CN102631910B - Stable graphene/titanium oxide composite nanosol and preparation method thereof - Google Patents
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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, with its clean, renewable, safe feature, receives increasing concern.Photocatalysis technology utilizes solar energy to carry out the new technology of Conversion of Energy just, and improving light-catalysed transformation efficiency is the most important thing that promotes this technology extensive use.Titanium oxide is with its nontoxic stable, concern that high, the low-cost feature of memory space is subject to photocatalysis field all the time.Be coated on transparent titania film in glass or plastic supporting base and be successfully applied to the fields such as antifog, fungi-proofing, mildew-resistant, automatically cleaning as functional film.Under illumination condition, titanium oxide in 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 around 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 the efficiency of titanium oxide not high.Numerous researchers have explored the method that improves titanium oxide efficiency from all angles, wherein find, the load (as fullerene, CNT etc.) of material with carbon element can effectively improve separating of light induced electron and hole.Graphene is a kind of New Two Dimensional material with carbon element of finding in recent years, is the highest material of at room temperature electric transmission speed existing in the world at present.The load of Graphene can be played the effect of electron propagation ducts, and the light induced electron on titanium oxide is derived in time, 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.
At present the composite of titanium oxide/Graphene is take powder as main, and needs by high temperature or HIGH PRESSURE TREATMENT more, and this has limited the use of this composite greatly.Find by literature search, in the patent of invention that the patent No. is 201010237588.4, the compound that adopts reactor to prepare is slurry, powder type, cannot prepare transparent membrane; The patent No. is in 200910196534.5 invention, adopts preparing graphene-based titanium dioxide composite photocatalyst by radiation of electron beams, and gained catalyst is also powder state; Chinese invention patent application number is 201110228170.1 patent of invention, though its composite catalyst exists with solation, but the titanium oxide of its use is P25 titanium oxide, its granular size is more than 30nm, according to the pH value of its solution, this titanium oxide Graphene colloidal sol stable existence for a long time, also cannot be adapted to the coating process of large-scale industrialization.
Summary of the invention
The object of this invention is to provide a kind of stable Graphene/titanium oxide composite Nano colloidal sol and preparation method thereof.
Graphene/titanium oxide composite Nano colloidal sol provided by the present invention is to prepare according to the method comprising the steps: 1) graphene oxide is dissolved in solvent, obtains graphene oxide solution, and with acid regulate its pH value to 1～6;
2) mixed liquor of tetra-n-butyl titanate and isopropyl alcohol is joined to step 1) in the graphene oxide solution that obtains, and mixture is carried out to condensing reflux, obtain colloidal sol;
3) in described colloidal sol, add reducing agent to react; Reaction finishes rear colloidal sol to be carried out to ultrasonic processing, dialysis purified treatment successively, obtains Graphene/titanium oxide composite Nano colloidal sol.
Wherein, step 1) described in solvent can be water or ethanol;
Step 1) described in acid-specific can be hydrochloric acid, nitric acid or sulfuric acid.
Step 2) described in graphene oxide in graphene oxide solution and the mass ratio of tetra-n-butyl titanate be 0.03125: 100～1.250: 100.
Step 2) described in condensing reflux undertaken by water-bath or oil bath heating, the temperature of described water-bath or oil bath is 50 ℃～150 ℃; The described condensing reflux time is no less than 12 hours, specifically can be 12～24 hours.
Step 3) described in reducing agent be hydrazine; In described reducing agent and described colloidal sol, the proportioning of graphene oxide is 1 μ L hydrazine: (0.1mg～5mg) graphene oxide; Described reaction is carried out under stirring, and the temperature of described reaction is more than 80 ℃, is specially 95 ℃～150 ℃, and the time of described reaction is greater than 1 hour, is specially 5～12 hours.
Step 3) power of described ultrasonic processing is more than 100W, ultrasonic time is greater than 20 minutes, is specially 1～5 hour.
Graphene/titanium oxide composite Nano colloidal sol prepared by the present invention can stable existence 3 months.
In this composite Nano colloidal sol, Graphene comprises its state of oxidation and reducing condition; 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 is to provide 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 substrate, after being dried, obtains.
Exist form and the multiple industrialization of Graphene/titanium oxide composite Nano colloidal sol of the present invention apply means as dripped the modes such as painting, spin coating, roller coating, spraying compatibility mutually, can be deposited on multiple substrate by these coating methods, hard substrates is as glass, silicon chip, and flexible substrate is as PET etc.After deposition is dry, obtain fine and close Titanium dioxide nanoparticle/graphene film, the colloidal sol amount that film forming thickness can deposit by control easily regulates.Graphene has played the beam action of electric transmission bridge in film, and light induced electron is transmitted on substrate in time from Titanium dioxide nanoparticle, promotes separating of light induced electron and hole.By the mensuration of electrochemical workstation, add the complex thin film depositing after Graphene without the film adding, photoelectric current intensity has improved five times nearly, and the film transparency is good, 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 plastics.Also can be used for preparing the heavy industrialization manufacture of flexible solar battery.
Accompanying drawing explanation
Fig. 1 is that pH is 1 o'clock, the Graphene of different quality ratio and the Zeta potential figure of titanium dioxide composite collosol.
Fig. 2 is the XRD collection of illustrative plates of titanium dioxide in the Graphene of preparation and titanium dioxide composite collosol.
Wherein, what in Fig. 1,2, sample A was corresponding is the product in embodiment 8 (RGO (reduced graphene) load capacity 0.1%), what sample B was corresponding is the product in embodiment 5 (RGO load capacity 0.5%), what sample C was corresponding is the product in embodiment 1,3,4,6 (RGO load capacity 1%), what sample D was corresponding is the product in embodiment 2 (RGO load capacity 2%), what sample E was corresponding is the product in embodiment 9 (RGO load capacity 3%), and what sample F was corresponding is the product in embodiment 7 (RGO load capacity 4%); Sample TiO in Fig. 2
2the pure zirconia titanium colloidal sol that replaces graphene oxide solution to make with pure water.
The specific embodiment
Below by specific embodiment, the present invention will be described, but the present invention is not limited thereto.
Experimental technique described in following embodiment, if no special instructions, is conventional method; Described reagent and material, if no special instructions, all can obtain from commercial channels.
In following embodiment, graphene oxide used is to adopt modified Hummers method to prepare in laboratory, concrete steps are as follows: 10g native graphite is put into 500ml conical flask, in ice bath, add after 230ml sulfuric acid, add again 30g potassium permanganate, by mixed liquor at 10 ℃ of vigorous stirring 60min.Mixed liquor is heated to stir 2h at 35 ℃, in ice bath, slowly adds afterwards 160ml deionized water, afterwards at 98 ℃ of stirred in water bath 1h.Solution with water is diluted to 1.4l, finally adds 35ml H
2o
2(30%).By after solution filter, with 3wt%HCl cleaning, after being dried, obtain graphene oxide (GO) brown color powder.Powder dissolution is obtained in deionized water to graphite oxide aqueous solution.
Embodiment 1:
1) 3.125mg graphene oxide is dissolved in 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 graphite oxide aqueous solution, with dropper by the mixed liquor of tetra-n-butyl titanate and isopropyl alcohol along stir rightabout slowly drip, 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 ℃, and the condensing reflux time is 24 hours;
5) in the colloidal sol after condensing reflux, add the hydrazine of 9.37 μ l, in 95 ℃ of water-baths, keep stirring 12 hours;
6) colloidal sol after stirring is carried out to dialysis processing for ultrasonic 1 hour to remove impurity in water after (200W), obtain finished product colloidal sol.In colloidal sol, the mass ratio of Graphene and titanium dioxide is about 1: 100.
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) using dried film as working electrode, Pt is as to electrode, 0.5M Na
2sO
4as electrolyte, 350W xenon lamp, as light source, in not biased situation, is measured the photoelectric current of film with CHI660D electrochemical workstation, and the photoelectric current obtaining is 1.02 μ A.In above-mentioned experiment, with pure water replacement graphite oxide aqueous solution, 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) 6.25mg graphene oxide is dissolved in 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 graphite oxide aqueous solution, with dropper by the mixed liquor of tetra-n-butyl titanate and isopropyl alcohol along stir rightabout slowly drip, 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) in the colloidal sol after condensing reflux, add the hydrazine of 18.74 μ l, in 95 degree water-baths, keep stirring 12 hours;
6) colloidal sol after stirring is carried out to dialysis processing for ultrasonic 1 hour to remove impurity in water after (200W), obtain finished product colloidal sol.In colloidal sol, the mass ratio of Graphene and titanium dioxide is about 2: 100.
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) using dried film as working electrode, Pt is as to electrode, 0.5M Na
2sO
4as electrolyte, 350W xenon lamp, as light source, in not biased situation, is measured the photoelectric current of film with CHI660D electrochemical workstation, and the photoelectric current obtaining is 0.92 μ A.
Embodiment 3:
1) 3.125mg graphene oxide is dissolved in 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 graphite oxide aqueous solution, with dropper by the mixed liquor of tetra-n-butyl titanate and isopropyl alcohol along stir rightabout slowly drip, 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) in the colloidal sol after condensing reflux, add the hydrazine of 9.37 μ l, in 150 degree oil baths, keep stirring 5 hours;
6) colloidal sol after stirring is carried out to dialysis processing for ultrasonic 1 hour to remove impurity in water after (250W), obtain finished product colloidal sol.In colloidal sol, the mass ratio of Graphene and titanium dioxide is about 1: 100.
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) using dried film as working electrode, Pt is as to electrode, 0.5M Na
2sO
4as electrolyte, 350W xenon lamp, as light source, in not biased situation, is measured the photoelectric current of film with CHI660D electrochemical workstation, and the photoelectric current obtaining is 0.98 μ A.
Embodiment 4:
1) 3.125mg graphene oxide is dissolved in 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 graphite oxide aqueous solution, with dropper by the mixed liquor of tetra-n-butyl titanate and isopropyl alcohol along stir rightabout slowly drip, 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) in the colloidal sol after condensing reflux, add the hydrazine of 9.37 μ l, in 150 degree oil baths, keep stirring 5 hours;
6) colloidal sol after stirring is carried out to dialysis processing for ultrasonic 1 hour to remove impurity in water after (250W), obtain finished product colloidal sol.In colloidal sol, the mass ratio of Graphene and titanium dioxide is about 1: 100.
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) using dried film as working electrode, Pt is as to electrode, and 0.5M Na2SO4 is as electrolyte, 350W xenon lamp is as light source, in not biased situation, measure the photoelectric current of film with CHI660D electrochemical workstation, the photoelectric current obtaining is 1.00 μ A.
Embodiment 5:
1) 1.563mg graphene oxide is dissolved in 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 graphite oxide aqueous solution, with dropper by the mixed liquor of tetra-n-butyl titanate and isopropyl alcohol along stir rightabout slowly drip, 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) in the colloidal sol after condensing reflux, add the hydrazine of 9.37 μ l, in 120 degree oil baths, keep stirring 12 hours;
6) colloidal sol after stirring is carried out to dialysis processing to remove impurity in water after ultrasonic 2 hours, obtain finished product colloidal sol.In colloidal sol, the mass ratio of Graphene and titanium dioxide is about 0.5: 100.
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) using dried film as working electrode, Pt is as to electrode, and 0.5M Na2SO4 is as electrolyte, 350W xenon lamp is as light source, in not biased situation, measure the photoelectric current of film with CHI660D electrochemical workstation, the photoelectric current obtaining is 1.25 μ A.
Embodiment 6:
1) 3.125mg graphene oxide is dissolved in 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 graphite oxide aqueous solution, with dropper by the mixed liquor of tetra-n-butyl titanate and isopropyl alcohol along stir rightabout slowly drip, 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) in the colloidal sol after condensing reflux, add the hydrazine of 9.37 μ l, in 100 degree oil baths, keep stirring 10 hours;
6) colloidal sol after stirring is carried out to dialysis processing for ultrasonic 1 hour to remove impurity in water after (160W), obtain finished product colloidal sol.In colloidal sol, the mass ratio of Graphene and titanium dioxide is about 1: 100.
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) using dried film as working electrode, Pt is as to electrode, and 0.5M Na2SO4 is as electrolyte, 350W xenon lamp is as light source, in not biased situation, measure the photoelectric current of film with CHI660D electrochemical workstation, the photoelectric current obtaining is 0.95 μ A.
Embodiment 7:
1) 12.5mg graphene oxide is dissolved in 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 graphite oxide aqueous solution, with dropper by the mixed liquor of tetra-n-butyl titanate and isopropyl alcohol along stir rightabout slowly drip, 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) in the colloidal sol after condensing reflux, add the hydrazine of 37.48 μ l, in 100 degree oil baths, keep stirring 10 hours;
6) colloidal sol after stirring is carried out to dialysis processing for ultrasonic 1 hour to remove impurity in water after (160W), obtain finished product colloidal sol.In colloidal sol, the mass ratio of Graphene and titanium dioxide is about 4: 100.
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) using dried film as working electrode, Pt is as to electrode, and 0.5M Na2SO4 is as electrolyte, 350W xenon lamp is as light source, in not biased situation, measure the photoelectric current of film with CHI660D electrochemical workstation, the photoelectric current obtaining is 0.45 μ A.
Embodiment 8:
1) 0.3125mg graphene oxide is dissolved in 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 graphite oxide aqueous solution, with dropper by the mixed liquor of tetra-n-butyl titanate and isopropyl alcohol along stir rightabout slowly drip, 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) in the colloidal sol after condensing reflux, add the hydrazine of 8.21 μ l, in 95 degree water-baths, keep stirring 6 hours;
6) colloidal sol after stirring is carried out to dialysis processing to remove impurity in water after ultrasonic 5 hours, obtain finished product colloidal sol.In colloidal sol, the mass ratio of Graphene and titanium dioxide is about 0.1: 100.
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) using dried film as working electrode, Pt is as to electrode, and 0.5M Na2SO4 is as electrolyte, 350W xenon lamp is as light source, in not biased situation, measure the photoelectric current of film with CHI660D electrochemical workstation, the photoelectric current obtaining is 0.68 μ A.
Embodiment 9:
1) 9.375mg graphene oxide is dissolved in 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 graphite oxide aqueous solution, with dropper by the mixed liquor of tetra-n-butyl titanate and isopropyl alcohol along stir rightabout slowly drip, 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) in the colloidal sol after condensing reflux, add the hydrazine of 8.24 μ l, in 100 degree oil baths, keep stirring 10 hours;
6) colloidal sol after stirring is carried out to dialysis processing to remove impurity in water after ultrasonic 1.5 hours, obtain finished product colloidal sol.In colloidal sol, the mass ratio of Graphene and titanium dioxide is about 3: 100.
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) using dried film as working electrode, Pt is as to electrode, and 0.5M Na2SO4 is as electrolyte, 350W xenon lamp is as light source, in not biased situation, measure the photoelectric current of film with CHI660D electrochemical workstation, the photoelectric current obtaining is 0.56 μ A.
Claims (5)
1. a method of preparing Graphene/titanium oxide composite Nano colloidal sol, comprises the steps:
1) graphene oxide is dissolved in solvent, obtains graphene oxide solution, and with acid regulate its pH value to 1～6;
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 to condensing reflux, obtain colloidal sol;
3) in described colloidal sol, add reducing agent to react; Reaction finishes rear colloidal sol to be carried out to ultrasonic processing, dialysis purified treatment successively, obtains Graphene/titanium oxide composite Nano colloidal sol;
Step 2) described in graphene oxide in graphene oxide solution and the mass ratio of tetra-n-butyl titanate be 0.03125:100～1.250:100;
Step 2) described in condensing reflux undertaken by water-bath or oil bath heating, the temperature of described water-bath or oil bath is 50 ℃～150 ℃; The described condensing reflux time is 12～24 hours;
Reducing agent described in step 3) is hydrazine; In described reducing agent and described colloidal sol, the proportioning of graphene oxide is 1 μ L hydrazine: (0.1mg～5mg) graphene oxide, and described reaction is carried out under stirring,
The temperature of described reaction is 95 ℃～150 ℃, and the time of described reaction is 5～12 hours;
Described in step 3), the power of ultrasonic processing is 100～1000W, and ultrasonic time is 1～5 hour.
2. method according to claim 1, is characterized in that: solvent described in step 1) is water or ethanol; Described in step 1), acid is hydrochloric acid, nitric acid or sulfuric acid.
3. Graphene/titanium oxide composite Nano colloidal sol that described in claim 1 or 2, method prepares, in described Graphene/titanium oxide composite Nano colloidal sol, the mass ratio of Graphene and oxide and titanium oxide is 0.1:100～4:100.
4. Graphene/titanium oxide composite Nano colloidal sol according to claim 3, is characterized in that: in described Graphene/titanium oxide composite Nano colloidal sol, the particle diameter of titan oxide particles is between 2-20 nanometer.
5. Graphene/titanium oxide composite film, is that the Graphene/titanium oxide composite Nano colloidal sol described in claim 3 or 4 is coated on substrate, after being dried, obtains.
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| 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 |
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