absorption, filter, gas adsorption media, Water warfare medium.
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| CN107226464B (en) * | 2017-07-24 | 2019-06-14 | 中国石油大学(华东) | The preparation method of graphene aerogel based on emulsion method |
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| CN102239114A (en) * | 2008-12-04 | 2011-11-09 | 泰科电子公司 | Graphene and graphene oxide aerogels |
| CN104495820A (en) * | 2014-12-17 | 2015-04-08 | 北京化工大学 | Porous graphene aerogel and preparation method thereof |
| CN104843676A (en) * | 2014-12-03 | 2015-08-19 | 北汽福田汽车股份有限公司 | Preparation method for graphene aerogel |
| CN105271213A (en) * | 2015-11-26 | 2016-01-27 | 河北工业大学 | Preparation method of high-density graphene-based carbon powder with structural orientation |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102239114A (en) * | 2008-12-04 | 2011-11-09 | 泰科电子公司 | Graphene and graphene oxide aerogels |
| CN104843676A (en) * | 2014-12-03 | 2015-08-19 | 北汽福田汽车股份有限公司 | Preparation method for graphene aerogel |
| CN104495820A (en) * | 2014-12-17 | 2015-04-08 | 北京化工大学 | Porous graphene aerogel and preparation method thereof |
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