CN102631910A - Stable graphene/titanium oxide composite nanosol and preparation method thereof - Google Patents
Stable graphene/titanium oxide composite nanosol and preparation method thereof Download PDFInfo
- Publication number
- CN102631910A CN102631910A CN201210074661XA CN201210074661A CN102631910A CN 102631910 A CN102631910 A CN 102631910A CN 201210074661X A CN201210074661X A CN 201210074661XA CN 201210074661 A CN201210074661 A CN 201210074661A CN 102631910 A CN102631910 A CN 102631910A
- Authority
- CN
- China
- Prior art keywords
- graphene
- colloidal sol
- titanium oxide
- oxide composite
- composite nano
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a graphene/titanium oxide composite nanosol and a preparation method thereof. The preparation method comprises the following steps: 1) dissolving graphene oxide in a solvent to obtain a graphene oxide solution, and regulating the pH value with acid; 2) adding a mixed liquid of tetra-n-butyl titanate and isopropanol into the graphene oxide solution obtained in the step 1), and carrying out condensation reflux on the mixture to obtain a sol; 3) adding a reducer into the sol to carry out the reaction; and after the reaction finishes, sequentially carrying out ultrasonic treatment and dialytic purifying treatment to obtain the graphene/titanium oxide composite nanosol. The titanium oxide particles in the composite nano sol are very small; the sol can stably exist for a long time by regulating the pH value; and a transparent titanium oxide/graphene composite functional film can be prepared on various substrates by spin coating, spray coating, roller coating and drip coating.
Description
Technical field
The present invention relates to a kind of stable Graphene/titanium oxide composite Nano colloidal sol and preparation method thereof.
Background technology
Solar energy receives increasing concern with its cleaning, renewable, safe characteristics.Photocatalysis technology utilizes solar energy to carry out the new technology that energy transforms just, and improving light-catalysed transformation efficiency is the most important thing that promotes this technological extensive use.Titanium oxide is with its nontoxic stable, concern that high, the low-cost characteristics of memory space receive photocatalysis field all the time.Be coated on the fields such as antifog, fungi-proofing, mildew-resistant, automatically cleaning that are applied to as functional film of the transparent titania film success on glass or the plastic.Under illumination condition, titanium oxide in the film produces light induced electron and hole, and the state variation of Ti atom makes film change into hydrophilicly from hydrophobic, makes film possess anti-fog function; Light induced electron and hole and reactant generation chemical reaction on every side that illumination produces make film possess the fungi-proofing and self-cleaning function of mildew-resistant.But in titanium oxide, the electronics that illumination produces very easily and hole-recombination makes that the efficient of titanium oxide is not high.Numerous researchers have explored the method that improves titanium oxide efficient from all angles, find that wherein the load of material with carbon element (like fullerene, CNT etc.) can effectively improve separating of light induced electron and hole.Graphene is a kind of novel two-dimentional material with carbon element of finding in recent years, is the highest material of the speed of electric transmission at room temperature that exists in the world at present.The load of Graphene can be played the effect of electron propagation ducts, and the light induced electron on the titanium oxide is in time derived, and avoids the compound of itself and hole, and then improves the electricity conversion of titanium oxide and then the function film effect that improves thin film of titanium oxide.
The composite of titanium oxide/Graphene is main with powder at present, and needs through high temperature or HIGH PRESSURE TREATMENT more, and this has limited the use of this composite greatly.Find that through document retrieval the patent No. is that adopting the compound of agitated reactor preparation is slurry, powder type, can't prepare transparent membrane in 201010237588.4 the patent of invention; The patent No. is in 200910196534.5 the invention, adopts preparing graphene-based titanium dioxide composite photocatalyst by radiation of electron beams, and the gained catalyst also is the powder state; The Chinese invention patent application number is 201110228170.1 patent of invention; Though its composite catalyst exists with solation; But its titanium oxide that uses is the P25 titanium oxide, and its granular size is more than 30nm, according to the pH value of its solution; This titanium oxide Graphene colloidal sol is stable existence for a long time, also can't be adapted to the industrial and large-scale coating process.
Summary of the invention
The purpose of this invention is to provide a kind of stable Graphene/titanium oxide composite Nano colloidal sol and preparation method thereof.
Graphene provided by the present invention/titanium oxide composite Nano colloidal sol is to prepare according to the method that comprises the steps: 1) graphene oxide is dissolved in the solvent, obtains graphene oxide solution, and regulate its pH value to 1～6 with acid;
2) mixed liquor of tetra-n-butyl titanate and isopropyl alcohol is joined in the graphene oxide solution that step 1) obtains, and mixture is carried out condensing reflux, obtain colloidal sol;
3) in said colloidal sol, adding reducing agent reacts; Reaction finishes the back colloidal sol is carried out sonicated, dialysis purified treatment successively, obtains Graphene/titanium oxide composite Nano colloidal sol.
Wherein, solvent described in the step 1) can be water or ethanol;
Acid-specific described in the step 1) can be hydrochloric acid, nitric acid or sulfuric acid.
Step 2) graphene oxide in the solution of graphene oxide described in and the mass ratio of tetra-n-butyl titanate are 0.03125: 100～1.250: 100.
Step 2) condensing reflux described in carries out through water-bath or oil bath heating, and the temperature of said water-bath or oil bath is 50 ℃～150 ℃; The said condensing reflux time is no less than 12 hours, specifically can be 12～24 hours.
Reducing agent described in the step 3) is a hydrazine; The proportioning of graphene oxide is 1 μ L hydrazine in said reducing agent and the said colloidal sol: (the graphene oxide of 0.1mg～5mg); Said being reflected under the stirring carried out, and the temperature of said reaction is more than 80 ℃, is specially 95 ℃～150 ℃, and the time of said reaction was specially 5～12 hours greater than 1 hour.
The power of the said sonicated of step 3) is more than the 100W, and ultrasonic time was specially 1～5 hour greater than 20 minutes.
Graphene/titanium oxide composite Nano the colloidal sol of the present invention preparation can stable existence 3 months.
Graphene comprises its state of oxidation and reducing condition in this composite Nano colloidal sol; The mass ratio of Graphene and oxide thereof and titanium dioxide is 0.01: 100～5: 100.Wherein, the particle diameter of titan oxide particles is between 2 nanometer to 20 nanometers, and principal phase is anatase crystal.
A further object of the present invention provides a kind of Graphene/titanium oxide composite film,
Graphene/titanium oxide composite film provided by the present invention is that above-mentioned Graphene/titanium oxide composite Nano colloidal sol is coated on the substrate, obtains after the drying.
The exist form and the multiple industrialization of Graphene of the present invention/titanium oxide composite Nano colloidal sol apply modes such as means are coated with as dripping, spin coating, roller coating, spraying compatibility mutually; Can be deposited on the multiple substrate through these coating methods; Hard substrates such as glass, silicon chip, flexible substrate such as PET etc.Obtain fine and close TiOx nano particle/graphene film after the deposition drying, film forming thickness can be regulated through the colloidal sol amount of control deposition easily.Graphene has played the effect of electric transmission bridge in film, light induced electron in time is transmitted on the substrate from the TiOx nano particle, promotes separating of light induced electron and hole.Through the mensuration of electrochemical workstation, to add the complex thin film that deposits behind the Graphene and do not had the film that adds, photoelectric current intensity has improved five times nearly, and the film transparency is good, and is high with various substrate conjugations.This film can be used for being coated on and has automatically cleaning, fungi-proofing, an antifog function film of mildew-resistant on glass or the plastics.Also can be used for preparing the heavy industrialization manufacturing of flexible solar battery.
Description of drawings
Fig. 1 is 1 o'clock for pH, the Graphene of different quality ratio and the Zeta potential figure of titanium dioxide complex sol.
Fig. 2 composes for the XRD figure of titanium dioxide in Graphene and the titanium dioxide complex sol of preparation.
Wherein, What sample A was corresponding among Fig. 1,2 is the product among the embodiment 8 (RGO (reduction Graphene) load capacity 0.1%); What sample B was corresponding is the product among the embodiment 5 (RGO load capacity 0.5%), and what sample C was corresponding is the product among the embodiment 1,3,4,6 (RGO load capacity 1%), and what sample D was corresponding is the product among the embodiment 2 (RGO load capacity 2%); What sample E was corresponding is the product among the embodiment 9 (RGO load capacity 3%), and what sample F was corresponding is the product among the embodiment 7 (RGO load capacity 4%); Sample TiO among Fig. 2
2Be the pure zirconia titanium colloidal sol that replaces graphene oxide solution to process with pure water.
The specific embodiment
The present invention will be described through specific embodiment below, but the present invention is not limited thereto.
Experimental technique described in the following embodiment like no specified otherwise, is conventional method; Said reagent and material like no specified otherwise, all can obtain from commercial sources.
Used graphene oxide is for adopting modified Hummers method in prepared in laboratory among the following embodiment; Concrete steps are following: the 10g native graphite is put into the 500ml conical flask; After in ice bath, adding 230ml sulfuric acid; Add 30g potassium permanganate again, with mixed liquor at 10 ℃ of vigorous stirring 60min.Mixed liquor is heated to 35 ℃ stirs 2h down, in ice bath, slowly add the 160ml deionized water afterwards, afterwards at 98 ℃ of stirred in water bath 1h.Solution with water is diluted to 1.4l, adds 35ml H at last
2O
2(30%).After the solution filtration, clean with 3wt%HCl, obtain the pale brown toner of graphene oxide (GO) end after the drying.Powder dissolution is obtained the graphite oxide aqueous solution in deionized water.
Embodiment 1:
1) the 3.125mg graphene oxide is dissolved in the 150ml water, obtaining concentration is the graphite oxide aqueous solution of 0.0208mg/ml; Add hydrochloric acid, the pH value of graphene aqueous solution is adjusted to 1;
2) get positive four butyl esters of 1ml metatitanic acid and 1.5ml isopropyl alcohol, vibration mixes;
3) on magnetic stirring apparatus, stir the graphite oxide aqueous solution, slowly drip along the rightabout that stirs with the mixed liquor of dropper with tetra-n-butyl titanate and isopropyl alcohol, rate of addition is 1ml/min;
4) with mixed solution in stirred in water bath heating and carry out condensing reflux, bath temperature remains on 80 ℃, the condensing reflux time is 24 hours;
5) hydrazine of adding 9.37 μ l in the colloidal sol behind condensing reflux keeps stirring 12 hours in 95 ℃ of water-baths;
6) ultrasonic 1 hour (200W) back of the colloidal sol after will stirring is carried out dialysis and is handled to remove impurity in water, obtains finished product colloidal sol.The mass ratio of Graphene and titanium dioxide is about 1: 100 in the colloidal sol.
7) 1ml finished product colloidal sol is dripped on the ITO-PET substrate of 2cm * 2cm size, at room temperature drying and forming-film.
8) with dried film as working electrode, Pt is as to electrode, 0.5M Na
2SO
4As electrolyte, the 350W xenon lamp is as light source, and under not biased situation, with the photoelectric current of CHI660D electrochemical workstation MEASUREMENTS OF THIN, the photoelectric current that obtains is 1.02 μ A.In the above-mentioned experiment, replace the graphite oxide aqueous solution with pure water, obtain pure zirconia titanium colloidal sol, the photoelectric current of its corresponding thin film of titanium oxide is 0.22 μ A.
Embodiment 2:
1) the 6.25mg graphene oxide is dissolved in the 150ml water, obtaining concentration is the graphite oxide aqueous solution of 0.0416mg/ml; Add hydrochloric acid, the pH value of graphene aqueous solution is adjusted to 1;
2) get positive four butyl esters of 1ml metatitanic acid and 1.5ml isopropyl alcohol, vibration mixes;
3) on magnetic stirring apparatus, stir the graphite oxide aqueous solution, slowly drip along the rightabout that stirs with the mixed liquor of dropper with tetra-n-butyl titanate and isopropyl alcohol, rate of addition is 1ml/min;
4) mixed solution is heated and carry out condensing reflux in stirred in water bath, bath temperature remains on 80 degree, and the condensing reflux time is 24 hours;
5) hydrazine of adding 18.74 μ l in the colloidal sol behind condensing reflux keeps stirring 12 hours in 95 degree water-baths;
6) ultrasonic 1 hour (200W) back of the colloidal sol after will stirring is carried out dialysis and is handled to remove impurity in water, obtains finished product colloidal sol.The mass ratio of Graphene and titanium dioxide is about 2: 100 in the colloidal sol.
7) 1ml finished product colloidal sol is dripped on the ITO-PET substrate of 2cm * 2cm size, at room temperature drying and forming-film.
8) with dried film as working electrode, Pt is as to electrode, 0.5M Na
2SO
4As electrolyte, the 350W xenon lamp is as light source, and under not biased situation, with the photoelectric current of CHI660D electrochemical workstation MEASUREMENTS OF THIN, the photoelectric current that obtains is 0.92 μ A.
Embodiment 3:
1) the 3.125mg graphene oxide is dissolved in the 150ml water, obtaining concentration is the graphite oxide aqueous solution of 0.0208mg/ml; Add hydrochloric acid, the pH value of graphene aqueous solution is adjusted to 1;
2) get positive four butyl esters of 1ml metatitanic acid and 1.5ml isopropyl alcohol, vibration mixes;
3) on magnetic stirring apparatus, stir the graphite oxide aqueous solution, slowly drip along the rightabout that stirs with the mixed liquor of dropper with tetra-n-butyl titanate and isopropyl alcohol, rate of addition is 1ml/min;
4) mixed solution is heated and carry out condensing reflux in stirred in water bath, bath temperature remains on 80 degree, and the condensing reflux time is 24 hours;
5) hydrazine of adding 9.37 μ l in the colloidal sol behind condensing reflux keeps stirring 5 hours in 150 degree oil baths;
6) ultrasonic 1 hour (250W) back of the colloidal sol after will stirring is carried out dialysis and is handled to remove impurity in water, obtains finished product colloidal sol.The mass ratio of Graphene and titanium dioxide is about 1: 100 in the colloidal sol.
7) 1ml finished product colloidal sol is dripped on the ITO-PET substrate of 2cm * 2cm size, at room temperature drying and forming-film.
8) with dried film as working electrode, Pt is as to electrode, 0.5M Na
2SO
4As electrolyte, the 350W xenon lamp is as light source, and under not biased situation, with the photoelectric current of CHI660D electrochemical workstation MEASUREMENTS OF THIN, the photoelectric current that obtains is 0.98 μ A.
Embodiment 4:
1) the 3.125mg graphene oxide is dissolved in the 150ml water, obtaining concentration is the graphite oxide aqueous solution of 0.0208mg/ml; Add sulfuric acid, the pH value of graphene aqueous solution is adjusted to 1;
2) get positive four butyl esters of 1ml metatitanic acid and 1ml isopropyl alcohol, vibration mixes;
3) on magnetic stirring apparatus, stir the graphite oxide aqueous solution, slowly drip along the rightabout that stirs with the mixed liquor of dropper with tetra-n-butyl titanate and isopropyl alcohol, rate of addition is 1ml/min;
4) mixed solution is heated and carry out condensing reflux in stirred in water bath, bath temperature remains on 80 degree, and the condensing reflux time is 24 hours;
5) hydrazine of adding 9.37 μ l in the colloidal sol behind condensing reflux keeps stirring 5 hours in 150 degree oil baths;
6) ultrasonic 1 hour (250W) back of the colloidal sol after will stirring is carried out dialysis and is handled to remove impurity in water, obtains finished product colloidal sol.The mass ratio of Graphene and titanium dioxide is about 1: 100 in the colloidal sol.
7) 1ml finished product colloidal sol is dripped on the ITO-PET substrate of 2cm * 2cm size, at room temperature drying and forming-film.
8) with dried film as working electrode, Pt is as to electrode, 0.5M Na2SO4 is as electrolyte; The 350W xenon lamp is as light source; Under not biased situation, with the photoelectric current of CHI660D electrochemical workstation MEASUREMENTS OF THIN, the photoelectric current that obtains is 1.00 μ A.
Embodiment 5:
1) the 1.563mg graphene oxide is dissolved in the 150ml water, obtaining concentration is the graphite oxide aqueous solution of 0.010mg/ml; Add sulfuric acid, the pH value of graphene aqueous solution is adjusted to 6;
2) get positive four butyl esters of 1ml metatitanic acid and 1ml isopropyl alcohol, vibration mixes;
3) on magnetic stirring apparatus, stir the graphite oxide aqueous solution, slowly drip along the rightabout that stirs with the mixed liquor of dropper with tetra-n-butyl titanate and isopropyl alcohol, rate of addition is 1ml/min;
4) mixed solution is heated and carry out condensing reflux in stirred in water bath, bath temperature remains on 85 degree, and the condensing reflux time is 30 hours;
5) hydrazine of adding 9.37 μ l in the colloidal sol behind condensing reflux keeps stirring 12 hours in 120 degree oil baths;
6) colloidal sol after will stirring carries out dialysis and handles to remove impurity in water after ultrasonic 2 hours, obtains finished product colloidal sol.The mass ratio of Graphene and titanium dioxide is about 0.5: 100 in the colloidal sol.
7) 1ml finished product colloidal sol is dripped on the ITO-PET substrate of 2cm * 2cm size, at room temperature drying and forming-film.
8) with dried film as working electrode, Pt is as to electrode, 0.5M Na2SO4 is as electrolyte; The 350W xenon lamp is as light source; Under not biased situation, with the photoelectric current of CHI660D electrochemical workstation MEASUREMENTS OF THIN, the photoelectric current that obtains is 1.25 μ A.
Embodiment 6:
1) the 3.125mg graphene oxide is dissolved in the 150ml water, obtaining concentration is the graphite oxide aqueous solution of 0.0208mg/ml; Add sulfuric acid, the pH value of graphene aqueous solution is adjusted to 1;
2) get positive four butyl esters of 1ml metatitanic acid and 1.5ml isopropyl alcohol, vibration mixes;
3) on magnetic stirring apparatus, stir the graphite oxide aqueous solution, slowly drip along the rightabout that stirs with the mixed liquor of dropper with tetra-n-butyl titanate and isopropyl alcohol, rate of addition is 1ml/min;
4) mixed solution is heated and carry out condensing reflux in stirred in water bath, bath temperature remains on 90 degree, and the condensing reflux time is 18 hours;
5) hydrazine of adding 9.37 μ l in the colloidal sol behind condensing reflux keeps stirring 10 hours in 100 degree oil baths;
6) ultrasonic 1 hour (160W) back of the colloidal sol after will stirring is carried out dialysis and is handled to remove impurity in water, obtains finished product colloidal sol.The mass ratio of Graphene and titanium dioxide is about 1: 100 in the colloidal sol.
7) 1ml finished product colloidal sol is dripped on the ITO-PET substrate of 2cm * 2cm size, at room temperature drying and forming-film.
8) with dried film as working electrode, Pt is as to electrode, 0.5M Na2SO4 is as electrolyte; The 350W xenon lamp is as light source; Under not biased situation, with the photoelectric current of CHI660D electrochemical workstation MEASUREMENTS OF THIN, the photoelectric current that obtains is 0.95 μ A.
Embodiment 7:
1) the 12.5mg graphene oxide is dissolved in the 150ml water, obtaining concentration is the graphite oxide aqueous solution of 0.0832mg/ml; Add sulfuric acid, the pH value of graphene aqueous solution is adjusted to 1;
2) get positive four butyl esters of 1ml metatitanic acid and 1.5ml isopropyl alcohol, vibration mixes;
3) on magnetic stirring apparatus, stir the graphite oxide aqueous solution, slowly drip along the rightabout that stirs with the mixed liquor of dropper with tetra-n-butyl titanate and isopropyl alcohol, rate of addition is 1ml/min;
4) mixed solution is heated and carry out condensing reflux in stirred in water bath, bath temperature remains on 75 degree, and the condensing reflux time is 12 hours;
5) hydrazine of adding 37.48 μ l in the colloidal sol behind condensing reflux keeps stirring 10 hours in 100 degree oil baths;
6) ultrasonic 1 hour (160W) back of the colloidal sol after will stirring is carried out dialysis and is handled to remove impurity in water, obtains finished product colloidal sol.The mass ratio of Graphene and titanium dioxide is about 4: 100 in the colloidal sol.
7) 1ml finished product colloidal sol is dripped on the ITO-PET substrate of 2cm * 2cm size, at room temperature drying and forming-film.
8) with dried film as working electrode, Pt is as to electrode, 0.5M Na2SO4 is as electrolyte; The 350W xenon lamp is as light source; Under not biased situation, with the photoelectric current of CHI660D electrochemical workstation MEASUREMENTS OF THIN, the photoelectric current that obtains is 0.45 μ A.
Embodiment 8:
1) the 0.3125mg graphene oxide is dissolved in the 150ml water, obtaining concentration is the graphite oxide aqueous solution of 0.0021mg/ml; Add sulfuric acid, the pH value of graphene aqueous solution is adjusted to 2;
2) get positive four butyl esters of 1ml metatitanic acid and 1.5ml isopropyl alcohol, vibration mixes;
3) on magnetic stirring apparatus, stir the graphite oxide aqueous solution, slowly drip along the rightabout that stirs with the mixed liquor of dropper with tetra-n-butyl titanate and isopropyl alcohol, rate of addition is 1ml/min;
4) mixed solution is heated and carry out condensing reflux in stirred in water bath, bath temperature remains on 90 degree, and the condensing reflux time is 24 hours;
5) hydrazine of adding 8.21 μ l in the colloidal sol behind condensing reflux keeps stirring 6 hours in 95 degree water-baths;
6) colloidal sol after will stirring carries out dialysis and handles to remove impurity in water after ultrasonic 5 hours, obtains finished product colloidal sol.The mass ratio of Graphene and titanium dioxide is about 0.1: 100 in the colloidal sol.
7) 1ml finished product colloidal sol is dripped on the ITO-PET substrate of 2cm * 2cm size, at room temperature drying and forming-film.
8) with dried film as working electrode, Pt is as to electrode, 0.5M Na2SO4 is as electrolyte; The 350W xenon lamp is as light source; Under not biased situation, with the photoelectric current of CHI660D electrochemical workstation MEASUREMENTS OF THIN, the photoelectric current that obtains is 0.68 μ A.
Embodiment 9:
1) the 9.375mg graphene oxide is dissolved in the 150ml water, obtaining concentration is the graphite oxide aqueous solution of 0.016mg/ml; Add sulfuric acid, the pH value of graphene aqueous solution is adjusted to 6;
2) get positive four butyl esters of 1ml metatitanic acid and 1ml isopropyl alcohol, vibration mixes;
3) on magnetic stirring apparatus, stir the graphite oxide aqueous solution, slowly drip along the rightabout that stirs with the mixed liquor of dropper with tetra-n-butyl titanate and isopropyl alcohol, rate of addition is 1ml/min;
4) mixed solution is heated and carry out condensing reflux in stirred in water bath, bath temperature remains on 150 degree, and the condensing reflux time is 30 hours;
5) hydrazine of adding 8.24 μ l in the colloidal sol behind condensing reflux keeps stirring 10 hours in 100 degree oil baths;
6) colloidal sol after will stirring carries out dialysis and handles to remove impurity in water after ultrasonic 1.5 hours, obtains finished product colloidal sol.The mass ratio of Graphene and titanium dioxide is about 3: 100 in the colloidal sol.
7) 1ml finished product colloidal sol is dripped on the ITO-PET substrate of 2cm * 2cm size, at room temperature drying and forming-film.
8) with dried film as working electrode, Pt is as to electrode, 0.5M Na2SO4 is as electrolyte; The 350W xenon lamp is as light source; Under not biased situation, with the photoelectric current of CHI660D electrochemical workstation MEASUREMENTS OF THIN, the photoelectric current that obtains is 0.56 μ A.
Claims (10)
1. a method for preparing Graphene/titanium oxide composite Nano colloidal sol comprises the steps:
1) graphene oxide is dissolved in the solvent, obtains graphene oxide solution, and regulate its pH value to 1～6 with acid;
2) mixed liquor of tetra-n-butyl titanate and isopropyl alcohol is joined in the graphene oxide solution that step 1) obtains, and mixture is carried out condensing reflux, obtain colloidal sol;
3) in said colloidal sol, adding reducing agent reacts; Reaction finishes the back colloidal sol is carried out sonicated, dialysis purified treatment successively, obtains Graphene/titanium oxide composite Nano colloidal sol.
2. method according to claim 1 is characterized in that: solvent described in the step 1) is water or ethanol; Acid is hydrochloric acid, nitric acid or sulfuric acid described in the step 1).
3. method according to claim 1 and 2 is characterized in that: step 2) described in graphene oxide and the mass ratio of tetra-n-butyl titanate in the graphene oxide solution be 0.03125: 100～1.250: 100.
4. according to each described method among the claim 1-3, it is characterized in that: step 2) described in condensing reflux carry out through water-bath or oil bath heating, the temperature of said water-bath or oil bath is 50 ℃～150 ℃; The said condensing reflux time is no less than 12 hours, is specially 12～24 hours.
5. according to each described method among the claim 1-4, it is characterized in that: reducing agent described in the step 3) is a hydrazine; The proportioning of graphene oxide is 1 μ L hydrazine in said reducing agent and the said colloidal sol: (0.1mg～5mg) said being reflected under the stirring of graphene oxide carried out; The temperature of said reaction is more than 80 ℃; Be specially 95 ℃～150 ℃, the time of said reaction was specially 5～12 hours greater than 1 hour.
6. according to each described method among the claim 1-5, it is characterized in that: the power of the said sonicated of step 3) is 100～1000W, and ultrasonic time was specially 1～5 hour greater than 20 minutes.
7. the Graphene that each said method prepares among the claim 1-6/titanium oxide composite Nano colloidal sol.
8. Graphene according to claim 7/titanium oxide composite Nano colloidal sol is characterized in that: the mass ratio of Graphene and oxide and titanium oxide is 0.1: 100～4: 100 in said Graphene/titanium oxide composite Nano colloidal sol.
9. according to claim 7 or 8 described Graphenes/titanium oxide composite Nano colloidal sol, it is characterized in that: the particle diameter of titan oxide particles is between the 2-20 nanometer in said Graphene/titanium oxide composite Nano colloidal sol.
10. a Graphene/titanium oxide composite film is that each described Graphene/titanium oxide composite Nano colloidal sol among the claim 7-9 is coated on the substrate, obtains after the drying.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210074661.XA CN102631910B (en) | 2012-03-20 | 2012-03-20 | Stable graphene/titanium oxide composite nanosol and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210074661.XA CN102631910B (en) | 2012-03-20 | 2012-03-20 | Stable graphene/titanium oxide composite nanosol and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102631910A true CN102631910A (en) | 2012-08-15 |
| CN102631910B CN102631910B (en) | 2014-06-18 |
Family
ID=46616592
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210074661.XA Active CN102631910B (en) | 2012-03-20 | 2012-03-20 | Stable graphene/titanium oxide composite nanosol and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102631910B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103021574A (en) * | 2012-12-27 | 2013-04-03 | 上海交通大学 | Graphene/inorganic semiconductor composite film and preparation method thereof |
| CN104001495A (en) * | 2014-06-06 | 2014-08-27 | 河南师范大学 | Preparation method of bismuth oxychloride/graphene composite visible light catalyst |
| CN104559348A (en) * | 2013-10-22 | 2015-04-29 | 现代自动车株式会社 | Graphene-ceramic hybrid coating layer, and method for preparing the same |
| CN105413669A (en) * | 2015-11-03 | 2016-03-23 | 同济大学 | Multifunctional graphene film material, preparation method therefor and application of multifunctional graphene film material |
| CN106345449A (en) * | 2016-07-29 | 2017-01-25 | 陕西科技大学 | Oxidized-reduced graphene/TiO2:Nd composite self-cleaning film and preparation method thereof |
| CN106944034A (en) * | 2017-04-24 | 2017-07-14 | 陕西科技大学 | （Si,Y）Codope TiO2The high-efficiency self-cleaning film and preparation method of/redox graphene complex |
| CN107469869A (en) * | 2017-08-23 | 2017-12-15 | 浙江理工大学 | A kind of preparation method of photocatalytic fiber net |
| CN108295827A (en) * | 2017-12-23 | 2018-07-20 | 佛山科学技术学院 | A kind of method of graphene-supported visible light-responsible titanium dioxide |
| CN109395709A (en) * | 2018-07-12 | 2019-03-01 | 重庆交通大学 | A kind of graphene quantum dot/two dimension titanium dioxide and preparation method thereof |
| CN110255550A (en) * | 2019-04-25 | 2019-09-20 | 武汉理工大学 | A kind of graphene/Two-dimensional Inorganic Material cladding film and its preparation method and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101937985A (en) * | 2010-08-19 | 2011-01-05 | 北京科技大学 | Graphene/titanium dioxide lithium ion battery cathode material and preparation method |
| CN102160995A (en) * | 2011-03-08 | 2011-08-24 | 上海交通大学 | Method for preparing nanometer metal oxide/graphene composite photocatalyst |
| CN102350335A (en) * | 2011-08-10 | 2012-02-15 | 东华大学 | Method for preparing nanometer titanium dioxide/graphene composite hydrogel at room temperature |
-
2012
- 2012-03-20 CN CN201210074661.XA patent/CN102631910B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101937985A (en) * | 2010-08-19 | 2011-01-05 | 北京科技大学 | Graphene/titanium dioxide lithium ion battery cathode material and preparation method |
| CN102160995A (en) * | 2011-03-08 | 2011-08-24 | 上海交通大学 | Method for preparing nanometer metal oxide/graphene composite photocatalyst |
| CN102350335A (en) * | 2011-08-10 | 2012-02-15 | 东华大学 | Method for preparing nanometer titanium dioxide/graphene composite hydrogel at room temperature |
Non-Patent Citations (1)
| Title |
|---|
| JINTAO ZHANG ET AL.: "Graphene-metal-oxide composites for the degradation of dyes under visible light irradiation", 《JOURNAL OF MATERIALS CHEMISTRY》 * |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103021574B (en) * | 2012-12-27 | 2016-01-13 | 上海交通大学 | A kind of Graphene/inorganic semiconductor composite film and preparation method thereof |
| CN103021574A (en) * | 2012-12-27 | 2013-04-03 | 上海交通大学 | Graphene/inorganic semiconductor composite film and preparation method thereof |
| CN104559348A (en) * | 2013-10-22 | 2015-04-29 | 现代自动车株式会社 | Graphene-ceramic hybrid coating layer, and method for preparing the same |
| CN104559348B (en) * | 2013-10-22 | 2018-09-04 | 现代自动车株式会社 | graphene-ceramic hybrid coating and preparation method thereof |
| CN104001495A (en) * | 2014-06-06 | 2014-08-27 | 河南师范大学 | Preparation method of bismuth oxychloride/graphene composite visible light catalyst |
| CN104001495B (en) * | 2014-06-06 | 2016-09-21 | 河南师范大学 | A kind of preparation method of bismuth oxychloride/Graphene composite visible light catalyst |
| CN105413669A (en) * | 2015-11-03 | 2016-03-23 | 同济大学 | Multifunctional graphene film material, preparation method therefor and application of multifunctional graphene film material |
| CN105413669B (en) * | 2015-11-03 | 2018-08-24 | 同济大学 | A kind of multifunctional graphite vinyl thin-film material and its manufacturing method and application |
| CN106345449B (en) * | 2016-07-29 | 2019-05-03 | 陕西科技大学 | Redox graphene/TiO2: Nd compound self-cleaning film and preparation method thereof |
| CN106345449A (en) * | 2016-07-29 | 2017-01-25 | 陕西科技大学 | Oxidized-reduced graphene/TiO2:Nd composite self-cleaning film and preparation method thereof |
| CN106944034A (en) * | 2017-04-24 | 2017-07-14 | 陕西科技大学 | （Si,Y）Codope TiO2The high-efficiency self-cleaning film and preparation method of/redox graphene complex |
| CN106944034B (en) * | 2017-04-24 | 2019-09-24 | 陕西科技大学 | (Si, Y)-codope TiO2The high-efficiency self-cleaning film and preparation method of/redox graphene complex |
| CN107469869A (en) * | 2017-08-23 | 2017-12-15 | 浙江理工大学 | A kind of preparation method of photocatalytic fiber net |
| CN107469869B (en) * | 2017-08-23 | 2020-06-23 | 浙江理工大学 | Preparation method of photocatalytic fiber web |
| CN108295827A (en) * | 2017-12-23 | 2018-07-20 | 佛山科学技术学院 | A kind of method of graphene-supported visible light-responsible titanium dioxide |
| CN109395709A (en) * | 2018-07-12 | 2019-03-01 | 重庆交通大学 | A kind of graphene quantum dot/two dimension titanium dioxide and preparation method thereof |
| CN110255550A (en) * | 2019-04-25 | 2019-09-20 | 武汉理工大学 | A kind of graphene/Two-dimensional Inorganic Material cladding film and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102631910B (en) | 2014-06-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102631910B (en) | Stable graphene/titanium oxide composite nanosol and preparation method thereof | |
| CN105056929B (en) | A kind of graphene/titania composite material with tiny balloon shape and preparation method thereof | |
| Liu et al. | Anatase TiO2 with dominant high-energy {001} facets: synthesis, properties, and applications | |
| Wu et al. | Nonaqueous production of nanostructured anatase with high-energy facets | |
| Zhang et al. | Titanium dioxide (TiO2) mesocrystals: Synthesis, growth mechanisms and photocatalytic properties | |
| Kemell et al. | Atomic layer deposition of nanostructured TiO2 photocatalysts via template approach | |
| Xu et al. | Size-dependent Mie’s scattering effect on TiO2 spheres for the superior photoactivity of H2 evolution | |
| Li et al. | Synthesis and investigation of TiO2 nanotube arrays prepared by anodization and their photocatalytic activity | |
| Lakshmi et al. | Sol− gel template synthesis of semiconductor oxide micro-and nanostructures | |
| Dai et al. | Synthesis of anatase TiO2 nanocrystals with exposed {001} facets | |
| Li et al. | Controllable synthesis of TiO2 single crystals with tunable shapes using ammonium-exchanged titanate nanowires as precursors | |
| Liu et al. | Carbon nanotubes supported mesoporous mesocrystals of anatase TiO2 | |
| Wang et al. | Reduced graphene oxide wrapped Bi2WO6 hybrid with ultrafast charge separation and improved photoelectrocatalytic performance | |
| Bao et al. | Highly Efficient Liquid-Phase Photooxidation of an Azo Dye Methyl Orange over Novel Nanostructured Porous Titanate-Based Fiber of Self-Supported Radially Aligned H2Ti8O17⊙ 1.5 H2O Nanorods | |
| Orel et al. | Cuprous oxide nanowires prepared by an additive-free polyol process | |
| Tahir et al. | Titanium carbide MXene nanostructures as catalysts and cocatalysts for photocatalytic fuel production: a review | |
| CN101693196B (en) | Preparation method of silver/titanium dioxide compound | |
| Wang et al. | Surface-mediated growth of transparent, oriented, and well-defined nanocrystalline anatase titania films | |
| CN102151561A (en) | Photocatalyst consisting of carbon nanotubes loaded with titanium dioxide and preparation method thereof | |
| CN104056611B (en) | One prepares nano-TiO2Method | |
| CN102674451A (en) | Preparation method of {001} face exposed titanium dioxide nanocrystals | |
| Liao et al. | New mechanistic insight of low temperature crystallization of anodic TiO2 nanotube array in water | |
| CN104759273A (en) | Preparation method for in-situ carbon doped hollow titanium dioxide visible light photocatalyst | |
| Liu et al. | Superb photocatalytic activity of 2D/2D Cl doped g-C3N4 nanodisc/Bi2WO6 nanosheet heterojunction: Exploration of photoinduced carrier migration in S-scheme heterojunction | |
| Li et al. | Ag-induced anatase-rutile TiO2− x heterojunction facilitating the photogenerated carrier separation in visible-light irradiation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |