CN107011783A - A kind of graphene/TiO2The preparation method of composite - Google Patents

A kind of graphene/TiO2The preparation method of composite Download PDF

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Publication number
CN107011783A
CN107011783A CN201710272217.1A CN201710272217A CN107011783A CN 107011783 A CN107011783 A CN 107011783A CN 201710272217 A CN201710272217 A CN 201710272217A CN 107011783 A CN107011783 A CN 107011783A
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tio
graphene
preparation
composite
added
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程俊
周雪
汤紫俊
鲁杰
戴宇
郭丽缨
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SICHUAN CARPOLY PAINT CO Ltd
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SICHUAN CARPOLY PAINT CO Ltd
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Abstract

The invention discloses a kind of graphene/TiO2The preparation method of composite, preparation of the present invention including graphene oxide, nano-TiO2Preparation, graphene/TiO2The preparation process of composite, the composite for preparing of the present invention has antibiotic property, applied to can improve the antibiotic property and environmental-protecting performance of coating in coating.

Description

A kind of graphene/TiO2The preparation method of composite
Technical field
The present invention relates to a kind of graphene/TiO2The preparation method of composite.
Background technology
Due to having unique and excellent performance in terms of physics and chemistry, polyurethane has as coating and adhesive And be widely applied.The development of aqueous polyurethane be largely because its excellent mechanical performance, fire resistance, hypotoxicity and Low environment endangers, but the carboxyl due to hydrophilic radical for example in its strand, and it has certain colony growth environment.
Chinese patent CN105949989A discloses a kind of aqueous UV antibiotic paints and preparation method thereof, including following weight The component of number：Urethane acrylate dispersoid, 60~80 parts；Nano silver colloidal sol, 5~15 parts；Reactive diluent, 5~20 Part；Light trigger, 3~6 parts；Levelling agent, 0.1~1 part；Dispersant, 0.1~1 part；Defoamer, 0.1~1 part, the patent is also carried A kind of preparation method of aqueous UV antibiotic paints is supplied.In above-mentioned aqueous UV antibiotic paints and preparation method thereof, the aqueous UV Antibiotic paint is all up to the sterilization rate of Escherichia coli and staphylococcus aureus to more than 95%, good anti-bacterial effect.
But there is the Nano Silver of costliness in the raw material of this method, production cost is higher, without large-scale mass production Prospect.
Chinese patent CN105925151A discloses a kind of preparation method of composite antibacterial coating, including following components：It is poly- Compound emulsion, Cu-Mn-F doping MgO nano antibacterial agents, Ag-ZnTiO3Nano antibacterial agent, organic antibacterial agent, toughener, emulsification Agent, coupling agent, stabilizer and solvent.
But this complex process equipment, and coating does not possess lipid-loweringing organics function, has very to the final using effect of coating Big influence.
Chinese patent CN103194935A discloses a kind of production technology of antibiotic paint, and it comprises the following steps：Prepare Include the mixed liquor of titanium dioxide granule and dispersant；Mechanical agitation is carried out to the mixed liquor with the mixed liquor Titanium dioxide granule carries out preliminary size degradation to form primary titanium dioxide particle dispersion；To the primary titanium dioxide particle point Dispersion liquid carries out ultrasonic vibration to form average grain diameter≤200nm nano-titania particle dispersion liquid；And by the nanometer TiO 2 particles dispersion liquid is mixed with coating easily forms the dispersed antibiotic paint for having a nano-titania particle, In the antibiotic paint, content >=5% of the nano-titania particle.
This method preparation technology is relatively easy, and titanium dioxide is evenly distributed in coating, what antibacterial ability was still improved Leeway.
The content of the invention
In order to improve above mentioned problem, the present invention provides a kind of graphene/TiO2The preparation method of composite, the composite wood Material can improve coating antibiosis.
Realize that technical scheme is as follows：
A kind of graphene/TiO2The preparation method of composite, it is characterised in that comprise the following steps：
The preparation of graphene oxide：
Graphite powder is put into container, and container is put into ice-water bath, the concentrated sulfuric acid is added into container, stirring 5~ 10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed in 21~26h of stirring under normal temperature；Then Container is put into ice-water bath, deionized water is added, 4~7min of ice-water bath is kept, hydrogen peroxide to bubble-free is added dropwise dropwise and produces； Finally filter, use salt acid elution, then be washed with deionized water to neutrality, ultrasound obtains graphene oxide after peeling off；
Nano-TiO2Preparation：
Absolute ethyl alcohol is slowly dropped in butyl titanate, stirring obtains uniform mixed solution in water bath with thermostatic control；So After add hydrochloric acid, then deionized water is slowly added dropwise, continues stirring and obtain butyl titanate colloidal sol, then carry out butyl titanate colloidal sol Dry, high-temperature calcination obtains light yellow crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, produces nanometer TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, carried out in ptfe autoclave anti- Should, solvent is removed after cooling, freeze-drying is pulverized, produce graphene/TiO2Composite.
Further, the present invention specifically includes following steps：
The preparation of graphene oxide：
Graphite powder is put into flask, and flask is put into ice-water bath, the concentrated sulfuric acid is added into flask, stirring 5~ 10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed in 21~26h of stirring under normal temperature；Then Container is put into ice-water bath, deionized water is added, 4~7min of ice-water bath is kept, hydrogen peroxide to bubble-free is added dropwise dropwise and produces； Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
Absolute ethyl alcohol is slowly dropped in butyl titanate, in water bath with thermostatic control with 400r/min speed stirring 25~ 35min obtains uniform mixed solution；Then hydrochloric acid is added, then deionized water is slowly added dropwise, continues 2~3h of stirring and obtains metatitanic acid Butyl titanate solution, is then put into vacuum drying chamber and 10~15h is dried, place into Muffle furnace by butyl acetate solution, and 3~5h is calcined at 450~600 DEG C and obtains light yellow crystal；Ground after finally light yellow crystal is mixed with absolute ethyl alcohol Mill, produces nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, in ptfe autoclave, and 2~12h is reacted under conditions of 160~180 DEG C, solvent is removed after cooling, drying and grinding produces graphene/TiO into powder2It is compound Material.
Yet further, the graphene oxide and nano-TiO2Weight ratio be 1:1~10.
The present invention has advantages below and beneficial effect：
Present invention process flow is simple, and raw material sources extensively, can effectively control production to prepare cost；Nano TiO 2 is in environment Had a wide range of applications in terms of protection, be primarily due to nano-TiO2With strong photochemical catalytic oxidation effect, can quickly, it is high Effect ground decomposing organic matter, generation carbon dioxide and water.Light-catalyzed reaction is main, and by efficient photocatalyst, its Strong oxdiative ability can be broken The structure of bad bacterium simultaneously decomposites bacterial body, solidifies virus protein, the activity of virus is controlled, to reach efficient sterilizing purpose. After the doping of some nonmetallic doping such as carbon, nitrogen, sulphur, above-mentioned entrance Detitanium-ore-type lattice, the position of oxygen is occupied, is reduced Band gap width, or impurity energy level is formed, or as gap ion, enable to the light absorbs after doping to extend to visible region Domain, the compound of photo-generate electron-hole is that another influences the key factor of photocatalytic activity, excites the electronics of generation empty by light Cave also can improve photocatalysis efficiency to being easily combined by reducing the compound of photo-generated carrier.New carbon graphene is answered Close TiO2Form composite, under both synergies, can reinforcing material to the photocatalysis performance of organic pollution. The hetero-junctions that graphene interface is formed cause between light induced electron and hole it is compound be improved, composite specific surface area Increase makes material be improved the adsorption capacity of organic pollution.
Embodiment
With reference to embodiment, the present invention is described further, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of graphene/TiO2The preparation method of composite, comprises the following steps：
The preparation of graphene oxide：
1g graphite powders are put into 500mL round-bottomed flasks, and flask is put into ice-water bath, 50mL is added into flask The concentrated sulfuric acid, stirs 5~10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature and stirred Mix 24h；Then container is put into ice-water bath, adds deionized water, keep ice-water bath 5min, hydrogen peroxide is added dropwise dropwise to without gas Bubble is produced；Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
12.5mL butyl titanates are added in 250mL three-necked flasks, 100mL absolute ethyl alcohols are then slowly dropped to metatitanic acid In butyl ester, uniform mixed solution is obtained with 400r/min speed stirring 30min in 25 DEG C of waters bath with thermostatic control；Then add 1.5mL hydrochloric acid, then 20mL deionized waters are slowly added dropwise, continue stirring 2.5h and obtain butyl titanate solution, then by butyl titanate Solution is put into 55 DEG C of vacuum drying chambers and 12h is dried, and places into Muffle furnace, and calcining 4h obtains yellowish at 500 DEG C Color crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, produces nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, wherein graphene and TiO2Mass ratio be 1: 2, in ptfe autoclave, and reacted under conditions of 180 DEG C solvent is removed after 6h, cooling, drying and grinding is into powder, i.e., Obtain graphene/TiO2Composite.
A kind of antibacterial aqueous polyurethane coating, includes the preparation of aqueous polyurethane：
13.32g IPDIs, 15g cetomacrogol 1000s are stirred at 80~90 DEG C, February is added Dilaurylate is incubated 1.5~2.5h as catalyst；It is cooled to after 65~75 DEG C, 2.7g is dissolved in the dihydroxy first of acetone Base butyric acid is added, and flow back 1.5~2.5h；55~64 DEG C are cooled to, 9.75g hydroxyethyl methacrylates are added, 5~7h is incubated； Be cooled to room temperature, add in appropriate triethylamine and 10min, be added dropwise 95mL deionized waters with 1300~1700r/min stirrings 20~ 40min；
The preparation of coating：
By graphene/TiO2Composite and light trigger are dissolved in acetone, the graphene/TiO2Composite and light draw The weight ratio for sending out agent is 3:1, solvent is steamed using Rotary Evaporators, graphene/TiO is obtained2Composite and light trigger Mixture, ultrasonic disperse is in the aqueous polyurethane prepared, and normal temperature cure film forming produces antibacterial aqueous polyurethane coating.
Anti-microbial property test：
Its bacteriostasis can be shown through AGP test using stripping property and non-stripping property antibacterial finishing agent, it is thin by observation The number of bacterium is to judge the stripping property of its antibacterial finishing agent and to whether there is biocidal property, bacteriostasis rate=(bacterial population-sample sets of contrast groups Bacterial population)/contrast groups bacterial population.
Using Escherichia coli and staphylococcus aureus as strain, the anti-microbial property of antibacterial aqueous polyurethane coating is determined.With 0.2ml bacteria suspensions are spread evenly across the culture medium after solidification by sterile working, and coating is uniform.Then treating that test sample is placed in training of carrying disease germs The center of base flat board is supported, culture dish is finally cultivated to the size that inhibition zone is observed after 18h in 37 DEG C.Compared with blank sample, plus Obvious inhibition zone is formd around the sample for entering graphene-TiO2 composites, shows graphene-TiO2Composite makes water Property polyurethane coating has obvious anti-microbial property.The antibiotic rate of antibacterial aqueous polyurethane coating reaches more than 0.9.
Embodiment 2
A kind of graphene/TiO2The preparation method of composite, comprises the following steps：
The preparation of graphene oxide：
1g graphite powders are put into 500mL round-bottomed flasks, and flask is put into ice-water bath, 50mL is added into flask The concentrated sulfuric acid, stirs 5~10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature and stirred Mix 24h；Then container is put into ice-water bath, adds deionized water, keep ice-water bath 5min, hydrogen peroxide is added dropwise dropwise to without gas Bubble is produced；Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
12.5mL butyl titanates are added in 250mL three-necked flasks, 100mL absolute ethyl alcohols are then slowly dropped to metatitanic acid In butyl ester, uniform mixed solution is obtained with 400r/min speed stirring 30min in 25 DEG C of waters bath with thermostatic control；Then add 1.5mL hydrochloric acid, then 20mL deionized waters are slowly added dropwise, continue stirring 2.5h and obtain butyl titanate solution, then by butyl titanate Solution is put into 55 DEG C of vacuum drying chambers and 12h is dried, and places into Muffle furnace, and calcining 4h obtains yellowish at 500 DEG C Color crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, produces nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, wherein graphene and TiO2Mass ratio be 1: 4, in ptfe autoclave, and reacted under conditions of 170 DEG C solvent is removed after 6h, cooling, drying and grinding is into powder, i.e., Obtain graphene/TiO2Composite.
Embodiment 3
A kind of graphene/TiO2The preparation method of composite, comprises the following steps：
The preparation of graphene oxide：
1g graphite powders are put into 500mL round-bottomed flasks, and flask is put into ice-water bath, 50mL is added into flask The concentrated sulfuric acid, stirs 5~10min；4g potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature Stir 24h；Then container is put into ice-water bath, adds deionized water, keep ice-water bath 5min, hydrogen peroxide is added dropwise dropwise to nothing Bubble is produced；Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
12.5mL butyl titanates are added in 250mL three-necked flasks, 100mL absolute ethyl alcohols are then slowly dropped to metatitanic acid In butyl ester, uniform mixed solution is obtained with 400r/min speed stirring 30min in 25 DEG C of waters bath with thermostatic control；Then add 1.5mL hydrochloric acid, then 20mL deionized waters are slowly added dropwise, continue stirring 2.5h and obtain butyl titanate solution, then by butyl titanate Solution is put into 55 DEG C of vacuum drying chambers and 12h is dried, and places into Muffle furnace, and calcining 4h obtains yellowish at 500 DEG C Color crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, produces nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, wherein graphene and TiO2Mass ratio be 1: 6, in ptfe autoclave, and reacted under conditions of 160 DEG C solvent is removed after 6h, cooling, drying and grinding is into powder, i.e., Obtain graphene/TiO2Composite.
Embodiment 4
A kind of graphene/TiO2The preparation method of composite, comprises the following steps：
The preparation of graphene oxide：
1g graphite powders are put into 500mL round-bottomed flasks, and flask is put into ice-water bath, 50mL is added into flask The concentrated sulfuric acid, stirs 5~10min；4g potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature Stir 24h；Then container is put into ice-water bath, adds deionized water, keep ice-water bath 5min, hydrogen peroxide is added dropwise dropwise to nothing Bubble is produced；Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
12.5mL butyl titanates are added in 250mL three-necked flasks, 100mL absolute ethyl alcohols are then slowly dropped to metatitanic acid In butyl ester, uniform mixed solution is obtained with 400r/min speed stirring 30min in 25 DEG C of waters bath with thermostatic control；Then add 1.5mL hydrochloric acid, then 20mL deionized waters are slowly added dropwise, continue stirring 2.5h and obtain butyl titanate solution, then by butyl titanate Colloidal sol is put into 55 DEG C of vacuum drying chambers and 12h is dried, and places into Muffle furnace, and calcining 4h obtains yellowish at 500 DEG C Color crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, produces nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, wherein graphene and TiO2Mass ratio be 1: 10, in ptfe autoclave, and reacted under conditions of 180 DEG C solvent removed after 2h, cooling, drying and grinding into powder, Produce graphene/TiO2Composite.
Embodiment 5
A kind of graphene/TiO2The preparation method of composite, comprises the following steps：
The preparation of graphene oxide：
1g graphite powders are put into 500mL round-bottomed flasks, and flask is put into ice-water bath, 50mL is added into flask The concentrated sulfuric acid, stirs 5~10min；4g potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature Stir 24h；Then container is put into ice-water bath, adds deionized water, keep ice-water bath 5min, hydrogen peroxide is added dropwise dropwise to nothing Bubble is produced；Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
12.5mL butyl titanates are added in 250mL three-necked flasks, 100mL absolute ethyl alcohols are added dropwise, in 25 DEG C of waters bath with thermostatic control In uniform mixed solution is obtained with 400r/min speed stirring 30min；Then 1.5mL hydrochloric acid is added, then is slowly added dropwise 20mL deionized waters, continue stirring 2.5h and obtain butyl titanate colloidal sol, butyl titanate colloidal sol then is put into 55 DEG C of vacuum drying 12h is dried in case, places into Muffle furnace, and 4h is calcined at 500 DEG C and obtains light yellow crystal；Finally by faint yellow crystalline substance Body is ground after being mixed with absolute ethyl alcohol, produces nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, wherein graphene and TiO2Mass ratio be 1: 5, in ptfe autoclave, and reacted under conditions of 170 DEG C solvent is removed after 6h, cooling, drying and grinding is into powder, i.e., Obtain graphene/TiO2Composite.
Embodiment 6
A kind of graphene/TiO2The preparation method of composite, comprises the following steps：
The preparation of graphene oxide：
1g graphite powders are put into 500mL round-bottomed flasks, and flask is put into ice-water bath, 50mL is added into flask The concentrated sulfuric acid, stirs 5~10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed under normal temperature and stirred Mix 24h；Then container is put into ice-water bath, adds deionized water, keep ice-water bath 5min, hydrogen peroxide is added dropwise dropwise to without gas Bubble is produced；Finally filter, with 3% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
12.5mL butyl titanates are added in 250mL three-necked flasks, 100mL absolute ethyl alcohols are then added dropwise, in 25 DEG C of constant temperature Uniform mixed solution is obtained with 400r/min speed stirring 30min in water-bath；Then 1.5mL hydrochloric acid, then slow drop are added Plus 20mL deionized waters, continue stirring 2.5h and obtain butyl titanate solution, butyl titanate solution then is put into 55 DEG C of vacuum does 12h is dried in dry case, places into Muffle furnace, and 4h is calcined at 500 DEG C and obtains light yellow crystal；Finally will be faint yellow Crystal is ground after being mixed with absolute ethyl alcohol, produces nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, wherein graphene and TiO2Mass ratio be 1: 7, in ptfe autoclave, and reacted under conditions of 160 DEG C solvent is removed after 6h, cooling, freeze-drying is ground to form Powder, produces graphene/TiO2Composite.
It should be noted that above example is only used to illustrative and not limiting technical scheme, although with reference to upper Embodiment is stated the present invention is described in detail, it will be understood by those within the art that：Still can be to the present invention Modify or equivalent substitution, any modification or partial replacement without departing from the spirit and scope of the present invention, it all should contain Cover in scope of the presently claimed invention.

Claims (3)

1. a kind of graphene/TiO2The preparation method of composite, it is characterised in that comprise the following steps：
The preparation of graphene oxide：
Graphite powder is put into container, and container is put into ice-water bath, the concentrated sulfuric acid is added into container, stirring 5~ 10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed in 21~26h of stirring under normal temperature；Then Container is put into ice-water bath, deionized water is added, 4~7min of ice-water bath is kept, hydrogen peroxide to bubble-free is added dropwise dropwise and produces； Finally filter, use salt acid elution, then be washed with deionized water to neutrality, ultrasound obtains graphene oxide after peeling off；
Nano-TiO2Preparation：
Absolute ethyl alcohol is slowly dropped in butyl titanate, stirring obtains uniform mixed solution in water bath with thermostatic control；Then plus Enter hydrochloric acid, then deionized water is slowly added dropwise, continue stirring and obtain butyl titanate solution, then done butyl titanate solution Dry, high-temperature calcination obtains light yellow crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, produces nanometer TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, reacted in ptfe autoclave, it is cold But solvent is removed afterwards, freeze-drying is pulverized, produce graphene/TiO2Composite.
2. a kind of graphene/TiO according to claim 12The preparation method of composite, it is characterised in that including following Step：
The preparation of graphene oxide：
Graphite powder is put into flask, and flask is put into ice-water bath, the concentrated sulfuric acid is added into flask, stirring 5~ 10min；Potassium permanganate is slowly added to, continues to stir 15~20min；Then container is placed in 21~26h of stirring under normal temperature；Then Container is put into ice-water bath, deionized water is added, 4~7min of ice-water bath is kept, hydrogen peroxide to bubble-free is added dropwise dropwise and produces； Finally filter, with 30% salt acid elution, then be washed with deionized water to neutrality, ultrasound peel off after graphene oxide；
Nano-TiO2Preparation：
Absolute ethyl alcohol is slowly dropped in butyl titanate, 25~35min is stirred with 400r/min speed in water bath with thermostatic control Obtain uniform mixed solution；Then hydrochloric acid is added, then deionized water is slowly added dropwise, continues 2~3h of stirring and obtains butyl titanate Butyl titanate colloidal sol, is then put into vacuum drying chamber and 10~15h is dried, place into Muffle furnace by colloidal sol, and 450 3~5h is calcined at~600 DEG C and obtains light yellow crystal；It is ground after finally light yellow crystal is mixed with absolute ethyl alcohol, i.e., Obtain nano-TiO2；
Graphene/TiO2The preparation of composite：
Graphene oxide is distributed in absolute ethyl alcohol, nano-TiO is added2, in ptfe autoclave, and 160~ 2~12h is reacted under conditions of 180 DEG C, solvent is removed after cooling, drying and grinding produces graphene/TiO into powder2Composite.
3. a kind of graphene/TiO according to claim 1 or 22The preparation method of composite, it is characterised in that described Graphene oxide and nano-TiO2Weight ratio be 1:1~10.
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