CN102553559A - Graphene/nanometer titanium dioxide compound and preparation method thereof - Google Patents
Graphene/nanometer titanium dioxide compound and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a method for preparing a graphene/nanometer titanium dioxide compound. The method comprises the steps as follows: 500 to 10000 parts by weight of nanometer titanium dioxide and about 1 part by weight of graphene are dispersed in water/alcohol solution with the volume ratio of 2:1 to 3:1; and under the conditions that the pressure is 10 to 15 MPa and the temperature is about 100 to 200 DEG C, the nanometer titanium dioxide and the graphene in the dispersion liquid react to obtain the graphene/nanometer titanium dioxide compound.
Description
Technical field
The invention relates to a kind of Graphene/nano titanium oxide compound and preparation method thereof.
Background technology
In science and technology progress, more and more organic pollutions (for example: chlorinated aromatics, surfactant, dyestuff, herbicide, herbicide or the like) and inorganic pollution have also appearred (like, CN in the environment
-, CrO
4 2-Deng), the lasting accumulation of these pollutants in natural environment tends to threaten environmental ecology and human health.
In order to handle these pollutants, developed the whole bag of tricks such as absorption method, oxidizing process, reducing process, filtration method, photocatalysis Decomposition at present, wherein photocatalysis Decomposition has advantages of higher easy and simple to handle, cheap, stable, therefore enjoys all circles to pay close attention to.
Titanium dioxide is present topmost commercially available photochemical catalyst, yet the catalytic efficiency of this kind photochemical catalyst is still not ideal enough.In view of this, association area is needed badly and is proposed a kind of new kenel photochemical catalyst with preferable photocatalysis efficiency.
Summary of the invention
Summary of the invention aims to provide the simplification summary of this disclosure, so that the reader possesses basic understanding to this disclosure.This summary of the invention is not the complete overview of this disclosure, and its purpose is not at the key/critical assembly of pointing out the embodiment of the invention or defines scope of the present invention.
One side of the present invention is the preparation method about a kind of Graphene/nano titanium oxide compound.According to principle of the present invention and spirit, can under HTHP, make the reaction of Graphene and nano titanium oxide, and then obtain Graphene/nano titanium oxide compound.
According to one embodiment of the invention, said method comprises following steps: the Graphene of the nano titanium oxide of about 500 to 10,000 weight portions and about 1 weight portion is scattered in water/ethanolic solution that volume ratio is about 2: 1 to 3: 1; Under the pressure of about 10-15MPa and about 100-200 ℃ temperature, nano titanium oxide and Graphene in the above-mentioned dispersion liquid are reacted, to obtain Graphene/nano titanium oxide compound.
According to another embodiment of the present invention, titania nanotube capable of using or titania nanoparticles are used as above-mentioned nano titanium oxide.
According to further embodiment of this invention, hydro-thermal method capable of using is made above-mentioned titania nanotube.
Another aspect of the present invention is about a kind of Graphene/nano titanium oxide compound.With commercially available titanium deoxide catalyst in comparison, this kind Graphene/nano titanium oxide compound has higher specific surface area, and also has preferable photocatalytic degradation speed.
According to further embodiment of this invention, this Graphene/nano titanium oxide compound mainly is made up of about 500: 1 of weight ratio to 10,000: 1 nano titanium oxide and Graphene.
After consulting the hereinafter embodiment, having common knowledge the knowledgeable under the present invention in the technical field ought can understand essence spirit of the present invention and other goal of the invention easily, and technological means that the present invention adopted and embodiment.
Description of drawings
For letting above-mentioned and other purpose of the present invention, characteristic, advantage and the embodiment can be more obviously understandable, description of drawings be following:
1A figure to 1C figure be the SEM photo of the prepared titania nanotube of experimental example according to the present invention;
2A figure and TEM photo and IR that 2B figure is respectively the prepared Graphene of one experimental example/titania nanotube compound according to the present invention scheme; And
The 3rd figure is the methyl blue test result of one experiment according to the present invention.
The specific embodiment
More detailed and complete for the narration that makes content of the present invention, hereinafter has been directed against embodiment of the present invention and specific embodiment has proposed illustrative description; But this is not unique form of implementing or using the specific embodiment of the invention.Contained in the embodiment a plurality of specific embodiments characteristic and in order to the method step of construction and these specific embodiments of operation with its in proper order.Yet, also can utilize other specific embodiment to reach identical or impartial function and sequence of steps.
With titanic oxide material more than the micron grade in comparison, nano titanium oxide has higher specific surface area, bigger photocatalysis area can be provided in theory, and can have preferable photocatalysis efficiency.Yet in fact, the surface of nano titanium oxide can be high, for reduce the surface can, the surface of the nano-titania particle back regular meeting that contacts with each other forms aggregate (aggregates).In addition, the reaction of many photocatalysis Decomposition will be in the aqueous solution or is had under the environment of water and carry out, and this moment, nano-titania particle equally can be because specific area be big, the surface can high factor, and with water, air cohesion and form agglomerate (coagulates).No matter be to form aggregate or agglomerate, all can reduce the specific area of nano titanium oxide, also correspondingly limited the photocatalysis efficiency of nano titanium oxide.
In view of this, one side of the present invention is the preparation method about a kind of Graphene/nano titanium oxide compound.According to principle of the present invention and spirit, can under HTHP, make the reaction of Graphene and nano titanium oxide, and then obtain Graphene/nano titanium oxide compound.By the method that proposes here, can and be fixed on the surface of Graphene the nano titanium oxide dispersion, and form a compound; Thus; Can reduce the chance that reunion or cohesion take place above-mentioned nano-titania particle effectively; And because composite provides bigger surface area; And then improve material to the organic pollutant adsorption ability, and this material is because the formation of heterogeneous interface reduces the recombination rate between electronics and the electric hole; After the carbon surface absorbed photon, electronics is injected into the conductive strips of titanium dioxide, can forms reaction carriers in order to degradable organic pollutant.
According to an embodiment of the present invention, the above-mentioned method of utilizing high temperature and high pressure method to prepare Graphene/nano titanium oxide compound comprises preparation nano titanium oxide and Graphene dispersion liquid and recombination reaction two large divisions, and is following at this division.
In the step of the dispersion liquid of preparation nano titanium oxide and Graphene, the Graphene of the nano titanium oxide of about 500 to 10,000 weight portions and about 1 weight portion is scattered in water/ethanolic solution that volume ratio is about 2: 1 to 3: 1.
According to the embodiment of the invention, the weight ratio of titanium dioxide and Graphene is about 500 to 10,000 to 1; Be preferably 1,000 to 3,000 to 1.For instance, when the use amount of titanium dioxide was 3g, the consumption of Graphene can be about 0.3 to 6mg; In more detail, the consumption of Graphene can be about 0.3,0.4,0.5,0.6,0.7,0.8,0.9,1,1.5,2,2.5,3,3.5,4,4.5,5,5.5 or 6mg.
According to principle of the present invention and spirit, in the method, the titanic oxide material of any nano-scale capable of using includes but not limited to: titania nanotube (TiO
2Nanotubes) and titania nanoparticles (TiO
2Nano-particles).
In general, the specific area of commercially available titania nanoparticles is about 50-60m
2About/g; And the specific area of titania nanotube is about 200-400m
2/ g.
In the embodiment that the present invention chooses wantonly, hydro-thermal method manufacturing capable of using has the titania nanotube of high specific surface area, with the photocatalysis usefulness of further lifting Graphene/nano titanium oxide compound.The hydro-thermal method that here proposes comprises following steps.
At first, after an amount of titania powder grinding, add in the sodium hydrate aqueous solution of high concentration, to make reaction solution.Suitable sodium hydrate aqueous solution concentration is about 5 to 15M, for example about 5,5.5,6,6.5,7,7.5,8,8.5,9,9.5,10,10.5,11,11.5,12,12.5,13,13.5,14,14.5 or 15M.In addition, the weight ratio of the NaOH in titania powder and the sodium hydrate aqueous solution is about 1: 1 to 1: 3.
Reaction solution is placed high-pressure reactor, under about 110 to 150 ℃ reaction temperature, making its reaction under the pressure of about 10MPa to 15MPa.In general, in about 4 to 24 hours of reaction time, can make the titanium dioxide in the reaction solution change titania nanotube into.
Result of the test shows that reaction temperature and reaction time can influence the caliber and the length of product, also therefore can influence the specific area of product.The various embodiments according to the present invention, suitable reaction temperature are about 110 to 150 ℃; Be preferably about 110 to 130 ℃; Specifically, this reaction temperature can be about 110,115,120,125,130,135,140,145 or 150 ℃.In addition, the suitable reaction time is about 4 to 24 hours; Be preferably about 10 to 20 hours; Specifically, the reaction time can be about 4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,22,23 or 24 hours.
Then, with 0.1M HCl and a large amount of deionized water titania nanotube of cleaning and filtering reaction gained repeatedly, till the aqueous solution presents neutrality.Then, dry titania nanotube through cleaning then further grinds again, can obtain titania nanotube.For instance, will place about 40 ℃ vacuum drying oven through the titania nanotube that cleans dry about 6-12 hour, can remove moisture wherein in fact.
Analysis result shows, the specific area of utilizing the titania nanotube that above method makes is for about 200 to 500m
2/ g.
According to principle of the present invention and spirit, can first acidified processing or other chemical modification in order to the Graphene of preparation dispersion liquid.
Graphene is called mono-layer graphite (mono layer graphite) again, is just confirmed in recent years two-dimentional carbon atom crystal.Under nature, can reunite together because of Van der Waals force to each other between the Graphene after the layering, and be difficult to keep the state of layering.This makes that also the dissolubility of Graphene in water and ethanol is not satisfactory usually.Therefore,, before the preparation dispersion liquid, can earlier Graphene be carried out acidification,, be increased in the dispersiveness in the water with the Graphene oxidation according to one embodiment of the invention.For instance, in one embodiment, can Graphene be placed about 0.5 to 5M sulfuric acid stir about 8 to 12 hours.
In addition, also can have the multiple functional group who supplies chemical modification in the Graphene, embodiment of the present invention also comprises these grapheme materials through chemical modification.
In the present invention, utilize volume ratio to be about 2: 1 to 3: 1 the mixed solution of water and ethanol as the solvent of this dispersion liquid; For instance, the ratio of water and ethanol can be about 2: 1,2.5: 1 or 3: 1.
In addition, technology well known in the art capable of using and/or equipment promote Graphene and the titanium dioxide dispersing uniformity in solvent.For instance, in one embodiment, ultrasonic concussion capable of using is to be scattered in nano titanium oxide and Graphene in the solvent equably.
After dispersion liquid preparation is accomplished, in the step of recombination reaction, under the pressure of about 10-15MPa and about 100-200 ℃ temperature, nano titanium oxide and Graphene in the dispersion liquid are reacted, to obtain Graphene/nano titanium oxide compound.For instance, suitable reaction pressure can be about 10,11,12,13,14 or 15MPa; And suitable reaction temperature can be about 100,110,120,130,140,150,160,170,180,190 or 200 ℃.
Can in high-pressure reactor, carry out this recombination reaction, in general the reaction time is the consumption that depends on reactant, also can influence compound degree simultaneously.According to the embodiment of the invention, about 5-10 of reaction time hour, promptly foot made Graphene and nano titanium oxide compound effectively.For instance, the reaction time can be about 5,6,7,8,9 or 10 hours.
After recombination reaction was accomplished, deionized water capable of using is cleaning and filtering Graphene/nano titanium oxide compound repeatedly, then dry more resulting Graphene/nano titanium oxide compound.For instance, can be placed on and make its drying in about 40 ℃ vacuum drying oven.
Another aspect of the present invention is about a kind of Graphene/nano titanium oxide compound.With commercially available titanium deoxide catalyst in comparison, this kind Graphene/nano titanium oxide compound has higher specific surface area, and also has preferable photocatalytic degradation speed.
According to one embodiment of the invention, this Graphene/main nano titanium oxide of nano titanium oxide compound and Graphene are formed, and wherein the weight ratio of titanium dioxide and Graphene is about 500-10,000: 1; Be preferably 1,000-3,000: 1, as 500,600,700,800,900,1000,2000,3000,4000,5000,6000,7000,8000,9000 or 10000 to 1.
In addition, according to principle of the present invention and spirit, in the method, above-mentioned nano titanium oxide includes but not limited to: titania nanotube and titania nanoparticles.
In an optional embodiment, can select specific area for use is about 200 to 500m
2The titania nanotube of/g.
In an optional embodiment, the part surface of the above-mentioned Graphene of oxidation at least.Or in optional embodiment, above-mentioned Graphene can pass through chemical modification.
In order to understand the photocatalysis Decomposition efficient of the Graphene/nano titanium oxide compound that goes out mentioned herein; Prepared different Graphenes/nano titanium oxide compound according to the method that proposes in the above embodiment of the present invention; The line correlation analysis of going forward side by side, at this that part of test results division is following.
Experiment one
In this serial experiment, according to the described hydro-thermal method of the embodiment of the invention, under different reaction time and reaction temperature, prepare titania nanotube, and inquire into its surface morphology and specific area.Table one summary has been put used reaction temperature and the reaction time of each experimental example in order, and the specific area of product.
Table one
| Reaction temperature (℃) | Reaction time (hour) | Specific area (m 2/g) | |
| Experimental example 1-1 | 110 | 5 | 203.3 |
| Experimental example 1-2 | 110 | 10 | 374.5 |
| Experimental example 1-3 | 110 | 20 | 376.1 |
| Experimental example 2-1 | 130 | 5 | 355.3 |
| Experimental example 2-2 | 130 | 10 | 403.1 |
| Experimental example 2-3 | 130 | 20 | 374.1 |
| Experimental example 3-1 | 150 | 5 | 312.4 |
| Experimental example 3-2 | 150 | 10 | 376.2 |
| Experimental example 3-3 | 150 | 20 | 279.2 |
The result listed by table one can find that when the reaction time was identical, along with reaction temperature increases, the specific area of titania nanotube presented the back downward trend that rises earlier.In addition, when reaction temperature was identical, along with the increase in reaction time, the specific area of titania nanotube also was to present the situation that rises and afterwards descend earlier.
1A figure is respectively scanning electron microscopy (scanning electronic microscope is hereinafter to be referred as the SEM) photo of the titania nanotube of experimental example 1-2,2-2 and 3-2 to 1C figure.Can clearly be seen that by these SEM photos the product outward appearance of these experimental examples presents nanotube-shaped kenel.
Experiment two
In this serial experiment, select the titania nanotube of above-mentioned experimental example 1-2 for use, and prepare Graphene/nano titanium oxide compound (experimental example 4) according to the described high temperature and high pressure method of the preceding text embodiment of the invention.
More particularly, the Graphene of about 3mg is soaked about 10 hours with the sulfuric acid of about 1M, so that the surface of Graphene partial oxidation and form graphene oxide at least.Titania nanotube and the above-mentioned graphene oxide of about 3g are added in about 2.5: the 1 water/alcohol solvent of volume ratio, to obtain a dispersion liquid.Afterwards, dispersion liquid is placed high-pressure reactor, under the temperature of the pressure of about 12MPa and about 110, carry out recombination reaction, about 6 hours of reaction time.After recombination reaction is accomplished,, and place about 40 ℃ vacuum drying oven dry the product with deionized water cleaning and filtering repeatedly.
2A figure is micro-(the transmission electron microscope of penetration type electron of the Graphene/nano titanium oxide compound of experimental example 4; Hereinafter to be referred as TEM) photo; The TEM photo can be found out thus, and after the experience recombination reaction, the kenel that nano titanium oxide is still kept nanotube (promptly; And these titania nanotubes are evenly dispersed on the graphene layer part of elongate in the TEM photo).
2B figure is infrared spectrum (infrared spectroscope is hereinafter to be referred as the IR) figure of the Graphene/nano titanium oxide compound of experimental example 4; In addition, presented titanium dioxide and Graphene IR figure separately among the 2B figure simultaneously.Can find that by 2B figure the Graphene of experimental example 4/nano titanium oxide compound has the characteristic absorption peak (be illustrated in the hydrothermal reaction process, Graphene and titanium dioxide form compound) of composite at about 1620nm place; Hence one can see that, and the high temperature and high pressure method that goes out mentioned herein can make really and between Graphene and the nanometer titanic oxide material compound action take place, but not merely mixes.
Experiment three
In this serial experiment, prepare different Graphenes/nano titanium oxide compound according to the described method of above-mentioned embodiment, and with not compound nanometer titanic oxide material as control group, analyze the photocatalysis Decomposition efficient of various materials.Material type and photocatalysis Decomposition usefulness thereof that table two and the 3rd figure make a summary and put each experimental example and control group in order respectively.
Table two
| Kenel | C/C after 55 minutes 0 | |
| Experimental example 4 | Graphene/titania nanotube compound | 13.89％ |
| Experimental example 5 | Graphene/titanium dioxide nano granule compound | 17.46％ |
| Reference examples 1 | Titania nanotube (experimental example 1-2) | 43.25％ |
| Reference examples 2 | Commercially available titanium dioxide nano granule | 72.40％ |
In this serial experiment, reference examples 1,2 is respectively the titania nanotube that makes of preceding text experimental example 1-2 and commercially available DEGUSSA P-25 titanium dioxide nano granule.The Graphene of experimental example 4/titania nanotube compound is exactly prepared Graphene/nano titanium oxide compound in the preceding text experiment two.The Graphene of experimental example 5/titanium dioxide nano granule compound then is to utilize preceding text to test two described methods, with commercially available DEGUSSA P-25 titanium dioxide nano granule and the compound prepared product of graphene oxide.
Utilize above-mentioned material to carry out methyl blue (methyl blue) test here, to assess its photocatalysis Decomposition efficient respectively.Methyl blue is a kind of organic dyestuff, and meeting soluble in water makes the aqueous solution present bluish violet; Methyl blue can be adsorbed in the surface of multiple material effectively, and is not easy to decompose because of irradiation; When impelling methyl blue to resolve into inorganic matter when the catalysis material irradiation, the color of the aqueous solution can be thin out gradually, therefore often utilizes the reagent of methyl blue as the photocatalysis Decomposition test.
In this experiment, the commercially available methyl blue of about 0.01 gram is dissolved in and is prepared into concentration about 2.7 * 10 in about 1 liter deionized water
-5The methyl blue aqueous solution of M is dispersed in the methyl blue aqueous solution with Graphene/titanium dioxide compound with ultrasonic concussion mode afterwards again.It is the target degradation product that the methyl blue of 10mg/L is adopted in the photocatalysis test, and uses ultraviolet ray/visible light (UV/VIS) light source to measure the methylene blue absorption spectrum.Measure the result and show four tangible absworption peaks, be respectively the about 246nm of wavelength, 292nm, 610nm and 665nm place, wherein 665nm is a maximum absorption band, therefore selects this absworption peak to come the concentration of quantitative analysis methylene blue.
The photocatalysis test process is for getting 30mg titania nanotube-graphene powder; Add volume and be in the methyl blue solution of 50ml and mix; Place quartz beaker to measure its photocatalysis usefulness again with the 250W UV-irradiation; Sampling in per ten minutes is once got supernatant liquid after centrifugal, measures its absorption spectrum.
Can find with the result shown in the 3rd figure that by table two in all test materials, with the photocatalysis Decomposition poor-performing of commercially available DEGUSSA P-25 titanium dioxide nano granule, after through 55 minutes, 72.40% the methyl blue of also having an appointment is still undecomposed.In comparison; Method according to propose is here processed Graphene/titanium dioxide nano granule compound (experimental example 5) with this commercially available prod; It can divide the methyl blue of terminate an agreement 82.54% (100%-17.46%=82.54%) in 55 minutes, its decomposition efficiency is 3 times of commercially available prod nearly.
In addition, according to the prepared titania nanotube of the embodiment of the invention (experimental example 1.2, that is reference examples 2), its light decomposition efficiency is also come highly (the light resolution ratio about 56.75% of methyl blue in 55 minutes) than commercially available DEGUSSA P-25 titanium dioxide nano granule.In addition, it is prepared into Graphene/titania nanotube compound (experimental example 4), then can be further the light resolution ratio of methyl blue in 55 minutes be increased to about 86.11%.
Can know that with the relevant narration of experimental example embodiment of the present invention has successfully proposed the preparation method of a kind of Graphene/nano titanium oxide compound by the preceding text embodiment.Utilize this kind method, can produce Graphene/nano titanium oxide compound easily, solved the problem that the Nano titanium dioxide material is reunited and/or condensed easily in the prior art with more satisfactory specific area.In addition, this method processing procedure is easy, but possesses the volume production ability.
Moreover the embodiment of the invention has more proposed a kind of preparation method of titania nanotube, can obtain having the titania nanotube of more satisfactory specific area.This kind titania nanotube is used for having proposed the compound preparation method here, can further promotes the specific area of Graphene/nano titanium oxide compound.
In addition, result of the test shows, utilizes the prepared Graphene of the method/nano titanium oxide compound that proposes to have comparatively ideal photocatalysis Decomposition efficient here.This kind composite is a kind of inorganic-organic composite material, has the advantage that inorganic compound stable in properties and organic compound are easy to upgrading concurrently; Thereby significantly promote the machinability and the application in industry scope of this material.
Though disclosed specific embodiment of the present invention in the preceding text embodiment; Right its is not in order to limit the present invention; Has common knowledge the knowledgeable in the technical field under the present invention; Be not contrary under the situation of principle of the present invention and spirit, when can carrying out various changes and modification to it, so protection scope of the present invention ought with claim of the present invention the person of being defined be as the criterion.
Claims (10)
1. the preparation method of Graphene/nano titanium oxide compound comprises following steps:
The Graphene of the nano titanium oxide of about 500 to 10,000 weight portions and about 1 weight portion is scattered in water/ethanolic solution that volume ratio is about 2: 1 to 3: 1; And
Under about 10 to 15MPa pressure and about 100 to 200 ℃ temperature, make nano titanium oxide and Graphene reaction in this dispersion liquid, to obtain described Graphene/nano titanium oxide compound.
2. the method for claim 1, wherein said nano titanium oxide is titania nanotube or titania nanoparticles.
3. method as claimed in claim 2, the preparation method of wherein said titania nanotube comprises following steps:
Titania powder is added in about sodium hydrate aqueous solution of 5 to 15M to obtain a reaction solution, and the weight ratio of the NaOH in wherein said titania powder and this sodium hydrate aqueous solution is about 1: 1 to 1: 3;
Said reaction solution is placed high-pressure reactor, under 110 to 150 ℃ reaction temperature, making its reaction under about pressure of 10 to 15MPa, to obtain titania nanotube.
4. method as claimed in claim 3, the specific area of wherein said titania nanotube are about 200 to 500m
2/ g.
5. the method for claim 1, wherein said Graphene is through an acidification, with this Graphene of oxidation.
6. method as claimed in claim 5, wherein said acidification comprise Graphene were placed about sulfuric acid of 0.5 to 5M about 10 to 12 hours.
7. Graphene/nano titanium oxide compound mainly is made up of about 500: 1 of weight ratio to 10,000: 1 nano titanium oxide and Graphene.
8. Graphene as claimed in claim 7/nano titanium oxide compound, wherein said nano titanium oxide are titania nanotube or titania nanoparticles.
9. Graphene as claimed in claim 8/nano titanium oxide compound, the specific area of wherein said titania nanotube are about 200 to 500m
2/ g.
10. Graphene as claimed in claim 7/nano titanium oxide compound, the surface of wherein said Graphene is partial oxidation at least.
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