CN108047806A - A kind of graphene/Ag- carbon microspheres aeroge coating and its preparation method and application - Google Patents
A kind of graphene/Ag- carbon microspheres aeroge coating and its preparation method and application Download PDFInfo
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- CN108047806A CN108047806A CN201711418625.XA CN201711418625A CN108047806A CN 108047806 A CN108047806 A CN 108047806A CN 201711418625 A CN201711418625 A CN 201711418625A CN 108047806 A CN108047806 A CN 108047806A
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0233—Compounds of Cu, Ag, Au
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
Abstract
The invention discloses a kind of graphene/Ag carbon microspheres aeroge coating and its preparation method and application, belong to coating new material technology field.The preparation process of coating of the present invention is：Nanometer Ag carbon microspheres are prepared first, then by itself and AgNO3Solution mixes, and by stirring, centrifuging, rinsing and ultrasonic disperse, obtains even Ag carbon microspheres；It then adds graphene oxide into nanometer Ag carbon microspheres solution, adds in 5~10%wt cysteines, stir to get aqueous gel mixture；Aqueous gel mixture is finally placed in 8 10h in 75 85 DEG C of deep fats, is rinsed, is post-processed using freeze-drying, obtain graphene/Ag carbon microspheres aeroges, be then added to as additive in coating and obtain graphene/Ag carbon microspheres aeroge coating.The coating of the present invention has the VOCs absorption properties of superelevation and self degradation ability, and anti-fog haze effect is preferable, has potential application prospect.
Description
Technical field
The invention belongs to coating new material technology field, more specifically to a kind of graphene/Ag- carbon microspheres airsettings
Glue coating and its preparation method and application.
Background technology
With Chinese national economy sustainable growth and the continuous improvement of living standards of the people, environmental protection has become a kind of people and has chased after
Seek the theme of healthy green living.And as people are higher and higher to the coating requirement of indoor exterior decoration, more people are selecting
During selecting functional coating, anti-fog haze environment-friendly type coating is considered emphatically, more and more people, which pursue, " gets close to nature, big gloomy
Fresh air as woods ", therefore, coating of the research and development with anti-fog haze effect have great importance.
Graphene is most thin most strong material known to the mankind, and comprising single layer of carbon atom, these atoms connect into honeycomb row
Row, the thickness of graphene are only a carbon atom diameter, carbon atom diameter D=0.14nm.The graphene experimentally prepared
Lamella is limited by preparation method and condition, can not prepare the two-dimensional graphene lamella of area infinity.It experimentally prepares at present
Maximum graphene sheet layer for University of Manchester Geim lead research group, be by mechanically pulling off method preparation graphite
Alkene, maximum width is up to 10 μm.Even graphene film size prepared by current experiment room, also more most of than other substances
Specific surface area will be much higher, therefore application of the graphene on modified coating receives the extensive concern of domestic and international researcher.
At present, graphene coating has been achieved with industrialization in developed countries such as South Korea, America and Europes, but simultaneously few, domestic main
It is protected with the alkene zinc-type wind power equipment based on graphene that the enterprises such as the hexa-atomic plain Science and Technology Ltd. in Changzhou research and develop jointly
Anticorrosive paint has been realized in industrialization, while the patent report on graphene modified coating also has more disclosure.
Such as, Chinese patent 201610813904.5 discloses a kind of graphene conductive anticorrosive paint, the coating be with aqueous epoxy resins,
Potassium water glass is film forming matter, and the Organic-inorganic composite bottom of black alkene and tin oxide nano particles as main stuffing is aoxidized using stone
Paint.This application effectively increases the electric conductivity and hardness of coating, and antiseptic property is good, suitable for all kinds of metallic conduits and metal
The anti-corrosion coating of component.For another example, Chinese patent 201510208892.9 discloses the heat-conductive coating that a kind of graphene is modified, the Shen
Please case ground is contacted by adding in graphene coating in coating even closer, while the antifriction of coating can be effectively improved
Wiping property and thermal conductivity.
But current graphene modified coating is concentrated mainly on the application fields such as anti-corrosion, electrically-conducting paint, and in the environmental protection of anti-fog haze
The study on the industrialization in field and application are also fewer.As the haze being on the rise pollutes, PM2.5 air pollutants are hazes
One of main component, this proposes severe challenge to environment for the survival of mankind, and as chief culprit's volatility of PM2.5
Organic compound (VOCs) becomes one of universally acknowledged major air pollutants.Therefore, research and development have VOCs high adsorption capacities
Graphene-based coating has important environment protection significance and wide application prospect.
Through retrieval, disclosed on application of the graphene in terms of haze is had related patents.
Such as, Chinese patent 201410722672.3 discloses a kind of graphene-based haze mask filter material and its preparation side
Method, this application are that the crosslinking agents such as ascorbic acid are added in graphene oxide water solution, make graphene film by hydro-thermal reaction
Layer self assembly is so as to obtaining porous spongiform three-dimensional graphite.For another example, Chinese patent 201410219506.1 discloses one kind
Haze mask filter material composition, said composition are made of the component of following parts by weight, 4-6 parts of cinnamaldehyde diethylacetal,
9-11 parts of nanoscale Tourmaline, 55-65 parts of activated carbon fibre, 15-25 parts of straw particle, 0.9-1.1 parts of nano silver, graphene
0.9-1.1 parts, 1.5-2.5 parts of drier.Above-mentioned two application case can improve the filtering of haze mask to a certain extent
Performance, but it is of limited application, and its anti-fog haze performance needs to be further improved.
The content of the invention
1. technical problems to be solved by the inivention
It is an object of the invention to overcome the shortcomings of that the anti-fog haze effect of existing coating is relatively poor, a kind of graphite is provided
Alkene/Ag- carbon microspheres aeroge coating and its preparation method and application.The VOCs that the aeroge coating of the present invention has superelevation is adsorbed
Performance and self degradation ability, anti-fog haze effect is preferable, and its preparation process is simple, at low cost, easy to utilize.
2. technical solution
In order to achieve the above objectives, technical solution provided by the invention is：
First, the present invention a kind of graphene/Ag- carbon microspheres aeroge coating preparation method, this method be pass through to
Graphene/Ag- carbon microspheres aeroges are added in coating to be prepared, and are comprised the following steps：
Step 1: the preparation of nanometer Ag-carbon microspheres
AgNO is added in into the carbon microspheres suspension that mass concentration is 0.3~0.5%wt3Solution obtains mixed solution, will
It is micro- to get even Ag- charcoals that gained mixed solution carries out magnetic agitation, centrifugation, flushing and ultrasonic disperse processing respectively
Ball；
Step 2: the preparation of graphene/Ag- carbon microspheres aeroges
Graphene oxide suspension is added in nanometer Ag-carbon microspheres solution and is uniformly mixed, then adds in cysteine
It is stirred, obtains aqueous gel mixture；Aqueous gel mixture is placed in 8-10h in 75-85 DEG C of deep fat, then washes off 3D
Structure handles block-like hydrogel to get to graphene/Ag- carbon microspheres aeroges using freeze-drying；
Step 3: the preparation of coating
It is added to gained aeroge as additive in coating to get graphene/Ag- carbon microspheres aeroge coating.
Further, in gained coating graphene/Ag- carbon microspheres aeroges additive amount for coating gross weight 5~
10%.
Further, gained carbon microspheres-AgNO in the step 13Ag in mixed solution+Concentration be 1~1.5mol/
L, the carbon microspheres are hollow structure, and specific surface area is 1800~2200g/m2。
Further, in the step 1 in gained nanometer Ag-carbon microspheres the size of nano-silver ionic for 50~
200nm。
Further, by carbon microspheres-AgNO in the step 13Mixed solution uses 180~220rpm magnetic rotors
After stirring 20~for 24 hours, 10~15min is centrifuged to remove extra silver ion with the rotating speed of 2800~3000rpm, it is then right
Gained nanometer Ag-carbon microspheres are rinsed using distilled water and alcohol, again using ultrasonic wave disperse 45~60min to get to
Even Ag- carbon microspheres.
Further, the preparation method of carbon microspheres is as follows in the step 1：
(1) cellulose according to the amount of 5~8g/100ml is uniformly dispersed in deionized water, is subsequently placed in hydrothermal reaction kettle
Interior cooled to room temperature after keeping the temperature 6~8h constant at 200~220 DEG C；
(2) substance of lower floor in hydrothermal reaction kettle is filtered, is washed with absolute ethyl alcohol and distilled water, then put
10~12h is dried at 100~110 DEG C；
(3) substance after drying obtained by step (2) is put into earthenware with KOH solution according to impregnating ratio KOH/C=1.3~1.5
In crucible, be subsequently placed in micro-wave oven and carry out activation process, and be passed through nitrogen, microwave power be 600~800W, soak time 8
~11min；
(4) gained activation products are added into dilute HCl to neutrality, is subsequently placed at 100~110 DEG C and processing is dried, i.e.,
It is 1800~2200g/m to obtain specific surface area2Carbon microspheres.
Further, the concentration of graphene oxide contained by graphene oxide suspension is 3~5mg/ in the step 2
Ml, the additive amount of cysteine are the 5~10% of nanometer Ag-carbon microspheres solution total amount.
Second, graphene/Ag- carbon microspheres aeroge coating that method using the present invention is prepared.
Third, a kind of compound anti-fog haze coating of graphene/Ag- carbon microspheres aeroges exterior decoration field indoors of the present invention
Application.
Further, when the coating being used as indoor and outdoor decoration coating, directly it coated on substrate surface or is incited somebody to action
It is as functional top coat in other coating surfaces.
3. advantageous effect
Using technical solution provided by the invention, compared with prior art, there is following remarkable result：
(1) preparation method of a kind of graphene/Ag- carbon microspheres aeroge coating of the invention, by graphene oxide with receiving
Rice Ag- carbon microspheres carry out it is compound, so as to which graphene/Ag- carbon microspheres aeroges be prepared, then using gained aeroge as adding
Agent is added to be added in coating to get graphene/Ag- carbon microspheres aeroge coating, the coating have superelevation VOCs absorption properties and
The ability of self degradation, anti-fog haze effect is preferable, therefore suitable for indoor and outdoor decoration.
(2) preparation method of a kind of graphene/Ag- carbon microspheres aeroge coating of the invention, the system of hollow carbon microspheres
Standby technology has the characteristics that easy to operate, pollution-free and raw material sources are abundant, can single step reaction it is complete, and carbon microspheres obtained by preparing
Specific surface area it is larger, further ensure gained aeroge coating absorption property.
(3) a kind of graphene/Ag- carbon microspheres aeroge coating of the invention, using graphene/Ag- carbon microspheres aeroges
As the additive of coating, the graphene/Ag- carbon microspheres aeroge is the complex three-dimensional network structure of cylindrical shape multiple-limb,
Inside has abundant microcellular structure, thus its specific surface area and the general material of pore volume rate ratio are much higher, to organic solvent
And organic substance, particularly there is superpower adsorption capacity to VOCs, therefore its addition can significantly improve the anti-fog haze of coating
Performance, so as to solve the problems, such as the anti-fog haze poor-performing of existing indoor and outdoor finishing paint.
(4) the compound anti-fog haze coating of a kind of graphene/Ag- carbon microspheres aeroges of the invention, compared with existing product,
Absorption property improves 2 times, and viscosity is up to 40000 or more CPS (mPas), and adhesive force is good, and performance is stablized, long lifespan；Simultaneously
Its is economic and environment-friendly, and low cost is low, possesses very strong competitive advantage, has huge applications prospect.
(5) application of the compound anti-fog haze coating of a kind of graphene/Ag- carbon microspheres aeroges of the invention, will be described anti-fog
Haze coating directly in other coating surfaces can be effectively improved coated on substrate surface or as functional top coat
Its anti-fog haze ability, and it is easy to operate.
Description of the drawings
Fig. 1 is the scanned picture of present invention gained carbon microspheres；
Fig. 2 is the scanned picture of present invention gained graphene oxide；
Fig. 3 is the preparation process schematic diagram of the compound anti-fog haze coating of graphene/Ag- carbon microspheres aeroges of the present invention；
Fig. 4 is the technological process of the preparation method of the compound anti-fog haze coating of graphene/Ag- carbon microspheres aeroges of the present invention
Figure.
Specific embodiment
Since anti-fog haze Coating Market is huge, indoor and outdoors are widely used, and as national policy gets over environmental requirement
Come it is higher, it is more and more stringenter for the control of VOCs in the future, therefore research and develop new anti-fog haze coating and have great importance.
Graphene is most thin most strong material known to the mankind, and comprising single layer of carbon atom, these atoms connect into honeycomb arrangement, ratio
Surface area is up to 2630m2/ g, and possess abundant central hole structure, after it is made to be uniformly dispersed in coating, relatively thin coating
The protective layer of large area is formed, it is crucial that the coating for having loaded graphene has powerful absorption property.However, many institute's weeks
Know, ideal graphite alkene is perfect two-dimensional network structure, the generally weaker physical absorption of the absorption to molecule.In order to realize
The excellent absorption property of graphene-based material for gaseous molecule, the present invention will be by that will have smooth surface, homogeneous and high adsorption
Hollow structure carbon microspheres and the graphene progress of energy are compound, can be in carbon microspheres and graphene list due to the intercalation of graphene oxide
Dispersion force is generated on layer interface, so as to ensure that coating has higher absorption property.Meanwhile present invention gained graphene airsetting
Glue has been provided simultaneously with the characteristic of graphene and aeroge, has higher porosity rate, ultralight density, high mechanical strength, with
And thermal conductivity and electrical conductivity well.In addition, the present invention is by carbon microspheres surface elder generation loading nano silvery ion, then with graphene
It is perfect compound, so as to achieve the effect that haze is catalytically decomposed.
Although the external research and development for having had graphene/carbon microsphere aeroge are reported, the country also has the graphene/carbon microsphere compound
The related patents of material disclose, as Chinese patent 201310235331.9 discloses a kind of graphene/carbon microsphere composite
Preparation method, this application is using water soluble starch and graphite oxide as raw material, successively through Starch Hydrolysis, ultrasonic disperse oxidation stone
Ink, two steps heating synthesis carbon microspheres, then through carbonization-activation, the graphene/carbon microsphere composite of obtained electrochemical performance.
But the preparation of existing graphene/carbon microsphere composite, and cannot be effective primarily to improve the chemical property of carbon microspheres
It is applied in anti-fog haze coating.The present invention is self-assembly of graphene/charcoal using the carbon microspheres of high adsorption capacity with graphene oxide
Microballoon aeroge, and add nano-silver ionic make it have catalytically bactericidal process effect, while inventor also by many experiments to each
The additive amount of component and specific preparation technology parameter optimize, so as to which low cost is prepared and has excellent suction
The aeroge can be significantly improved the anti-fog haze of coating by the graphene/carbon microsphere aeroge of attached VOCs performances as additive
Performance.
Specifically, a kind of graphene/Ag- carbon microspheres aeroge coating of the present invention, is prepared by following steps：
Step 1: the preparation of nanometer Ag-carbon microspheres
AgNO is added in into the carbon microspheres suspension that mass concentration is 0.3~0.5%wt3Solution obtains mixed solution, mixes
Close Ag in solution+Concentration for 1~1.5mol/L, by gained carbon microspheres-AgNO3Mixed solution is turned using 180~220rpm magnetic force
After son stirring 20~for 24 hours, 10~15min is centrifuged to remove extra silver ion with the rotating speed of 2800~3000rpm, then
Gained nanometer Ag-carbon microspheres are rinsed using distilled water and alcohol, again using ultrasonic wave disperse 45~60min to get
To even Ag- carbon microspheres.The carbon microspheres are hollow structure, and specific surface area is 1800~2200g/m2, gained nanometer
The size of nano-silver ionic is 50~200nm in Ag- carbon microspheres.The preparation method of carbon microspheres is as follows in the present invention：
(1) cellulose according to the amount of 5~8g/100ml is uniformly dispersed in deionized water, is subsequently placed in hydrothermal reaction kettle
Interior cooled to room temperature after keeping the temperature 6~8h constant at 200~220 DEG C；
(2) substance of lower floor in hydrothermal reaction kettle is filtered, is washed with absolute ethyl alcohol and distilled water, then put
10~12h is dried at 100~110 DEG C；
(3) substance after drying obtained by step (2) is put into earthenware with KOH solution according to impregnating ratio KOH/C=1.3~1.5
In crucible, be subsequently placed in micro-wave oven and carry out activation process, and be passed through nitrogen, microwave power be 600~800W, soak time 8
~11min；
(4) gained activation products are added into dilute HCl to neutrality, is subsequently placed at 100~110 DEG C and processing is dried, i.e.,
It is 1800~2200g/m to obtain specific surface area2Carbon microspheres.
Step 2: the preparation of graphene/Ag- carbon microspheres aeroges
6~10ml graphene oxide suspensions (concentration of graphene oxide is 3~5mg/ml) are added to nanometer Ag-charcoal
It is uniformly mixed in microspheres solution, the cysteine for then adding in nanometer Ag-carbon microspheres solution total amount 5~10% is stirred, and is obtained
To aqueous gel mixture；Aqueous gel mixture is placed in 8-10h in 75-85 DEG C of deep fat, then washes off 3D structures, use is cold
Freeze seasoning and handle block-like hydrogel to get to graphene/Ag- carbon microspheres aeroges.Gained graphene/Ag- carbon microspheres gas
Gel is the complex three-dimensional network structure of cylindrical shape multiple-limb, and large number of microcellular structure, thus its specific surface are contained in inside
Product and the general material of pore volume rate ratio are much higher, to organic solvent and organic substance, particularly have superpower suction to VOCs
Attached ability, therefore its addition can significantly improve the anti-fog haze performance of coating, resist so as to solve existing indoor and outdoor finishing paint
The problem of haze poor-performing.Above-mentioned graphene oxide purchased in market can obtain, and can also prepare in accordance with the following methods：
(1) by 10~15g native graphites, the dense H of 230~250ml2SO4And 5~10g NaNO3Powder mixing is placed on ice water
In bath, in 3~4 DEG C of 0.5h stirred below, and 3~5g KMnO are added in by several times in whipping process4Common 3g after addition, is protected
Temperature 1.5~2h of reaction, completes low-temp reaction；(2) system temperature is increased to 35 DEG C, insulation reaction 3h, completes medium temperature reaction；
(3) system temperature is risen to 100 DEG C, and distilled water is added dropwise with constant pressure funnel, reacted 1h, complete pyroreaction；(4) reaction terminates
Afterwards, during addition 70mL distilled water and 10mL hydrogen peroxide persistently stir 15min, and product is adjusted to by the dilute HCl of use and distilled water
Property；Finally, gained graphite oxide is dispersed in water, ultrasonic 8h is placed in drying for standby in vacuum drying chamber.
Step 3: the preparation of coating
It is added to gained aeroge as additive in coating to get graphene/Ag- carbon microspheres aeroge coating.
The present invention is compound by the way that graphene oxide is carried out with nanometer Ag-carbon microspheres, so as to which graphene/Ag- be prepared
Carbon microspheres aeroge, gained aeroge have the ability of superelevation VOCs absorption properties and self degradation, add as additive
The anti-fog haze ability of coating can be effectively improved by being added in coating, the additive amount of graphene/Ag- carbon microspheres aeroges accounts in coating
The 5~10% of coating gross weight.There are the technology of preparing of the hollow carbon microspheres of the present invention easy to operate, pollution-free and raw material sources to enrich
The features such as, can single step reaction it is complete, and the specific surface area for preparing gained carbon microspheres is larger, it is spherical it is homogeneous, surface is smooth, further
Ensure that gained aeroge absorption property, while also for carbon microspheres uniform load on graphene, prepare graphene/carbon microsphere
Aeroge (G/CS hybrid aerogel) functional paint is laid a good foundation.Meanwhile by rationally controlling technological parameter can be into one
Step ensures the absorption property of gained graphene/carbon microsphere aeroge, by adding nano-silver ionic, adds its antibacterial and catalysis
Performance.
To further appreciate that present disclosure, the present invention is further described in conjunction with specific embodiment.
Embodiment 1
A kind of preparation method of the graphene of the present embodiment/Ag- carbon microspheres aeroge coating, preparation process schematic diagram and
Flow chart as shown in Figure 3, Figure 4, specifically includes following steps：
(1) preparation of carbon microspheres：Using cellulose as raw material, carbon microspheres are prepared using hydro-thermal charring.
Specifically, weighing 0.8g celluloses in 20ml sample bottles, the deionized water of 15mL is added in, in turning for 30r/min
The lower magnetic agitation 30min of speed, makes cellulose uniformly disperse in the solution, is then placing it in the hydrothermal reaction kettle of 25mL.
After hydrothermal reaction kettle good seal, the constant heat preservation 7h at 220 DEG C is put into Muffle furnace, is naturally cooled to afterwards in Muffle furnace
Room temperature.The substance of lower floor in hydrothermal reaction kettle is filtered, is washed with absolute ethyl alcohol and distilled water, is dried at 110 DEG C
Dry 12h.Carbon microspheres are put into according to impregnating ratio KOH/C=1.3 in crucible, is subsequently placed in micro-wave oven and carries out activation process, and
It is passed through nitrogen, microwave power 700W, soak time 10min；Then products therefrom is added into dilute HCl to neutrality, at 110 DEG C
Dry, last products therefrom is that specific surface area is 1800~2200g/m2Carbon microspheres, scanned picture is shown in Fig. 1.
(2) preparation of nanometer Ag-carbon microspheres
The carbon microspheres of 0.4%wt are taken, pours into the distilled water of 15ml, then adds in AgNO3Solution, Ag in mixed solution+'s
Concentration is 1mol/L, and mixed solution is shaken up and uses the stirring of 200rpm magnetic rotors for 24 hours；Centrifuge is used to turn with 3000rpm
Speed separation 15min removes extra silver ion, then to nanometer Ag-carbon microspheres (AgCS) of gained using distilled water and alcohol into
Row rinses, and scattered 1h is carried out using ultrasonic wave again, to obtain even Ag- carbon microspheres, the wherein specific surface area of carbon microspheres
For 2000~2100g/m2, the size of nano-silver ionic is 50~150nm in gained nanometer Ag-carbon microspheres.
(3) preparation of graphene/Ag- carbon microspheres aeroges
The graphene oxide suspension (concentration of graphene oxide is 3mg/ml) of 5ml is added in the AgCS solution of 10ml
It is uniformly mixed, the cysteine for then adding in nanometer Ag-carbon microspheres solution total amount 5% carries out ultrasonication 1h, aoxidizes 2D
Graphene film changes into the graphene hydrogel of 3D, obtains aqueous gel mixture, and aqueous gel mixture then is put into 80 DEG C of heat
9h in oil.Finally, 3D structures are washed off using ultra-pure water.Remaining bulk hydrogel changes into gas using freeze-drying
Gel, until spare.
(4) it is added to gained aeroge as additive in coating to get to the anti-fog haze composite coating of the present embodiment,
The additive amount of graphene/Ag- carbon microspheres aeroges accounts for the 7% of coating gross weight in the coating.
For indoor and outdoor decoration, when specifically used, gained coating is directly coated for aeroge coating obtained by the present embodiment
In substrate surface or as functional top coat in other coating surface uses, there is good catalysis point
The effect of haze is solved, and it is easy to operate.Compared with existing product, the absorption property of the graphene composite coating of the present embodiment can
2 times are effectively improved, and the cost of product is basically unchanged, technical indicator is specific as follows：(a) absorption property：Adsorption rate reaches
80% and more than；(b) viscosity：40000 or more CPS (mPas)；(c) adhesive force：600 adhesive tapes of 3M are pasted, quiet
It puts 90 ° of directions of more than 1min to remove rapidly, substantially without carbon granules on adhesive tape, adhesive force is good, and performance is stablized, long lifespan, therefore possesses
Very strong competitive advantage has huge applications prospect.
Embodiment 2
A kind of preparation method of the graphene of the present embodiment/Ag- carbon microspheres aeroge coating, preparation process schematic diagram and
Flow chart as shown in Figure 3, Figure 4, specifically includes following steps：
(1) preparation of carbon microspheres：Using cellulose as raw material, carbon microspheres are prepared using hydro-thermal charring.
Specifically, weighing 0.8g celluloses in 20ml sample bottles, the deionized water of 10mL is added in, in turning for 40r/min
The lower magnetic agitation 20min of speed, makes cellulose uniformly disperse in the solution, is then placing it in the hydrothermal reaction kettle of 25mL.
After hydrothermal reaction kettle good seal, the constant heat preservation 8h at 200 DEG C is put into Muffle furnace, is naturally cooled to afterwards in Muffle furnace
Room temperature.The substance of lower floor in hydrothermal reaction kettle is filtered, is washed with absolute ethyl alcohol and distilled water, is dried at 105 DEG C
Dry 11h.Carbon microspheres are put into according to impregnating ratio KOH/C=1.5 in crucible, is subsequently placed in micro-wave oven and carries out activation process, and
It is passed through nitrogen, microwave power 600W, soak time 11min；Then products therefrom is added into dilute HCl to neutrality, at 100 DEG C
Dry, last products therefrom is the carbon microspheres of high-specific surface area, and scanned picture is shown in Fig. 1.
(2) preparation of nanometer Ag-carbon microspheres
The carbon microspheres of 0.3%wt are taken, pours into the distilled water of 15ml, then adds in AgNO3Solution, Ag in mixed solution+'s
Concentration is 1.3mol/L, and mixed solution is shaken up and 180rpm magnetic rotors is used to stir 20h；Centrifuge is used with 2800rpm
Rotating speed separation 12min removes extra silver ion, then uses distilled water and alcohol to nanometer Ag-carbon microspheres (AgCS) of gained
It is rinsed, scattered 45min is carried out using ultrasonic wave again, to obtain the ratio table of even Ag- carbon microspheres, wherein carbon microspheres
Area is 1900~2000g/m2, the size of nano-silver ionic is 100~170nm in gained nanometer Ag-carbon microspheres.
(3) preparation of graphene/Ag- carbon microspheres aeroges
The graphene oxide suspension (concentration of graphene oxide is 5mg/ml) of 5ml is added in the AgCS solution of 10ml
It is uniformly mixed, the cysteine for then adding in nanometer Ag-carbon microspheres solution total amount 10% carries out ultrasonication 40min, obtains
Then aqueous gel mixture is put into 10h in 75 DEG C of deep fats by aqueous gel mixture.Finally, 3D is washed off using ultra-pure water
Structure.Remaining bulk hydrogel changes into aeroge using freeze-drying, until spare.The present embodiment passes through native graphite
Hummer chemical oxidization methods are prepared into graphite oxide, and gained graphite oxide is dispersed in water, and ultrasonic 8h is subsequently placed in vacuum and does
Drying for standby in dry case, the scanned picture of gained graphene oxide are shown in Fig. 2.
(4) it is added to gained aeroge as additive in coating to get to the anti-fog haze composite coating of the present embodiment,
The additive amount of graphene/Ag- carbon microspheres aeroges accounts for the 10% of coating gross weight in the coating.Aeroge obtained by the present embodiment is applied
When material is for indoor and outdoor decoration, anti-fog haze effect is closer to embodiment 1.
Embodiment 3
A kind of preparation method of the graphene of the present embodiment/Ag- carbon microspheres aeroge coating, preparation process schematic diagram and
Flow chart as shown in Figure 3, Figure 4, specifically includes following steps：
(1) preparation of carbon microspheres：Using cellulose as raw material, carbon microspheres are prepared using hydro-thermal charring.
Specifically, weighing 0.5g celluloses in 20ml sample bottles, the deionized water of 10mL is added in, in turning for 35r/min
The lower magnetic agitation 40min of speed, makes cellulose uniformly disperse in the solution, is then placing it in the hydrothermal reaction kettle of 25mL.
After hydrothermal reaction kettle good seal, the constant heat preservation 6h at 215 DEG C is put into Muffle furnace, is naturally cooled to afterwards in Muffle furnace
Room temperature.The substance of lower floor in hydrothermal reaction kettle is filtered, is washed with absolute ethyl alcohol and distilled water, is dried at 100 DEG C
Dry 10h.Carbon microspheres are put into according to impregnating ratio KOH/C=1.4 in crucible, is subsequently placed in micro-wave oven and carries out activation process, and
It is passed through nitrogen, microwave power 650W, soak time 9min；Then products therefrom is added into dilute HCl to neutrality, at 105 DEG C
Dry, last products therefrom is the carbon microspheres of high-specific surface area, and scanned picture is shown in Fig. 1.
(2) preparation of nanometer Ag-carbon microspheres
The carbon microspheres of 0.5%wt are taken, pours into the distilled water of 15ml, then adds in AgNO3Solution, Ag in mixed solution+'s
Concentration is 1.5mol/L, and mixed solution is shaken up and 190rpm magnetic rotors is used to stir 21h；Centrifuge is used with 2900rpm
Rotating speed separation 10min removes extra silver ion, then uses distilled water and alcohol to nanometer Ag-carbon microspheres (AgCS) of gained
It is rinsed, scattered 55min is carried out using ultrasonic wave again, to obtain even Ag- carbon microspheres.The wherein ratio table of carbon microspheres
Area is 2100~2200g/m2, the size of nano-silver ionic is 130~200nm in gained nanometer Ag-carbon microspheres.
(3) preparation of graphene/Ag- carbon microspheres aeroges
The graphene oxide suspension (concentration of graphene oxide is 4mg/ml) of 5ml is added in the AgCS solution of 10ml
It is uniformly mixed, the cysteine for then adding in nanometer Ag-carbon microspheres solution total amount 8% carries out ultrasonication 50min, obtains water
Then aqueous gel mixture is put into 8h in 85 DEG C of deep fats by gel mixture.Finally, 3D knots are washed off using ultra-pure water
Structure.Remaining bulk hydrogel changes into aeroge using freeze-drying, until spare.
(4) it is added to gained aeroge as additive in coating to get to the anti-fog haze composite coating of the present embodiment,
The additive amount of graphene/Ag- carbon microspheres aeroges accounts for the 5% of coating gross weight in the coating.Aeroge obtained by the present embodiment is applied
When material is for indoor and outdoor decoration, anti-fog haze effect is closer to embodiment 1.
Embodiment 4
A kind of preparation method of the graphene of the present embodiment/Ag- carbon microspheres aeroge coating, preparation process schematic diagram and
Flow chart as shown in Figure 3, Figure 4, specifically includes following steps：
(1) preparation of carbon microspheres：Using cellulose as raw material, carbon microspheres are prepared using hydro-thermal charring.
Specifically, weighing 0.7g celluloses in 20ml sample bottles, the deionized water of 10mL is added in, in turning for 30r/min
The lower magnetic agitation 25min of speed, makes cellulose uniformly disperse in the solution, is then placing it in the hydrothermal reaction kettle of 25mL.
After hydrothermal reaction kettle good seal, the constant heat preservation 6.5h at 210 DEG C is put into Muffle furnace, afterwards the natural cooling in Muffle furnace
To room temperature.The substance of lower floor in hydrothermal reaction kettle is filtered, is washed with absolute ethyl alcohol and distilled water, at 108 DEG C
Dry 10.5h.Carbon microspheres are put into according to impregnating ratio KOH/C=1.3 in crucible, is subsequently placed in micro-wave oven and carries out at activation
Reason, and nitrogen is passed through, microwave power 800W, soak time 8min；Then products therefrom is added into dilute HCl to neutrality, 110
Dry at DEG C, last products therefrom is the carbon microspheres of high-specific surface area, and scanned picture is shown in Fig. 1.
(2) preparation of nanometer Ag-carbon microspheres
The carbon microspheres suspension that mass concentration is taken to be 0.4%wt, pours into the distilled water of 15ml, then adds in AgNO3It is molten
Liquid, Ag in mixed solution+Concentration for 1.2mol/L, mixed solution is shaken up and use 220rpm magnetic rotors stirring 22h；It adopts
Extra silver ion is removed with 2850rpm rotating speeds separation 13min with centrifuge, then to nanometer Ag-carbon microspheres of gained
(AgCS) it is rinsed using distilled water and alcohol, scattered 50min is carried out using ultrasonic wave again, to obtain even Ag-
The specific surface area of carbon microspheres, wherein carbon microspheres is 1800~1900g/m2, the ruler of nano-silver ionic in gained nanometer Ag-carbon microspheres
Very little is 50~90nm.
(3) preparation of graphene/Ag- carbon microspheres aeroges
Graphene oxide suspension (concentration of graphene oxide is 3.5mg/ml) is added to nanometer Ag-carbon microspheres solution
In be uniformly mixed, then add in nanometer Ag-carbon microspheres solution total amount 7% cysteine be stirred, obtain hydrogel mixing
Object；Aqueous gel mixture is placed in 8h in 78 DEG C of deep fats, then washes off 3D structures, is handled using freeze-drying block-like
Hydrogel is to get to graphene/Ag- carbon microspheres aeroges.
(4) it is added to gained aeroge as additive in coating to get to the anti-fog haze composite coating of the present embodiment,
The additive amount of graphene/Ag- carbon microspheres aeroges accounts for the 8% of coating gross weight in the coating.Aeroge obtained by the present embodiment is applied
When material is for indoor and outdoor decoration, anti-fog haze effect is slightly better than embodiment 1.
Claims (10)
1. the preparation method of a kind of graphene/Ag- carbon microspheres aeroge coating, which is characterized in that this method is by coating
Middle addition graphene/Ag- carbon microspheres aeroges are prepared, and comprise the following steps：
Step 1: the preparation of nanometer Ag-carbon microspheres
AgNO is added in into the carbon microspheres suspension that mass concentration is 0.3~0.5%wt3Solution obtains mixed solution, and gained is mixed
It closes solution and carries out magnetic agitation, centrifugation, flushing and ultrasonic disperse processing respectively to get even Ag- carbon microspheres；
Step 2: the preparation of graphene/Ag- carbon microspheres aeroges
Graphene oxide suspension is added in nanometer Ag-carbon microspheres solution and is uniformly mixed, cysteine is then added in and carries out
Stirring, obtains aqueous gel mixture；Aqueous gel mixture is placed in 8~10h in 75~85 DEG C of deep fats, then washes off 3D knots
Structure handles block-like hydrogel to get to graphene/Ag- carbon microspheres aeroges using freeze-drying；
Step 3: the preparation of coating
It is added to gained aeroge as additive in coating to get graphene/Ag- carbon microspheres aeroge coating.
2. a kind of preparation method of graphene according to claim 1/Ag- carbon microspheres aeroge coating, it is characterised in that：
The additive amount of graphene/Ag- carbon microspheres aeroges is the 5~10% of coating gross weight in gained coating.
3. a kind of preparation method of graphene according to claim 1/Ag- carbon microspheres aeroge coating, it is characterised in that：
Gained carbon microspheres-AgNO in the step 13Ag in mixed solution+Concentration for 1~1.5mol/L, during the carbon microspheres are
Hollow structure, specific surface area are 1800~2200g/m2。
4. a kind of preparation method of graphene according to claim 3/Ag- carbon microspheres aeroge coating, it is characterised in that：
The size of nano-silver ionic is 50~200nm in gained nanometer Ag-carbon microspheres in the step 1.
5. a kind of preparation method of graphene/Ag- carbon microspheres aeroge coating according to any one of claim 1-4,
It is characterized in that：By carbon microspheres-AgNO in the step 13Mixed solution using 180~220rpm magnetic rotors stirring 20~
After for 24 hours, 10~15min is centrifuged to remove extra silver ion with the rotating speed of 2800~3000rpm, then to gained nanometer
Ag- carbon microspheres are rinsed using distilled water and alcohol, disperse 45~60min using ultrasonic wave to get to even again
Ag- carbon microspheres.
6. a kind of preparation method of graphene/Ag- carbon microspheres aeroge coating according to any one of claim 1-4,
It is characterized in that：The preparation method of carbon microspheres is as follows in the step 1：
(1) cellulose is uniformly dispersed in deionized water according to the amount of 5~8g/100ml, be subsequently placed in hydrothermal reaction kettle in
Cooled to room temperature after 6~8h of constant heat preservation at 200~220 DEG C；
(2) substance of lower floor in hydrothermal reaction kettle is filtered, is washed with absolute ethyl alcohol and distilled water, is subsequently placed in
10~12h is dried at 100~110 DEG C；
(3) substance after drying obtained by step (2) is put into according to impregnating ratio KOH/C=1.3~1.5 in crucible with KOH solution,
Be subsequently placed in micro-wave oven and carry out activation process, and be passed through nitrogen, microwave power is 600~800W, soak time for 8~
11min；
(4) gained activation products are added into dilute HCl to neutrality, be subsequently placed at 100~110 DEG C be dried processing to get than
Surface area is 1800~2200g/m2Carbon microspheres.
7. a kind of preparation method of graphene/Ag- carbon microspheres aeroge coating according to any one of claim 1-4,
It is characterized in that：In the step 2 concentration of graphene oxide contained by graphene oxide suspension be 3~5mg/ml, half Guang ammonia
The additive amount of acid is the 5~10% of nanometer Ag-carbon microspheres solution total amount.
8. the graphene being prepared according to the described method of any one of claim 1-7/Ag- carbon microspheres aeroge coating.
9. a kind of application in graphene as claimed in claim 8/Ag- carbon microspheres aeroges coating exterior decoration field indoors.
10. the application of graphene according to claim 9/Ag- carbon microspheres aeroge coating, it is characterised in that：By described in
Coating be used as indoor and outdoor decoration coating when, directly by its coated on substrate surface or as functional top coat in
Other coating surfaces.
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