CN102698728A - Titanium dioxide nanotube/ graphene composite material and preparation method thereof - Google Patents
Titanium dioxide nanotube/ graphene composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a titanium dioxide (TiO2) nanotube/ graphene composite material and a preparation method thereof. The method includes utilizing graphite as a raw material, conducting oxidizing and peeling to obtain graphene oxide stably dispersed in solution, conducting suction filtering and drying to obtain graphene oxide powder, stirring TiO2P25 nanometer particles, alkali liquid and alcohol organic solvent in mixing mode, then adding the the graphene oxide powder into the mixture to be dispersed, delivering obtained mixed liquid into a reaction kettle, conducting closed reaction, conduct cooling to the room temperature, conducting separation to obtain white precipitate and conducting washing and burning to obtain the TiO2 nanometer/ graphene composite material. The TiO2 nanometer/ graphene composite material is high in solar energy utilization ratio, free of self particle agglomeration and free of re-accumulation of graphene slice layers. Simultaneously, raw materials are easy to obtain and low in cost. The preparation process is simple and safe. The material has potential application value in the fields of electrode materials, photocatalysis, solar energy splitting water, solar cells, environment and the like.
Description
Technical field
The present invention relates to the photochemical catalyst field, be specifically related to a kind of titania nanotube/graphene composite material powder and preparation method thereof.
Background technology
The photoelectricity transformation technology is with its room temperature reaction and can directly utilize solar energy to drive special performances such as reaction as light source, and becomes a kind of ideal environment pollution control technology and clear energy sources production technology.On the one hand; People hope to use the photoelectricity transformation technology and develop efficiently, and free of contamination clean energy resource utilizes solar energy rationally and effectively; This not only can solve present shortage of energy sources problem, the more important thing is to alleviate a large amount of at present pollutions of using fossil fuel to bring to environment; And on the other hand, people hope that again the photoelectricity method for transformation also can play the part of useful role in the processing of harmful waste.Therefore, the research of opto-electronic conversion is of great immediate significance for the solution energy, pollution problem.Wherein, it is the photoelectric property about semiconductor nano material that people study more, and the photoelectric property that it showed makes no matter it is aspect opto-electronic conversion, and good actual application prospect is still all arranged in the degradation treatment of refuse.
In numerous semiconductor nano materials, TiO
2Nano particle causes widely in fields such as Optical Electro-Chemistry and to pay close attention to because of it has unique photoelectrochemical behaviour, excellent heat endurance, biologically inert, nontoxic and prepare easyly etc.But, because TiO
2The forbidden band of nano particle own is wide, and the electron-hole pair of generation is not only very easily compound but also the life-span is shorter, and the photoresponse scope is narrower, makes its Optical Electro-Chemistry activity receive certain restriction.Therefore, how to improve TiO
2The photoelectrochemical behaviour of nano particle has become TiO
2At one of the Optical Electro-Chemistry field important research direction and research focus.Calendar year 2001 professor Grimes of Univ Pennsylvania USA leader's scientific research group has pointed out new thinking with its excellent physicochemical characteristics to us in the TiO2 nano-tube array that calendar year 2001 takes the lead in studying preparation.The nano-array pipe height open top that Grimes is prepared, oriented growth, big, the aperture uniformity of specific area, can be firm under certain-length attached on the Ti basis, be a kind of nano material with ideal stability three-dimensional structure.
With TiO
2Nano particle is compared, and has the TiO of linear electron transmittability
2Nanotube possesses more superior performance in the transmission of photogenerated charge.Under photoelectric action, light induced electron can get into TiO fast
2The nanotube conducting base, thus greatly reduce the possibility of light induced electron hole-recombination, show photoelectrochemical behaviour preferably.Therefore, TiO
2Aspect the Optical Electro-Chemistry fields such as the pollutant of nano-tube material in the big G&W of photocatalytic degradation, DSSC, photolysis water hydrogen wide application prospect is arranged, caused people's very big concern and interest.But titanium dioxide can only utilize the ultraviolet light in the sunshine, and ultraviolet light accounts for the ratio less than 6% of sunshine as wide bandgap semiconductor, causes TiO
2The problem that nanotube/linear array is lower to the sunshine utilization rate.
CN102151561A provides a kind of preparation method of photochemical catalyst of nano-carbon tube load titanium dioxide.This photochemical catalyst is that the outer surface at CNT is attached with nano titanium oxide.The photochemical catalyst catalytic efficiency that this method prepares is high.
On the other hand, as found new carbon just in 2004, Graphene (Graphene) was intensive by one deck, be wrapped in the two dimensional crystal that the carbon atom on the honeycomb crystal lattice is formed.Though Graphene is a two-dimensional structure, in fact be not smooth, but wavy, in one two coating systems, this fluctuating is not clearly, can complete obiteration in multilayer system.Link to each other with special singly-bound between each carbon atom and on every side three carbon atoms in the Graphene, a remaining electronics can move freely, so Graphene can conduct electricity.Understand to a certain extent, can think, whole Graphene lamella forms a big π key.Therefore; Graphene possesses higher specific surface area and special electronic conduction ability; Have the electrical properties more more excellent, good electrical conductivity, light transmission and chemical stability and machinability than CNT; And the chirality control, metal mold and the semi-conductor type that have been difficult to go beyond in having avoided CNT research and having used separate and a difficult problem such as catalyst impurities, and this makes it can become the multi-functional decorative material than better electronics of CNT or hole-transfer.Such as: Paek etc. have synthesized Graphene-SnO
2Composite finds that Graphene can play the effect of electronics transmission channels.Graphene and titanium dioxide is compound, can utilize the electric conductivity of Graphene to increase the separative efficiency in electronics-hole, improve the photocatalytic activity of composite.
CN101704511A has announced a kind of preparation method with titania nanotube (or titanium dioxide nano thread) array heterojunction of visible light catalysis activity, comprises the steps: one, the preparation of electrolyte; Two, titania nanotube/linear array and graphite deposition in the parallel immersion electrolyte is obtained titania nanotube/linear array hetero-junctions; Three, put into Muffle furnace after the titania nanotube that step 2 is obtained/the linear array hetero-junctions dries up and calcine 2h～5h; Cool to room temperature again with the furnace; Promptly get titania nanotube/linear array hetero-junctions, solved titania nanotube/linear array problem lower the sunshine utilization rate with visible light catalysis activity.But the anodizing that this method adopted is strict to pH, the long nano-tube array of electrolysis fluid power preparation of high pH value, and the surface can cover many sediments, though the nano-tube array surface clean that the electrolyte of low pH value obtains, nano-array is short.
The preparation of existing titanium dioxide optical catalyst exists nanotube length short, and is prone to the problem of reunion, and the Graphene lamella is piled up simultaneously, has had a strong impact on photocatalysis performance.
Summary of the invention
To the deficiency of prior art, one of the object of the invention is to provide a kind of preparation method of nano titania graphene composite material.The present invention is that preparation is a kind of based on Graphene/TiO
2The new function composite of nanotube is in the hope of utilizing character and Graphene/TiO such as the unique two dimensional crystal structure of Graphene, good electric conductivity and light transmission
2The cooperative compensating effect that the two coupling of nanotube is produced reaches and improves TiO
2The purpose of nanotube photoelectrochemical behaviour.
For achieving the above object, the present invention realizes through following technical scheme:
A kind of preparation method of titania nanotube/graphene composite material; It is characterized in that said method comprises: graphite is handled with strong protonic acid earlier in (1), forms compound between graphite layers; Add strong oxidizer then it is carried out oxidation, form hydrophilic graphite oxide;
(2) graphite oxide is after supercooling, dilution, ultrasonic peeling off, and the centrifugal graphene oxide that obtains stably dispersing in the solution through suction filtration, oven dry, obtains the graphene oxide powder;
(3) with TiO
2P25 nano particle, alkali lye, alcohol organic solvent are mixed stirring, the graphene oxide powder is dispersed in the mixed solution stirs then;
(4) mixed solution system that step (3) is obtained is transferred in the agitated reactor, behind the confined reaction, is cooled to room temperature, separates to obtain white precipitate, and washing, calcining obtain TiO
2Nanotube/graphene composite material.
Graphite is a kind of allotrope of carbon, and the periphery of each carbon atom is linking other three carbon atoms (arrangement mode is cellular a plurality of hexagons) with covalent bonds, constitutes covalent molecule.Because each carbon atom all can be emitted an electronics, those electronics can move freely, so graphite belongs to electric conductor.Different according to crystal habit, in the industry native graphite is divided three classes: compact crystal shape graphite, crystalline flake graphite, aphanitic graphite etc.The present invention does not have particular provisions to the selection of graphite, and those skilled in the art can be selected from the kind of graphite according to actual conditions.
The all molecule or ions that can provide proton all are Bronsted acid (being Bronsted acid), for example HCl, H
2SO
4, CH
3COOH, HCO
3 2-, NH
4+, HNO
3, H
3PO
4, fluorosulfuric acid.Strong protonic acid is that molecule or the ion that is inclined to proton strongly arranged, and any strong protonic acid that those skilled in the art can be known all can be used for the present invention.The used strong protonic acid of the present invention is selected from a kind or at least 2 kinds combination in the concentrated sulfuric acid, red fuming nitric acid (RFNA), perchloric acid, concentrated hydrochloric acid, SPA, potassium peroxydisulfate, the phosphorus pentoxide, the combination of the preferred concentrated sulfuric acid, potassium peroxydisulfate, phosphorus pentoxide.
Graphite is after strong protonic acid is handled, and graphite layers is apart from being enlarged by preliminary, and interlaminar action power is weakened by preliminary, further with strong oxidizer it is carried out oxidation, reaches in the purpose of graphite linings with oxide groups such as interlayer insertion hydroxyl, carboxyls.Strong oxidizer is the material with strong oxidisability; After just the position is leaned in the normal potential order; In chemical reaction, be very easy to the material (like molecule, atom or ion) of electron gain;, all be strong oxidizer for example like trivalent cobalt salt, persulfate, peroxide, potassium bichromate, potassium permanganate, oxygen hydrochlorate, the concentrated sulfuric acid etc.Any strong oxidizer that those skilled in the art can be known all can be used for the present invention.Strong oxidizer according to the invention is selected from a kind or at least 2 kinds combination in the concentrated sulfuric acid, red fuming nitric acid (RFNA), potassium permanganate, potassium peroxydisulfate, phosphorus pentoxide and the potassium hyperchlorate; The combination of the for example combination of the combination of the concentrated sulfuric acid, red fuming nitric acid (RFNA), red fuming nitric acid (RFNA), potassium permanganate, the concentrated sulfuric acid/potassium chromate, red fuming nitric acid (RFNA)/potassium peroxydisulfate, the concentrated sulfuric acid/red fuming nitric acid (RFNA)/potassium permanganate, the combination of red fuming nitric acid (RFNA)/perchloric acid/phosphorus pentoxide, a kind or at least 2 kinds combination in the preferred concentrated sulfuric acid, red fuming nitric acid (RFNA), the potassium permanganate.
The mass ratio of strong protonic acid according to the invention and graphite is (6-10): 1, and for example 6: 1,6.05: 1,7.72: 1,8: 1,8.86: 1,9.32: 1,9.98: 1 etc., preferred 6.13: 1.
Strong protonic acid processing procedure according to the invention is preferably carried out in oil bath, and preferably, said oil bath temperature is 50-150 ℃.
Graphite is three-layer laminated crystal, is to be formed by in layer two-dimentional Graphene stacking, and through peeling off layer by layer, people can make the Graphene of individual layer.It is low to prepare the graphene oxide cost with graphite, is the starting point of large-scale production Graphene, and prior art has also been carried out certain research to peeling off of graphene oxide.The present invention selects ultrasonic peeling off for use.When the propagation of ultrasonic velocity density interphase in liquid; Liquid flow produces thousands of micro-bubble; These bubbles form at the negative pressuren zone that the ultrasonic wave longitudinal propagation forms, growth; At the zone of positive pressure rapid closing, this process can form the hot localised points temperature that surpasses 500 atmospheric instantaneous pressures and 5000 ℃, and hot cold exchange rate is greater than 10
9K/s similarly is that a succession of little " blast " constantly impacted graphite oxide, and graphene film is peeled off rapidly.The ultrasonic ultrasonic power of peeling off according to the invention is 800-1500W, and ultrasonic time is 150-300S.
In order to obtain the graphene oxide of stably dispersing in the solution, the present invention ultrasonic peel off the back gained Graphene solution is carried out centrifugal, said centrifugal be high speed centrifugation, preferred ultracentrifugal centrifugal rotational speed is 4000-6000 rev/min, centrifugation time is 300-800S.
The present invention obtains the graphene oxide powder with the graphene oxide of stably dispersing in the solution through suction filtration, drying.The operation that described suction filtration, drying process are well known to those skilled in the art is repeated no more here.The temperature and time that the present invention is dry, those skilled in the art can select according to actual conditions, and preferred baking temperature is 40-80 ℃, for example 40 ℃, 45 ℃, 51 ℃, 58 ℃, 55 ℃, 65 ℃, 71 ℃, 77 ℃, 80 ℃ etc., preferred 60 ℃.Preferred drying time >=10h, for example 10h, 11h, 14h, 18h, 21h etc., preferably 12h.
TiO
2P25 type nano titanium oxide belongs to mixed crystal type, is that average grain diameter is anatase and the rutile of 25nm is approximately 80/20 mixed with weight ratio a titanium dioxide.TiO
2Among the P25, because two kinds of mixing up of structure have increased TiO
2Intracell defect concentration has increased the concentration of carrier, has stronger photo-catalysis capability.
Step of the present invention (3) is selected TiO for use
2P25 mixes stirring as raw material with alkali lye and alcohol organic solvent, the graphene oxide powder is dispersed in the mixed solution stirs then.Alkali lye according to the invention is selected from sodium hydrate aqueous solution and/or potassium hydroxide aqueous solution; Said concentration of lye is 5-20mol/L, for example 5mol/L, 8mol/L, 12mol/L, 15mol/L, 18mol/L, 20mol/L etc.;
Said alcohol organic solvent is selected from a kind or at least 2 kinds combination in methyl alcohol, ethanol, propyl alcohol, isobutanol, isopropyl alcohol, glycerine, enanthol, the amylalcohol, particular methanol.。
Hydro-thermal method (Hydrothermal); Be meant in special closed reactor (autoclave); Adopt the aqueous solution as reaction system,, pressurize (or spontaneous vapour pressure) through to the reaction system heating; Create the reaction environment of a relatively-high temperature, high pressure, make common indissoluble or insoluble substance dissolves and recrystallization form new crystal.The present invention uses hydro-thermal method, and next step synthesizes the composite that titania nanotube is arranged along the Graphene superficial growth with titania nanoparticles, graphene oxide powder at HTHP.Graphene and titania nanotube have stronger active force between the two, can effectively avoid the reunion of self particle, and have effectively prevented the heavily accumulation of Graphene lamella.
The present invention selects the synthetic TiO that obtains of one step of hydro-thermal method for use
2Nanotube/graphene composite material, specifically realize through following scheme: the mixed solution system that step (3) is obtained is transferred in the agitated reactor, behind the confined reaction, is cooled to room temperature, separates to obtain white precipitate, and washing, calcining obtain TiO
2Nanotube/graphene composite material.
Preferably, said agitated reactor is a closed container, the closed reactor of preferably polytetrafluoroethylene material; Said confined reaction temperature is 100 ℃ ~ 250 ℃, preferred 180 ℃ ~ 190 ℃; The said confined reaction time is 5-25h.
Preferably, saidly be separated into centrifugation, preferably centrifugalizing rotating speed is 4000-6000 rev/min; The terminal point of said washing is 6.0-8.0 for being washed till mother liquor pH value; Diluted acid and washed with de-ionized water are adopted in said washing, and preferred watery hydrochloric acid and water clean; Preferably, said olefin(e) acid preferred concentration is the aqueous acid less than 0.2M.
Preferably, described calcining heat is 300-800 ℃, preferred 300-500 ℃.
Two of the object of the invention provide a kind of titania nanotube that obtains by method for preparing graphene composite material.Preferably, said titania nanotube graphene composite material be the nano-powder below the particle diameter 300nm.
Three of the object of the invention provide a kind of titania nanotube the purposes of graphene composite material.
Said titania nanotube Graphene can be used for fields, field such as electrode material, photocatalysis, solar energy splitting water, solar cell, environmental protection; For example can utilize solar energy; Carry out the photocatalytic degradation organic industrial sewage, can prepare electrode of lithium cell etc.
Compared with prior art, the present invention has following beneficial effect:
(1) the present invention has utilized character such as the unique two dimensional crystal structure of Graphene, good electric conductivity and light transmission, through with TiO
2The two is coupled nanotube/Graphene, produces the cooperative compensating effect, has reached and has improved TiO
2The nanotube photoelectrochemical behaviour has improved the utilization rate to solar energy;
(2) raw materials used common being easy to get of the present invention, with low cost, the preparation process is simple and safe;
(3) the resulting titanium dioxide of the present invention in the graphene composite material, TiO
2Nanotube can have stronger active force between the two along the Graphene superficial growth, has both avoided the reunion of self particle, has also effectively prevented the heavily accumulation of Graphene lamella.
(4) the resulting titanium dioxide of the present invention the graphene composite material particle diameter below 300nm, have good photocatalytic activity, in fields such as photocatalysis, environmental protection, electrode material, solar cells potential using value is arranged all.
Description of drawings
The titania nanotube that Fig. 1 prepares for the present invention/Graphene transmission electron microscope (TEM) figure.
The specific embodiment
For ease of understanding the present invention, it is following that the present invention enumerates embodiment.Those skilled in the art should understand, and said embodiment helps to understand the present invention, should not be regarded as concrete restriction of the present invention.
Embodiment one
(1) graphene oxide is synthetic
Native graphite (1.5g) is carried out strong protonic acid oxidation processes in early stage with the mixed solution of the concentrated sulfuric acid (6mL), potassium peroxydisulfate (1.25g) and phosphorus pentoxide (1.25g) earlier in 80 ℃ oil bath; Product is after the cooling dilution and filtering; In the concentrated sulfuric acid (60mL), sodium nitrate (6g) and potassium permanganate (7.5g) mixed solution, carry out oxidation processes under the 20-50 ℃ of condition and obtain graphite oxide; The graphite oxide that obtains is diluted the graphite oxide that can obtain fine dispersion in the solution through cooling, ethanol; Graphite oxide is carried out ultrasonic peeling off (ultrasonic power 1200W, ultrasonic time 300S) obtain graphene oxide; Graphene oxide is carried out the graphene oxide that high speed centrifugation (5000 rev/mins of centrifugal rotational speeds, centrifugation time 600S) obtains stably dispersing in the solution, and then through suction filtration, oven dry is 12 hours under 60 ℃ of conditions, obtains the graphene oxide powder.
(2) with hydro-thermal method redox graphene synthesizing nano compound material
With P25TiO
2The NaOH aqueous solution of nano particle 10g, 10M, each 30mL of methyl alcohol mix and stir, and then the graphite oxide powder are dispersed in the mixed solution, stir one hour; Be transferred in the polytetrafluoroethylene (PTFE) agitated reactor at 180 ℃ of following confined reactions above-mentioned mixed solution after 18 hours; Naturally cool to room temperature; Centrifugation obtains white precipitate; And to use 0.1M dilute hydrochloric acid solution and washed with de-ionized water be 7 up to final pH for several times, then with sediment in air 350 ℃ calcined 4 hours, obtained TiO
2Nanotube/graphene composite material.
Prepared TiO
2The average particle granularity of nanotube/graphene composite material is 250nm.
Embodiment two
(1) graphene oxide is synthetic
Native graphite (1.5g) is carried out strong protonic acid oxidation processes in early stage with the mixed solution of the concentrated sulfuric acid (8mL), potassium peroxydisulfate (1.5g) and phosphorus pentoxide (1.5g) earlier in 90 ℃ oil bath; Product is after the cooling dilution and filtering; In the concentrated sulfuric acid (80mL), sodium nitrate (8g) and potassium permanganate (9g) mixed solution, carry out oxidation processes under the 20-50 ℃ of condition and obtain graphite oxide; The graphite oxide that obtains is diluted the graphite oxide that can obtain fine dispersion in the solution through cooling, ethanol; Graphite oxide is carried out ultrasonic peeling off (ultrasonic power 800W, ultrasonic time 350S) obtain graphene oxide; Graphene oxide is carried out the graphene oxide that high speed centrifugation (4000 rev/mins of centrifugal rotational speeds, centrifugation time 800S) obtains stably dispersing in the solution.
(2) with hydro-thermal method redox graphene synthesizing nano compound material
With P25TiO
2The NaOH aqueous solution of nano particle 15g, 12M, each 30mL of amylalcohol mix and stir, and then the graphite oxide powder are dispersed in the mixed solution, stir one hour; Be transferred in the polytetrafluoroethylene (PTFE) agitated reactor at 190 ℃ of following confined reactions above-mentioned mixed solution after 18 hours; Naturally cool to room temperature; Centrifugation obtains white precipitate; And to use 0.1M dilute hydrochloric acid solution and washed with de-ionized water be 7 up to final pH for several times, then with sediment in air 400 ℃ calcined 4 hours, obtained TiO
2Nanotube/graphene composite material.
Prepared TiO
2The particle mean size of nanotube/graphene composite material is 230nm.
Embodiment three
(1) graphene oxide is synthetic
Native graphite (1.5g) is carried out strong protonic acid oxidation processes in early stage with the mixed solution of the concentrated sulfuric acid (5mL), potassium peroxydisulfate (1g) and phosphorus pentoxide (1g) earlier in 80 ℃ oil bath; Product is after the cooling dilution and filtering; In the concentrated sulfuric acid (50mL), sodium nitrate (5g) and potassium permanganate (6g) mixed solution, carry out oxidation processes under the 20-50 ℃ of condition and obtain graphite oxide; The graphite oxide that obtains is diluted the graphite oxide that can obtain fine dispersion in the solution through cooling, ethanol; Graphite oxide is carried out ultrasonic peeling off (ultrasonic power 1500W, ultrasonic time 150S) obtain graphene oxide; Graphene oxide is carried out the graphene oxide that high speed centrifugation (6000 rev/mins of centrifugal rotational speeds, centrifugation time 300S) obtains stably dispersing in the solution, pass through suction filtration, oven dry then, obtain the graphene oxide powder.
(2) with hydro-thermal method redox graphene synthesizing nano compound material
With P25TiO
2The NaOH aqueous solution of nano particle 8g, 8M, each 30mL of butanols mix and stir, and then graphite oxide powder powder are dispersed in the mixed solution, stir one hour; Be transferred in the polytetrafluoroethylene (PTFE) agitated reactor at 150 ℃ of following confined reactions above-mentioned mixed solution after 15 hours; Naturally cool to room temperature; Centrifugation obtains white precipitate; And to use 0.1M dilute hydrochloric acid solution and washed with de-ionized water be 7 up to final pH for several times, then with sediment in air 300 ℃ calcined 4 hours, obtained TiO
2Nanotube/graphene composite material.
Prepared TiO
2The particle mean size of nanotube/graphene composite material is 290nm.
Embodiment four
(1) graphene oxide is synthetic
Native graphite (1.5g) is carried out strong protonic acid oxidation processes in early stage with the mixed solution of the concentrated sulfuric acid (5mL), potassium peroxydisulfate (1g) and phosphorus pentoxide (1g) earlier in 80 ℃ oil bath; Product is after the cooling dilution and filtering; In the concentrated sulfuric acid (50mL), sodium nitrate (5g) and potassium permanganate (6g) mixed solution, carry out oxidation processes under the 20-50 ℃ of condition and obtain graphite oxide; The graphite oxide that obtains is diluted the graphite oxide that can obtain fine dispersion in the solution through cooling, ethanol; Graphite oxide is carried out ultrasonic peeling off (ultrasonic power 1500W, ultrasonic time 150S) obtain graphene oxide; Graphene oxide is carried out the graphene oxide that high speed centrifugation (6000 rev/mins of centrifugal rotational speeds, centrifugation time 300S) obtains stably dispersing in the solution, pass through suction filtration, oven dry then, obtain the graphene oxide powder.
(2) with hydro-thermal method redox graphene synthesizing nano compound material
With P25TiO
2The NaOH aqueous solution of nano particle 8g, 5M, each 30mL of butanols mix and stir, and then graphite oxide powder powder are dispersed in the mixed solution, stir one hour; Be transferred in the polytetrafluoroethylene (PTFE) agitated reactor at 100 ℃ of following confined reactions above-mentioned mixed solution after 25 hours; Naturally cool to room temperature; Centrifugation obtains white precipitate; And to use 0.1M dilute hydrochloric acid solution and washed with de-ionized water be 7 up to final pH for several times, then with sediment in air 100 ℃ calcined 4 hours, obtained TiO
2Nanotube/graphene composite material.
Prepared TiO
2The particle mean size of nanotube/graphene composite material is 270nm.
Embodiment five
(1) graphene oxide is synthetic
Native graphite (1.5g) is carried out strong protonic acid oxidation processes in early stage with the mixed solution of the concentrated sulfuric acid (5mL), potassium peroxydisulfate (1g) and phosphorus pentoxide (1g) earlier in 80 ℃ oil bath; Product is after the cooling dilution and filtering; In the concentrated sulfuric acid (50mL), sodium nitrate (5g) and potassium permanganate (6g) mixed solution, carry out oxidation processes under the 20-50 ℃ of condition and obtain graphite oxide; The graphite oxide that obtains is diluted the graphite oxide that can obtain fine dispersion in the solution through cooling, ethanol; Graphite oxide is carried out ultrasonic peeling off (ultrasonic power 1500W, ultrasonic time 150S) obtain graphene oxide; Graphene oxide is carried out the graphene oxide that high speed centrifugation (6000 rev/mins of centrifugal rotational speeds, centrifugation time 300S) obtains stably dispersing in the solution, pass through suction filtration, oven dry then, obtain the graphene oxide powder.
(2) with hydro-thermal method redox graphene synthesizing nano compound material
With P25TiO
2The NaOH aqueous solution of nano particle 8g, 20M, each 30mL of butanols mix and stir, and then graphite oxide powder powder are dispersed in the mixed solution, stir one hour; Be transferred in the polytetrafluoroethylene (PTFE) agitated reactor at 250 ℃ of following confined reactions above-mentioned mixed solution after 20 hours; Naturally cool to room temperature; Centrifugation obtains white precipitate; And to use 0.1M dilute hydrochloric acid solution and washed with de-ionized water be 7 up to final pH for several times, then with sediment in air 500 ℃ calcined 3 hours, obtained TiO
2Nanotube/graphene composite material.
Prepared TiO
2The particle mean size of nanotube/graphene composite material is 240nm.
Applicant's statement; The present invention explains detailed process equipment of the present invention and technological process through the foregoing description; But the present invention is not limited to above-mentioned detailed process equipment and technological process, does not mean that promptly the present invention must rely on above-mentioned detailed process equipment and technological process could be implemented.The person of ordinary skill in the field should understand, and to any improvement of the present invention, to the interpolation of the equivalence replacement of each raw material of product of the present invention and auxiliary element, the selection of concrete mode etc., all drops within protection scope of the present invention and the open scope.
Claims (10)
1. the preparation method of a titania nanotube/graphene composite material; It is characterized in that; Said method comprises: oxidation processes processing in early stage graphite is carried out with strong protonic acid earlier in (1); Form compound between graphite layers, add strong oxidizer then it is carried out oxidation, form hydrophilic graphite oxide;
(2) graphite oxide is after supercooling, dilution, ultrasonic peeling off, and the centrifugal graphene oxide that obtains stably dispersing in the solution through suction filtration, oven dry, obtains the graphene oxide powder;
(3) with TiO
2P25 nano particle, alkali lye, alcohol organic solvent are mixed stirring, the graphene oxide powder is dispersed in the mixed solution stirs then;
(4) mixed solution system that step (3) is obtained is transferred in the agitated reactor, behind the confined reaction, is cooled to room temperature, separates to obtain white precipitate, and washing, calcining obtain TiO
2Nanotube/graphene composite material.
2. method according to claim 1; It is characterized in that; The said strong protonic acid of step (1) is selected from a kind or at least 2 kinds combination in the concentrated sulfuric acid, red fuming nitric acid (RFNA), perchloric acid, concentrated hydrochloric acid, SPA, potassium peroxydisulfate, the phosphorus pentoxide, the combination of the preferred concentrated sulfuric acid, potassium peroxydisulfate, phosphorus pentoxide;
Preferably, the mass ratio of said strong protonic acid and graphite is (6-10): 1, and preferred 6.13: 1;
Preferably, said strong protonic acid processing procedure is preferably carried out in oil bath, and preferably, said oil bath temperature is 50-150 ℃.
3. method according to claim 1 and 2; It is characterized in that; The said strong oxidizer of step (1) is selected from a kind or at least 2 kinds combination in the concentrated sulfuric acid, red fuming nitric acid (RFNA), potassium permanganate, potassium peroxydisulfate, phosphorus pentoxide and the potassium hyperchlorate, a kind or at least 2 kinds combination in the preferred concentrated sulfuric acid, red fuming nitric acid (RFNA), the potassium permanganate.
4. according to each described method of claim 1-3, it is characterized in that the said ultrasonic ultrasonic power of peeling off of step (2) is 800-1500W, ultrasonic time is 150-350S;
Said centrifugal be high speed centrifugation, preferred ultracentrifugal centrifugal rotational speed is 4000-6000 rev/min, centrifugation time is 300-800S.
5. according to each described method of claim 1-4, it is characterized in that the said alkali lye of step (3) is selected from sodium hydrate aqueous solution and/or potassium hydroxide aqueous solution; Said concentration of lye is 5-20mol/L;
Said alcohol organic solvent is selected from a kind or at least 2 kinds combination in methyl alcohol, ethanol, propyl alcohol, isobutanol, isopropyl alcohol, glycerine, enanthol, the amylalcohol, particular methanol.
6. according to each described method of claim 1-5, it is characterized in that the said agitated reactor of step (4) is a closed container, the closed reactor of preferably polytetrafluoroethylene material; Said confined reaction temperature is 100 ℃ ~ 250 ℃, preferred 180 ℃ ~ 190 ℃; The said confined reaction time is 5-25h.
7. according to each described method of claim 1-6, it is characterized in that step (4) is said to be separated into centrifugation, preferably centrifugalizing rotating speed is 4000-6000 rev/min; The terminal point of said washing is 6.0-8.0 for being washed till mother liquor pH value; Diluted acid and washed with de-ionized water are adopted in said washing, preferred watery hydrochloric acid and water.
8. according to each described method of claim 1-7, it is characterized in that the described calcining heat of step (4) is 100-500 ℃, preferred 100-200 ℃.
9. a Er Yanghuatainamiguan graphene composite material is prepared by each described method of claim 1-8, it is characterized in that, said composite is the nano-powder below the particle diameter 300nm.
10. the purposes of a Er Yanghuatainamiguan graphene composite material as claimed in claim 9 is characterized in that, said composite is used for fields, field such as electrode material, photocatalysis, solar energy splitting water, solar cell, environmental protection.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210149532.2A CN102698728B (en) | 2012-05-14 | 2012-05-14 | Titanium dioxide nanotube/ graphene composite material and preparation method thereof |
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| CN102872848A (en) * | 2012-10-17 | 2013-01-16 | 东南大学 | Preparation method for adsorption enhanced graphene titanium dioxide nano-composite photocatalyst |
| CN102872846A (en) * | 2012-10-12 | 2013-01-16 | 合肥工业大学 | Coal ash microsphere loaded one-dimensional nanometer titanium dioxide (TiO2) composite photocatalyst and preparation method thereof |
| CN104084186A (en) * | 2014-07-23 | 2014-10-08 | 武汉理工大学 | Graphene/titanium dioxide photocatalysis composite material and preparation method thereof |
| CN104332611A (en) * | 2014-08-27 | 2015-02-04 | 中国工程物理研究院化工材料研究所 | Graphene/titanium dioxide nano fiber composite material, preparation method and applications thereof |
| CN104785235A (en) * | 2015-03-25 | 2015-07-22 | 中南大学 | Preparation method for modified graphene-loaded titanium dioxide composite photocatalyst |
| CN105070522A (en) * | 2015-08-31 | 2015-11-18 | 南京林业大学 | Flexible bending foldable thin-film electrode prepared by using graphene/titanium dioxide nanotube |
| CN106000377A (en) * | 2016-05-25 | 2016-10-12 | 中国科学院城市环境研究所 | Nano-composite of two types of titanium oxides/graphene |
| CN106492777A (en) * | 2016-12-13 | 2017-03-15 | 常州大学 | A kind of nano composite photo-catalyst with visible light activity and preparation method thereof |
| CN107879338A (en) * | 2017-12-29 | 2018-04-06 | 天津市天波科达科技有限公司 | A kind of technical grade graphene oxide process units |
| CN108069730A (en) * | 2016-11-15 | 2018-05-25 | 许美凤 | A kind of electric transducer |
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| US11896956B2 (en) | 2018-01-30 | 2024-02-13 | Anaphite Limited | Process for producing composite material |
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| CN102872846A (en) * | 2012-10-12 | 2013-01-16 | 合肥工业大学 | Coal ash microsphere loaded one-dimensional nanometer titanium dioxide (TiO2) composite photocatalyst and preparation method thereof |
| CN102872848A (en) * | 2012-10-17 | 2013-01-16 | 东南大学 | Preparation method for adsorption enhanced graphene titanium dioxide nano-composite photocatalyst |
| CN104084186A (en) * | 2014-07-23 | 2014-10-08 | 武汉理工大学 | Graphene/titanium dioxide photocatalysis composite material and preparation method thereof |
| CN104084186B (en) * | 2014-07-23 | 2016-06-01 | 武汉理工大学 | A kind of Graphene/optically catalytic TiO 2 matrix material and its preparation method |
| CN104332611A (en) * | 2014-08-27 | 2015-02-04 | 中国工程物理研究院化工材料研究所 | Graphene/titanium dioxide nano fiber composite material, preparation method and applications thereof |
| CN104332611B (en) * | 2014-08-27 | 2016-09-07 | 中国工程物理研究院化工材料研究所 | Graphene/titanium dioxide nanofiber composite and its preparation method and application |
| CN104785235A (en) * | 2015-03-25 | 2015-07-22 | 中南大学 | Preparation method for modified graphene-loaded titanium dioxide composite photocatalyst |
| CN105070522B (en) * | 2015-08-31 | 2018-01-02 | 南京林业大学 | Graphene/titania nanotube prepares flexible bending folding thin-film electrode |
| CN105070522A (en) * | 2015-08-31 | 2015-11-18 | 南京林业大学 | Flexible bending foldable thin-film electrode prepared by using graphene/titanium dioxide nanotube |
| CN106000377A (en) * | 2016-05-25 | 2016-10-12 | 中国科学院城市环境研究所 | Nano-composite of two types of titanium oxides/graphene |
| CN108069730A (en) * | 2016-11-15 | 2018-05-25 | 许美凤 | A kind of electric transducer |
| CN108069730B (en) * | 2016-11-15 | 2020-06-30 | 许美凤 | Electric sensor |
| CN106492777A (en) * | 2016-12-13 | 2017-03-15 | 常州大学 | A kind of nano composite photo-catalyst with visible light activity and preparation method thereof |
| CN107879338A (en) * | 2017-12-29 | 2018-04-06 | 天津市天波科达科技有限公司 | A kind of technical grade graphene oxide process units |
| US11896956B2 (en) | 2018-01-30 | 2024-02-13 | Anaphite Limited | Process for producing composite material |
| CN109465002A (en) * | 2018-11-12 | 2019-03-15 | 齐鲁工业大学 | A kind of nano-TiO2The preparation method of/graphene composite material |
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