CN102698728B - 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 photochemical catalyst field, be specifically related to a kind of titania nanotube/graphene composite material powder and preparation method thereof.
Background technology
Photoelectric conversion technology is using its room temperature reaction and can directly utilize solar energy to drive the special performances such as reaction as light source, and becomes a kind of desirable environmental pollution treatment technology and clear energy sources production technology.On the one hand, people wish to apply photoelectric conversion technological development and go out efficiently, and free of contamination clean energy resource, utilizes solar energy rationally and effectively, this not only can solve the shortage problem of the current energy, the more important thing is and can alleviate a large amount of pollutions that use fossil fuel to bring to environment at present; And on the other hand, people wish that again photoelectric conversion method also can be in the processing of harmful waste, play the part of useful role.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 shows makes no matter it is aspect opto-electronic conversion, or in the degradation treatment of refuse, has good actual application prospect.
In numerous semiconductor nano materials, TiO
2nano particle, because it has unique photoelectrochemical behaviour, excellent heat endurance, biologically inert, nontoxic and prepare easyly etc., causes in fields such as Optical Electro-Chemistry widely and pays close attention to.But, due to 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 photoresponse scope is narrower, makes its Optical Electro-Chemistry activity be subject to certain restriction.Therefore, how to improve TiO
2the photoelectrochemical behaviour of nano particle, has become TiO
2at one of Optical Electro-Chemistry field important research direction and study hotspot.Calendar year 2001 professor Grimes of Univ Pennsylvania USA leader's scientific research group takes the lead in studying in calendar year 2001 the TiO2 nano-tube array of preparing and has pointed out new thinking with its excellent physicochemical characteristics to us.The nano-array pipe height open top that Grimes is prepared, oriented growth, specific area is large, aperture uniformity, under certain length, can firmly be attached on 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 enter TiO fast
2nanotube conducting base, thus greatly reduce the possibility of light induced electron hole-recombination, show good photoelectrochemical behaviour.Therefore, TiO
2aspect the Optical Electro-Chemistry fields such as the pollutant of nano-tube material in the large G&W of photocatalytic degradation, DSSC, photolysis water hydrogen, have broad application prospects, caused people's very big concern and interest.But titanium dioxide, as wide bandgap semiconductor, can only utilize the ultraviolet light in sunshine, and ultraviolet light accounts for the ratio less than 6% of sunshine, causes TiO
2the problem that nanotube/linear array is lower to sunshine utilization rate.
CN102151561A provides a kind of preparation method of photochemical catalyst of consisting of carbon nanotubes loaded with titanium dioxide.This photochemical catalyst is to be attached with nano titanium oxide at the outer surface of CNT.The photochemical catalyst catalytic efficiency that the 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 in honeycomb crystal lattice forms.Although Graphene is two-dimensional structure, be not in fact smooth, but wavy, in two coating systems, this fluctuating is not clearly, in multilayer system, can disappear completely.In Graphene, between each carbon atom and three carbon atoms around, be connected with special singly-bound, a remaining electronics can move freely, and therefore Graphene can conduct electricity.Understand to a certain extent, can think, whole graphene sheet layer forms a large π key.Therefore, Graphene possesses higher specific area and special electronic conduction ability, there is the electrical properties more more excellent than CNT, good electric conductivity, light transmission and chemical stability and machinability, and avoided CNT research to separate with the chirality control, metal mold and the semi-conductor type that are difficult to go beyond in application and the difficult problem such as catalyst impurities, this can become than the multi-functional decorative material of the better electronics of CNT or hole-transfer it.Such as: Paek etc. have synthesized Graphene-SnO
2composite, finds that Graphene can play the effect of electronics transmission channels.By compound to Graphene and titanium dioxide, can utilize the separative efficiency of the electric conductivity increase electron-hole of Graphene, improve the photocatalytic activity of composite.
CN101704511A has announced a kind of preparation method of titania nanotube (or titanium dioxide nano thread) array heterojunction with visible light catalysis activity, comprises the steps: one, the preparation of electrolyte; Two, titania nanotube/linear array is just obtained to titania nanotube/linear array hetero-junctions to deposition in parallel immersion electrolyte with graphite; Three, after titania nanotube/linear array hetero-junctions step 2 being obtained dries up, put into Muffle furnace and calcine 2h～5h, cool to again room temperature with the furnace, must there is titania nanotube/linear array hetero-junctions of visible light catalysis activity, solve titania nanotube/linear array problem lower to sunshine utilization rate.But it is strict that the anodizing that the method adopts requires pH, and the electrolyte of high pH value can be prepared longer nano-tube array, 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 the problem of easily reuniting, and graphene sheet layer is piled up simultaneously, has had a strong impact on photocatalysis performance.
Summary of the invention
For the deficiencies in the prior art, one of object of the present 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, to utilizing the two dimensional crystal structure of Graphene uniqueness, the good character such as electric conductivity and light transmission and Graphene/TiO
2the cooperative compensating effect that the two coupling of nanotube produces, reaches and improves TiO
2the object of nanotube photoelectrochemical behaviour.
For achieving the above object, the present invention is achieved through the following technical solutions:
A kind of preparation method of titania nanotube/graphene composite material, it is characterized in that, described method comprises: (1) first processes graphite with strong protonic acid, forms compound between graphite layers, then add strong oxidizer to be oxidized it, form hydrophilic graphite oxide;
(2) graphite oxide is after supercooling, dilution, ultrasonic peeling off, and the centrifugal graphene oxide that obtains stably dispersing in solution, through suction filtration, oven dry, obtains graphene oxide powder;
(3) by TiO
2p25 nano particle, alkali lye, alcohol organic solvent mix and blend, be then dispersed to graphene oxide powder in mixed solution and stir;
(4) mixed solution system step (3) being obtained is transferred in reactor, after confined reaction, is cooled to room temperature, separates and obtains 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 multiple hexagons) with covalent bonds, forms covalent molecule.Because each carbon atom all can be emitted an electronics, those electronics can move freely, and therefore graphite belongs to electric conductor.According to crystal habit difference, industrial native graphite is divided three classes: compact crystal shape graphite, crystalline flake graphite, aphanitic graphite etc.The present invention there is no particular provisions to the selection of graphite, and those skilled in the art can be selected from according to actual conditions the kind of graphite.
All molecule or ions that can provide proton are all 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 to have the molecule or the ion that are strongly inclined to proton, and any strong protonic acid that those skilled in the art can be known all can be used for the present invention.The present invention's strong protonic acid used is selected from a kind or the combination of at least 2 kinds in the concentrated sulfuric acid, red fuming nitric acid (RFNA), perchloric acid, concentrated hydrochloric acid, SPA, potassium peroxydisulfate, phosphorus pentoxide, preferably the combination of the concentrated sulfuric acid, potassium peroxydisulfate, phosphorus pentoxide.
Graphite is after strong protonic acid is processed, and graphite layers is apart from tentatively being expanded, and interlaminar action power is tentatively weakened, and further with strong oxidizer, it is oxidized, and reaches the object at oxide groups such as graphite linings and interlayer insertion hydroxyl, carboxyls.Strong oxidizer is the material with strong oxidisability, after namely in normal potential order, position is leaned on, in chemical reaction, be very easy to the material (as molecule, atom or ion) of electron gain,, as trivalent cobalt salt, persulfate, peroxide, potassium bichromate, potassium permanganate, oxygen hydrochlorate, the concentrated sulfuric acid etc., be for example all strong oxidizer.Any strong oxidizer that those skilled in the art can be known all can be used for the present invention.Strong oxidizer of the present invention is selected from a kind or the combination of at least 2 kinds in the concentrated sulfuric acid, red fuming nitric acid (RFNA), potassium permanganate, potassium peroxydisulfate, phosphorus pentoxide and potassium hyperchlorate, the for example combination of the combination of the 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, red fuming nitric acid (RFNA)/perchloric acid/phosphorus pentoxide, preferably a kind or the combination of at least 2 kinds in the concentrated sulfuric acid, red fuming nitric acid (RFNA), potassium permanganate.
The mass ratio of strong protonic acid of the present 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., preferably 6.13: 1.
Strong protonic acid processing procedure of the present invention is preferably carried out in oil bath, and preferably, described oil bath temperature is 50-150 DEG C.
Graphite is three-layer laminated crystal, is to be formed by two-dimentional Graphene stacking in layer, and by peeling off layer by layer, people can make the Graphene of individual layer.Low for graphene oxide cost with graphite-made, be the starting point of large-scale production Graphene, prior art has also been carried out certain research to peeling off of graphene oxide.The present invention selects ultrasonic peeling off.In the time of the propagation of ultrasonic velocity density interphase in liquid, liquid flow produces thousands of micro-bubble, the negative pressuren zone that these bubbles form in ultrasonic wave longitudinal propagation forms, growth, at zone of positive pressure rapid closing, this process can form the hot localised points temperature that exceedes 500 atmospheric instantaneous pressures and 5000 DEG C, and hot cold exchange rate is greater than 10
9k/s, similarly is that a succession of little " blast " constantly impacts graphite oxide, and graphene film is peeled off rapidly.The ultrasonic ultrasonic power of peeling off of the present invention is 800-1500W, and ultrasonic time is 150-300S.
In order to obtain the graphene oxide of stably dispersing in solution, the present invention carries out centrifugal after ultrasonic peeling off to gained graphene solution, described centrifugal be high speed centrifugation, preferred ultracentrifugal centrifugal rotational speed is 4000-6000 rev/min, centrifugation time is 300-800S.
The present invention is by the graphene oxide process suction filtration of stably dispersing in solution, the dry graphene oxide powder that obtains.Described suction filtration, the operation that drying process is well known to those skilled in the art repeat no more herein.The temperature and time that the present invention is dry, those skilled in the art can select according to actual conditions, and preferably baking temperature is 40-80 DEG C, for example 40 DEG C, 45 DEG C, 51 DEG C, 58 DEG C, 55 DEG C, 65 DEG C, 71 DEG C, 77 DEG C, 80 DEG C etc., preferably 60 DEG C.Preferably drying time >=10h, such as 10h, 11h, 14h, 18h, 21h etc., preferably 12h.
TiO
2p25 type nano titanium oxide belongs to mixed crystal type, is that to be the anatase of 25nm and rutile be approximately with weight ratio the titanium dioxide that 80/20 ratio is mixed to average grain diameter.TiO
2in 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
2p25, as raw material, with alkali lye and alcohol organic solvent mix and blend, is then dispersed to graphene oxide powder in mixed solution and stirs.Alkali lye of the present invention is selected from sodium hydrate aqueous solution and/or potassium hydroxide aqueous solution; Described concentration of lye is 5-20mol/L, such as 5mol/L, 8mol/L, 12mol/L, 15mol/L, 18mol/L, 20mol/L etc.;
Described alcohol organic solvent is selected from a kind or the combination of at least 2 kinds in methyl alcohol, ethanol, propyl alcohol, isobutanol, isopropyl alcohol, glycerine, enanthol, amylalcohol, particular methanol.。
Hydro-thermal method (Hydrothermal), refer in special closed reactor (autoclave), adopt the aqueous solution as reaction system, by reaction system is heated, pressurization (or spontaneous vapour pressure), 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's application hydro-thermal method, at HTHP, titania nanoparticles, graphene oxide powder are synthesized the composite that has titania nanotube along Graphene superficial growth by next step.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 sheet layer.
The present invention selects hydro-thermal method one-step synthesis to obtain TiO
2nanotube/graphene composite material, specifically realizes by following scheme: the mixed solution system that step (3) is obtained is transferred in reactor, after confined reaction, is cooled to room temperature, separates and obtains white precipitate, and washing, calcining, obtain TiO
2nanotube/graphene composite material.
Preferably, described reactor is closed container, the closed reactor of preferably polytetrafluoroethylene material; Described confined reaction temperature is 100 DEG C ~ 250 DEG C, preferably 180 DEG C ~ 190 DEG C; The described confined reaction time is 5-25h.
Preferably, described in be separated into centrifugation, preferably centrifugation rotating speed is 4000-6000 rev/min; The terminal of described washing is for being washed till mother liquor pH value for 6.0-8.0; Described washing adopts diluted acid and washed with de-ionized water, and preferably watery hydrochloric acid and water clean; Preferably, described olefin(e) acid preferred concentration is the aqueous acid that is less than 0.2M.
Preferably, described calcining heat is 300-800 DEG C, preferably 300-500 DEG C.
Two of object of the present invention be to provide a kind of titania nanotube being prepared by said method graphene composite material.Preferably, described titania nanotube graphene composite material be the nano-powder below particle diameter 300nm.
Three of object of the present invention be to provide a kind of titania nanotube the purposes of graphene composite material.
Described Er Yanghuataina meter Guan Graphene can be for fields, field such as electrode material, photocatalysis, solar energy splitting water, solar cell, environmental protection; for example can utilize solar energy; carry out 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 the two dimensional crystal structure of Graphene uniqueness, the good character such as electric conductivity and light transmission, by by TiO
2the two is coupled nanotube/Graphene, produces cooperative compensating effect, has reached and has improved TiO
2nanotube 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, preparation process is simple and safe;
(3) in the Er Yanghuatai graphene composite material that the present invention obtains, TiO
2nanotube can, along Graphene superficial growth, have stronger active force between the two, has both avoided the reunion of self particle, has also effectively prevented the heavily accumulation of graphene sheet layer.
(4) the Er Yanghuatai graphene composite material particle diameter that the present invention obtains, below 300nm, has good photocatalytic activity, has potential using value in fields such as photocatalysis, environmental protection, electrode material, solar cells.
Brief description of the drawings
Fig. 1 is titania nanotube/Graphene transmission electron microscope (TEM) figure that the present invention prepares.
Detailed description of the invention
For ease of understanding the present invention, it is as follows that the present invention enumerates embodiment.Those skilled in the art should understand, described embodiment helps to understand the present invention, should not be considered as concrete restriction of the present invention.
Embodiment mono-
(1) graphene oxide is synthetic
First use the mixed solution of the concentrated sulfuric acid (6mL), potassium peroxydisulfate (1.25g) and phosphorus pentoxide (1.25g) in the oil bath of 80 DEG C, to carry out strong protonic acid oxidation processes in early stage native graphite (1.5g), product is after cooling dilution filtering, in the concentrated sulfuric acid (60mL), sodium nitrate (6g) and potassium permanganate (7.5g) mixed solution, under 20-50 DEG C of condition, carry out oxidation processes and obtain graphite oxide; The graphite oxide obtaining is diluted to the graphite oxide that can obtain fine dispersion in solution through cooling, ethanol; Graphite oxide is carried out to ultrasonic peeling off (ultrasonic power 1200W, ultrasonic time 300S) and obtain graphene oxide; Graphene oxide is carried out to high speed centrifugation (5000 revs/min of centrifugal rotational speeds, centrifugation time 600S) and obtain the graphene oxide of stably dispersing in solution, and then through suction filtration, under 60 DEG C of conditions, dry 12 hours, obtain graphene oxide powder.
(2) with hydro-thermal method redox graphene synthesizing nano compound material
By P25TiO
2the NaOH aqueous solution of nano particle 10g, 10M, the each 30mL of methyl alcohol, mix and blend, is then dispersed to graphite oxide powder in mixed solution, stirs one hour; Above-mentioned mixed solution was transferred in polytetrafluoroethylene (PTFE) reactor at 180 DEG C to confined reaction after 18 hours, naturally cool to room temperature, centrifugation obtains white precipitate, and by 0.1M dilute hydrochloric acid solution and washed with de-ionized water for several times until final pH is 7, then by sediment in air 350 DEG C calcining 4 hours, obtained TiO
2nanotube/graphene composite material.
Prepared TiO
2the average particle granularity of nanotube/graphene composite material is 250nm.
Embodiment bis-
(1) graphene oxide is synthetic
First use the mixed solution of the concentrated sulfuric acid (8mL), potassium peroxydisulfate (1.5g) and phosphorus pentoxide (1.5g) in the oil bath of 90 DEG C, to carry out strong protonic acid oxidation processes in early stage native graphite (1.5g), product is after cooling dilution filtering, in the concentrated sulfuric acid (80mL), sodium nitrate (8g) and potassium permanganate (9g) mixed solution, under 20-50 DEG C of condition, carry out oxidation processes and obtain graphite oxide; The graphite oxide obtaining is diluted to the graphite oxide that can obtain fine dispersion in solution through cooling, ethanol; Graphite oxide is carried out to ultrasonic peeling off (ultrasonic power 800W, ultrasonic time 350S) and obtain graphene oxide; Graphene oxide is carried out to high speed centrifugation (4000 revs/min of centrifugal rotational speeds, centrifugation time 800S) and obtains the graphene oxide of stably dispersing in solution.
(2) with hydro-thermal method redox graphene synthesizing nano compound material
By P25TiO
2the NaOH aqueous solution of nano particle 15g, 12M, the each 30mL of amylalcohol, mix and blend, is then dispersed to graphite oxide powder in mixed solution, stirs one hour; Above-mentioned mixed solution was transferred in polytetrafluoroethylene (PTFE) reactor at 190 DEG C to confined reaction after 18 hours, naturally cool to room temperature, centrifugation obtains white precipitate, and by 0.1M dilute hydrochloric acid solution and washed with de-ionized water for several times until final pH is 7, then by sediment in air 400 DEG C calcining 4 hours, obtained TiO
2nanotube/graphene composite material.
Prepared TiO
2the particle mean size of nanotube/graphene composite material is 230nm.
Embodiment tri-
(1) graphene oxide is synthetic
First use the mixed solution of the concentrated sulfuric acid (5mL), potassium peroxydisulfate (1g) and phosphorus pentoxide (1g) in the oil bath of 80 DEG C, to carry out strong protonic acid oxidation processes in early stage native graphite (1.5g), product is after cooling dilution filtering, in the concentrated sulfuric acid (50mL), sodium nitrate (5g) and potassium permanganate (6g) mixed solution, under 20-50 DEG C of condition, carry out oxidation processes and obtain graphite oxide; The graphite oxide obtaining is diluted to the graphite oxide that can obtain fine dispersion in solution through cooling, ethanol; Graphite oxide is carried out to ultrasonic peeling off (ultrasonic power 1500W, ultrasonic time 150S) and obtain graphene oxide; The graphene oxide that graphene oxide is carried out to high speed centrifugation (6000 revs/min of centrifugal rotational speeds, centrifugation time 300S) and obtains stably dispersing in solution, then passes through suction filtration, oven dry, obtains graphene oxide powder.
(2) with hydro-thermal method redox graphene synthesizing nano compound material
By P25TiO
2the NaOH aqueous solution of nano particle 8g, 8M, the each 30mL of butanols, mix and blend, is then dispersed to graphite oxide powder powder in mixed solution, stirs one hour; Above-mentioned mixed solution was transferred in polytetrafluoroethylene (PTFE) reactor at 150 DEG C to confined reaction after 15 hours, naturally cool to room temperature, centrifugation obtains white precipitate, and by 0.1M dilute hydrochloric acid solution and washed with de-ionized water for several times until final pH is 7, then by sediment in air 300 DEG C calcining 4 hours, obtained TiO
2nanotube/graphene composite material.
Prepared TiO
2the particle mean size of nanotube/graphene composite material is 290nm.
Embodiment tetra-
(1) graphene oxide is synthetic
First use the mixed solution of the concentrated sulfuric acid (5mL), potassium peroxydisulfate (1g) and phosphorus pentoxide (1g) in the oil bath of 80 DEG C, to carry out strong protonic acid oxidation processes in early stage native graphite (1.5g), product is after cooling dilution filtering, in the concentrated sulfuric acid (50mL), sodium nitrate (5g) and potassium permanganate (6g) mixed solution, under 20-50 DEG C of condition, carry out oxidation processes and obtain graphite oxide; The graphite oxide obtaining is diluted to the graphite oxide that can obtain fine dispersion in solution through cooling, ethanol; Graphite oxide is carried out to ultrasonic peeling off (ultrasonic power 1500W, ultrasonic time 150S) and obtain graphene oxide; The graphene oxide that graphene oxide is carried out to high speed centrifugation (6000 revs/min of centrifugal rotational speeds, centrifugation time 300S) and obtains stably dispersing in solution, then passes through suction filtration, oven dry, obtains graphene oxide powder.
(2) with hydro-thermal method redox graphene synthesizing nano compound material
By P25TiO
2the NaOH aqueous solution of nano particle 8g, 5M, the each 30mL of butanols, mix and blend, is then dispersed to graphite oxide powder powder in mixed solution, stirs one hour; Above-mentioned mixed solution was transferred in polytetrafluoroethylene (PTFE) reactor at 100 DEG C to confined reaction after 25 hours, naturally cool to room temperature, centrifugation obtains white precipitate, and by 0.1M dilute hydrochloric acid solution and washed with de-ionized water for several times until final pH is 7, then by sediment in air 100 DEG C calcining 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
First use the mixed solution of the concentrated sulfuric acid (5mL), potassium peroxydisulfate (1g) and phosphorus pentoxide (1g) in the oil bath of 80 DEG C, to carry out strong protonic acid oxidation processes in early stage native graphite (1.5g), product is after cooling dilution filtering, in the concentrated sulfuric acid (50mL), sodium nitrate (5g) and potassium permanganate (6g) mixed solution, under 20-50 DEG C of condition, carry out oxidation processes and obtain graphite oxide; The graphite oxide obtaining is diluted to the graphite oxide that can obtain fine dispersion in solution through cooling, ethanol; Graphite oxide is carried out to ultrasonic peeling off (ultrasonic power 1500W, ultrasonic time 150S) and obtain graphene oxide; The graphene oxide that graphene oxide is carried out to high speed centrifugation (6000 revs/min of centrifugal rotational speeds, centrifugation time 300S) and obtains stably dispersing in solution, then passes through suction filtration, oven dry, obtains graphene oxide powder.
(2) with hydro-thermal method redox graphene synthesizing nano compound material
By P25TiO
2the NaOH aqueous solution of nano particle 8g, 20M, the each 30mL of butanols, mix and blend, is then dispersed to graphite oxide powder powder in mixed solution, stirs one hour; Above-mentioned mixed solution was transferred in polytetrafluoroethylene (PTFE) reactor at 250 DEG C to confined reaction after 20 hours, naturally cool to room temperature, centrifugation obtains white precipitate, and by 0.1M dilute hydrochloric acid solution and washed with de-ionized water for several times until final pH is 7, then by sediment in air 500 DEG C calcining 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 illustrates detailed process equipment and process flow process of the present invention by above-described embodiment, but the present invention is not limited to above-mentioned detailed process equipment and process flow process, do not mean that the present invention must rely on above-mentioned detailed process equipment and process flow process and could implement.Person of ordinary skill in the field should understand, any improvement in the present invention, and the selections of the equivalence replacement to the each raw material of product of the present invention and the interpolation of auxiliary element, concrete mode etc., within all dropping on protection scope of the present invention and open scope.
Claims (21)
1. the preparation method of a titania nanotube/graphene composite material, it is characterized in that, described method comprises: (1) first carries out oxidation processes processing in early stage graphite with strong protonic acid, form compound between graphite layers, then add strong oxidizer to be oxidized it, form hydrophilic graphite oxide;
(2) graphite oxide is after supercooling, dilution, ultrasonic peeling off, and the centrifugal graphene oxide that obtains stably dispersing in solution, through suction filtration, oven dry, obtains graphene oxide powder;
(3) by TiO
2alkali lye, alcohol organic solvent mix and blend that P25 nano particle, concentration are 5-20mol/L, be then dispersed to graphene oxide powder in mixed solution and stir;
(4) mixed solution system step (3) being obtained is transferred in reactor, after confined reaction, is cooled to room temperature, separates and obtains white precipitate, and washing, calcining, obtain TiO
2nanotube/graphene composite material;
The described reactor of described step (4) is closed container, and described confined reaction temperature is 100 DEG C～250 DEG C, and the described confined reaction time is 5-25h.
2. method according to claim 1, is characterized in that, the described strong protonic acid of step (1) is selected from a kind or the combination of at least 2 kinds in the concentrated sulfuric acid, red fuming nitric acid (RFNA), perchloric acid, concentrated hydrochloric acid, SPA, potassium peroxydisulfate, phosphorus pentoxide.
3. method according to claim 1, is characterized in that, the described strong protonic acid of step (1) is the combination of the concentrated sulfuric acid, potassium peroxydisulfate, phosphorus pentoxide.
4. method according to claim 1, is characterized in that, the mass ratio of described strong protonic acid and graphite is (6-10): 1.
5. method according to claim 1, is characterized in that, the mass ratio of described strong protonic acid and graphite is 6.13:1.
6. method according to claim 1, is characterized in that, described strong protonic acid processing procedure is preferably carried out in oil bath.
7. method according to claim 6, is characterized in that, described oil bath temperature is 50-150 DEG C.
8. method according to claim 1, is characterized in that, the described strong oxidizer of step (1) is selected from a kind or the combination of at least 2 kinds in the concentrated sulfuric acid, red fuming nitric acid (RFNA), potassium permanganate, potassium peroxydisulfate, phosphorus pentoxide and potassium hyperchlorate.
9. method according to claim 1, is characterized in that, the described strong oxidizer of step (1) is selected from a kind or the combination of at least 2 kinds in the concentrated sulfuric acid, red fuming nitric acid (RFNA), potassium permanganate.
10. method according to claim 1, is characterized in that, the described ultrasonic ultrasonic power of peeling off of step (2) is 800-1500W, and ultrasonic time is 150-350S; Described centrifugal be high speed centrifugation.
11. methods according to claim 10, is characterized in that, described ultracentrifugal centrifugal rotational speed is 4000-6000 rev/min, and centrifugation time is 300-800S.
12. methods according to claim 1, is characterized in that, the described alkali lye of step (3) is selected from sodium hydrate aqueous solution and/or potassium hydroxide aqueous solution;
Described alcohol organic solvent is selected from a kind or the combination of at least 2 kinds in methyl alcohol, ethanol, propyl alcohol, isobutanol, isopropyl alcohol, glycerine, enanthol, amylalcohol.
13. methods according to claim 1, is characterized in that, described alcohol organic solvent is methyl alcohol.
14. methods according to claim 1, is characterized in that, the described reactor of step (4) is the closed reactor of polytetrafluoroethylene (PTFE) material; Described confined reaction temperature is 180 DEG C～190 DEG C.
15. methods according to claim 1, is characterized in that, step is separated into centrifugation described in (4); The terminal of described washing is for being washed till mother liquor pH value for 6.0-8.0; Described washing adopts diluted acid and washed with de-ionized water.
16. methods according to claim 15, is characterized in that, described centrifugation rotating speed is turn/clock of 4000-6000.
17. methods according to claim 1, is characterized in that, described washing adopts watery hydrochloric acid and water.
18. methods according to claim 1, is characterized in that, the described calcining heat of step (4) is 100-500 DEG C.
19. methods according to claim 1, is characterized in that, described calcining heat is 100-200 DEG C.
20. 1 kinds of Er Yanghuataina meter Guan graphene composite materials, are prepared by method claimed in claim 1, it is characterized in that, described composite is the nano-powder below particle diameter 300nm.
The purposes of 21. 1 kinds of Er Yanghuataina meter Guan graphene composite materials as claimed in claim 20, is characterized in that, described composite is for electrode material, photocatalysis, solar energy splitting water, solar cell, field of environment protection field.
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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 |
| 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 |
| 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 |
| CN104785235B (en) * | 2015-03-25 | 2017-03-01 | 中南大学 | A kind of preparation method of modified graphene carried titanium dioxide composite photo-catalyst |
| CN105070522B (en) * | 2015-08-31 | 2018-01-02 | 南京林业大学 | Graphene/titania nanotube prepares flexible bending folding thin-film electrode |
| CN106000377B (en) * | 2016-05-25 | 2019-04-19 | 中国科学院城市环境研究所 | Two kinds of titanium oxide/graphene nanocomposite materials |
| 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 |
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| CN101973620A (en) * | 2010-09-21 | 2011-02-16 | 上海大学 | Method for removing heavy metal ions in water by using graphene oxide sheet |
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