CN106622202A - Preparation method of graphene-TiO2 nanotube/FTO double-layer composite film - Google Patents
Preparation method of graphene-TiO2 nanotube/FTO double-layer composite film Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 239000002071 nanotube Substances 0.000 title claims abstract description 97
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 239000002131 composite material Substances 0.000 title abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 40
- 239000000843 powder Substances 0.000 claims abstract description 33
- 150000001875 compounds Chemical class 0.000 claims abstract description 27
- 239000011521 glass Substances 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 37
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 229910002804 graphite Inorganic materials 0.000 claims description 9
- 239000010439 graphite Substances 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 230000004044 response Effects 0.000 claims description 8
- 238000002604 ultrasonography Methods 0.000 claims description 8
- 239000003513 alkali Substances 0.000 claims description 7
- 238000001556 precipitation Methods 0.000 claims description 7
- 239000002585 base Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 238000010828 elution Methods 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- -1 oxygen Graphite alkene Chemical class 0.000 claims description 4
- 239000002244 precipitate Substances 0.000 claims description 4
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000001301 oxygen Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000000034 method Methods 0.000 abstract description 4
- 238000000151 deposition Methods 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 230000000536 complexating effect Effects 0.000 abstract 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- 238000009718 spray deposition Methods 0.000 abstract 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 16
- 229960000907 methylthioninium chloride Drugs 0.000 description 16
- 238000007146 photocatalysis Methods 0.000 description 12
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 11
- 239000012528 membrane Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 238000002189 fluorescence spectrum Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
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- 239000007921 spray Substances 0.000 description 5
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- 206010013786 Dry skin Diseases 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
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- 238000005215 recombination Methods 0.000 description 3
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
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- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000002156 adsorbate Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- MEYZYGMYMLNUHJ-UHFFFAOYSA-N tunicamycin Natural products CC(C)CCCCCCCCCC=CC(=O)NC1C(O)C(O)C(CC(O)C2OC(C(O)C2O)N3C=CC(=O)NC3=O)OC1OC4OC(CO)C(O)C(O)C4NC(=O)C MEYZYGMYMLNUHJ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
Abstract
The invention discloses a preparation method of a graphene-TiO2 nanotube/FTO double-layer composite film. The preparation method is mainly characterized by taking TiO2 and graphene oxide as raw materials, and preparing graphene-TiO2 nanotube compound powder through a hydrothermal method; then dispersing the graphene-TiO2 nanotube compound powder into a polyvinyl alcohol water solution; depositing a graphene-TiO2 nanotube compound to FTO glass by adopting a spray deposition film formation method, thus preparing the graphene-TiO2 nanotube/FTO double-layer composite film. According to the preparation method disclosed by the invention, the specific surface area of TiO2 nanotubes can be increased, and the adsorbability can be increased; meanwhile, photo-induced electrons can be migrated to graphene and FTO, so that complexing of photo-induced electrons and holes can be effectively inhibited, and the photocatalytic efficiency of TiO2 is remarkably enhanced.
Description
Technical field
The present invention relates to a kind of photocatalysis film material and preparation method thereof.
Background technology
Photocatalitic Technique of Semiconductor can be used for eliminating various pollutants, such as:Alkene, dyestuff and pesticide residue etc., have
Prestige becomes the effective means for solving environmental problem, has important practical significance.From Fujishima and Honda A. in 1972
(Fujishima,K.Honda,1972.Electrochemical Photolysis of Water at a
Semiconductor Electrode[J],Nature,238:37-38) utilize TiO2Realize under ultraviolet light as electrode
Decomposition water produces H2And O2Since, TiO2Extensive concern is received as a kind of conductor photocatalysis material.It is excellent additionally, due to its
Chemical stability, the property such as non-toxic and cheap also become study in many conductor photocatalysis materials it is most wide
Material.
Detitanium-ore-type TiO2After by photon irradiation of the energy more than its band gap, electron-hole pair, detached electronics can be produced
A series of redox reaction can occur with the adsorbate with suitable oxidizing reduction potential with hole, i.e., so-called photocatalysis is made
With, and then realize the functions such as organic matter degradation, anti-(killing) bacterium.But as catalysis material, TiO2In actual use
Yet suffer from some problems:1) spectral response range is narrow, TiO2Greater band gap 3.2 (eV) so that only wavelength be less than 387nm
Ultraviolet light its can be excited to produce electron-hole pair, but this part ultraviolet light only accounts for the 4% of sunshine；2) photoproduction electricity
Son-hole easily occurs to be combined during migrating to surface, causes photo-generate electron-hole to burying in oblivion；3) nanoscale
Grain is because the characteristic easily reunited causes the useable surface area of particle to reduce；4) powder photocatalyst is reclaimed in actual application
Property is too poor.These factors result in TiO2The photocatalysis efficiency of photochemical catalyst is relatively low, so as to significantly limit its practical application.
It is not enough for these, domestic and international researcher carried out it is a series of targetedly study, such as to TiO2Carry out various metals, nonmetallic
It is atom doped to increase visible absorption, widen spectral response range；To TiO2Construction heterojunction semiconductor, heterojunction boundary
Both sides are due to the difference of position of energy band so that photo-generate electron-hole easily transmit to different directions by migration, so as to promote light
Separation of raw electron-hole pair etc..
In recent years, due to a series of excellent performances of Graphene, such as the electric conductivity of superelevation, huge theoretical specific surface area,
Mechanical strength of superelevation etc. so that Graphene and TiO2There are many advantages during construction composite photo-catalyst：Graphene is relatively low
Fermi level causes TiO2In light induced electron tend to Graphene migrate, efficiently separated photo-generate electron-hole pair；Stone
The two-dimensional sheet structure of black alkene can be conducive to the contaminant molecule of light induced electron and adsorption as the sports ground of light induced electron
React, so as to drastically increase photocatalytic activity.In addition, the two-dimensional structure advantage in order to make full use of Graphene,
TiO2It is requisite that large-scale interracial contact is formed between Graphene.Many researchers are by Graphene and nanoscale
TiO2Particles dispersed makees photochemical catalyst, but particle is more little more tends to reunite so that effective interface contact is reduced.Opening
TiO2Nanotube has larger specific surface area so that TiO2Nanotube has more avtive spot, and its tubular structure also has
Beneficial to the absorption of photon.Disorder distribution can largely reduce the generation of reunion when nanotube is attached on graphene sheet layer,
Large-scale interracial contact is advantageously formed, this is greatly promoted light induced electron from TiO2To the migration of graphene film.However,
Although these researchs improve to a certain extent photocatalysis efficiency, final product is powder catalyst so that it is in reality
Recyclability in application process is too poor, thus significantly limit its range of application.Multiple means are taken to lift its photocatalysis effect
Rate simultaneously increases the rate of recovery of catalyst sample, reduces practical application into the striving direction that should be the research of photocatalysis from now on.
The content of the invention
The invention provides a kind of can increase specific surface area, improve adsorptivity, suppress being combined, carrying for electron-hole pair
Graphene-the TiO of high recuperability and utilization rate2The preparation method of nanotube/FTO double-layered compound films.
The preparation method of the present invention is as follows：
(1) ratio of 0.18-5.46mg graphene oxides is added in every ml deionized water, is added graphene oxide into
In 55ml deionized waters, by it in instrument is cleaned by ultrasonic ultrasound 30-60 minutes, make graphene oxide dispersed, then by oxidation
Graphene and TiO2The mass ratio of powder is 0.01-0.3:1 ratio adds TiO2, it is preferably in a proportion of 0.15：1, continue ultrasound
30-60 minutes so that TiO2With graphene oxide it is dispersed and anchor together with；
The TiO2Powder is the mixed phase of anatase and rutile, and rutile is 0-0.33 with the mass ratio of anatase:
1。
(2) NaOH is added in the solution of step (1), makes alkali concn in solution be 1-10mol/L, stirred and then turn
In moving on to 100ml teflon-lined reactors, 12～48h is incubated at a temperature of 110～180 DEG C；
(3) question response kettle naturally cools to room temperature, by the hydrochloric acid that the precipitation reaction thing concentration for obtaining is 0.1～1mol/L
Wash to PH between 2-3,12h is then stirred at room temperature, then precipitate with deionized water is washed to neutrality, do at a temperature of 60 DEG C
It is dry, 1h is then heat-treated at a temperature of 300-500 DEG C, Graphene-TiO is obtained2Nanotube complex powder；Hydro-thermal reaction is obtained
TiO2Nanotube is unformed shape, and the purpose of heat treatment is by the TiO of unformed shape2Nanotube crystallizes to form anatase
TiO2Nanotube；
(4) by the Graphene-TiO of step (3)2Nanotube complex powder is added to mass fraction for the poly- of 0.5-2%
Disperseed in vinyl alcohol aqueous solution, by addition Graphene-TiO in every liter of polyvinyl alcohol water solution2Nanotube complex powder
The ratio of 1-5g is obtained Graphene-TiO2The dispersion liquid of nanotube complex powder, by stone by way of sprayed deposit film forming
Black alkene-TiO2The dispersion liquid of nanotube complex powder is deposited on the FTO glass that base reservoir temperature is 100-300 DEG C, and stone is obtained
Black alkene-TiO2Nanotube/FTO double-layered compound films.
The present invention has the advantage that compared with prior art：
1st, specific surface area is increased, adsorptivity is improved.TiO2For nanotube-shaped, with huge specific surface area, Ke Yiti
Adsorb more contaminant molecules for more avtive spots；The huge specific surface area of Graphene and rich pi-electron characteristic make it
Can be acted on by π-π and adsorb more contaminant molecules.
2nd, the compound of electron-hole pair is inhibited.TiO2Nanotube is attached to graphenic surface growth, reduces reunion
There is and formed large-scale interracial contact, light induced electron carries out migration transmission by its interface, is stored in graphene film, because
And restrained effectively the compound of electron-hole pair.The multiphase semiconductor combinations of different band gap can effectively suppress electron-hole
To compound cause TiO2Light induced electron not only can be transferred on graphene sheet layer, can also be transferred in FTO.Graphene
Greatly inhibit photo-generate electron-hole to being combined with the collective effect of FTO, be obviously improved its photocatalysis performance.
3rd, recuperability and utilization rate are improve.Optic catalytic composite material load to the Graphene constructed on electro-conductive glass-
TiO2Nanotube/FTO double-layered compound films, can reuse.
Description of the drawings：
Fig. 1 is Graphene-TiO prepared by embodiment 12The TEM pictures of nanotube complex.
Fig. 2 is Graphene-TiO2The structural representation of nanotube/FTO double-layered compound films.
Fig. 3 is Graphene-TiO in embodiment 12The XRD spectrum of nanotube/FTO two-layer compound membrane samples.
Fig. 4 is the photocatalytic degradation methylene blue efficiency curve comparison diagram of different samples.Wherein：A, b, c, d are respectively real
Apply the Graphene-TiO of example 12Graphene-the TiO of nanotube/FTO samples, comparative example 12Nanotube/glass sample, comparative example 2
TiO2Nanotube/FTO samples, the TiO of comparative example 32Nanotube/glass sample.C/C in figure0For real-time methylene blue solution and just
Beginning methylene blue solution concentration ratio, C/C when photocatalytic degradation is initial0For 1, it can be seen that Graphene-TiO2Nanotube/FTO is double-deck
The photocatalytic degradation efficiency of composite membrane is relative to only composite graphite alkene or a kind of and pure TiO of FTO2Nanotube films have and carry greatly very much
Rise.
Fig. 5 is fluorescence spectrum (PL) figure of different samples.A, b, c, d respectively with accompanying drawing 5 in a, b, c, d sample phase
Together.
Specific embodiment：
Embodiment 1
By 0.15g graphene oxides in 55ml deionized waters ultrasonic disperse 60min, add 1g TiO2(100% it is sharp
Titanium ore) continue ultrasound 60min.22g NaOH are added in above-mentioned solution, the concentration for making alkali in solution reaches 10mol/L, stirs
It is transferred in 100ml teflon-lined reactors after mixing uniformly, at a temperature of 120 DEG C 24h is incubated.Question response kettle nature
Room temperature is cooled to, is 3 to PH by the salt acid elution that the precipitation obtained after reaction uses 0.1mol/L, 12h is then stirred at room temperature, will be heavy
Shallow lake deionized water continues to wash to neutrality, 60 DEG C of dryings, then is heat-treated 1h under 400 DEG C of air atmospheres, and prepared Graphene-
TiO2Nanotube complex powder.Take the above-mentioned powder of 0.1g to be added in the polyvinyl alcohol water solution that 100ml mass fractions are 1%
Ultrasonic disperse, is obtained Graphene-TiO2The dispersion liquid of nanotube complex powder, will dispersion by way of sprayed deposit film forming
Liquid is deposited on the FTO glass of 150 DEG C of base reservoir temperatures, and spray time is 5min, obtains Graphene-TiO2Nanotube/FTO is double-deck
Composite membrane.
The TiO in hydrothermal reaction process2Nanotube curled into by particle dissociation, simultaneous oxidation graphene film surface contains
Oxygen functional group is removed and is reduced into Graphene.As shown in Figure 1, it can be seen that TiO2Nano tube structure, and TiO2Nanotube
Unordered is attached on graphene sheet layer, TiO2Nanotube external diameter about 8nm.As shown in Fig. 21 is TiO2Nanotube, 2 is graphite
Alkene, 3 is FTO films, and 4 is FTO substrates, and the structure of double-deck membrane sample is TiO2Nanotube is attached on graphene film, and it is combined
Thing loads to again FTO surfaces and constitutes double-layered compound film.As shown in Figure 3, it can be seen that sample is anatase TiO2And SnO2Deposit jointly
Can't detect because XRD investigative ranges are limited in, Graphene and doped chemical fluorine.
To the Graphene-TiO for preparing2Nanotube/FTO double-layered compound films, Graphene-TiO2Nanotube powder sprays to general
Obtained Graphene-TiO on logical slide2The pure TiO for not adding Graphene to obtain in nanotube/glass, hydro-thermal reaction2Receive
Nanotube deposition obtained TiO on FTO2The pure TiO for not adding Graphene to obtain in nanotube/FTO, and hydro-thermal reaction2Receive
Nanotube deposition is obtained TiO on common slide24 kinds of samples of nanotube/glass carry out photocatalysis performance test.Experiment condition
For：The methylene blue solution for taking 40ml0.1g/L is placed in 50ml round bottom beakers, and sample of the size for 2cm × 2cm is put into into burning
Cup bottom simultaneously keeps sample apart from light source 10cm, methylene blue solution of degrading in the case where dominant wavelength is for the Hg lamp irradiation of 365nm, often according to
The absorbance of solution of 20 minutes records is penetrated, is urged as light using the degradation rate that irradiates the methylene blue solution after 100 minutes
Change the evaluation index of performance.
Graphene-TiO2The photocatalytic degradation methylene blue solution efficiency curve of nanotube/FTO two-layer compound membrane samples is such as
In Fig. 4 shown in curve a, it is shown that highest photocatalysis efficiency.Jing after Hg lamp irradiation 100 minutes, the degraded of methylene blue solution
Rate reaches 92%, compares the TiO of individual layer same thickness2Film lifts 30%.In addition, having done fluorescence spectrum test, phase to sample
Under the conditions of light source activation, peak is weaker to show that photo-generate electron-hole separative efficiency is higher, Graphene-TiO2Nanotube/FTO is double-deck
In the fluorescence spectrum such as Fig. 5 of composite membrane shown in a curves, it is shown that minimum fluorescence intensity, show electron hole pair separative efficiency
Highest, with reference to photocatalytic degradation efficiency Dependence Results, the raising for showing its photocatalysis efficiency is attributed to the effective of electron hole pair
Separate.
Comparative example 1
As different from Example 1 during spraying film forming, by Graphene-TiO2Nanotube is deposited directly to commonly
On slide, i.e., condition same as Example 1 changes FTO into common slides and Graphene-TiO is obtained2Nanotube/glass.
Graphene-TiO2Graphene-the TiO of nanotube layer thickness and embodiment 12Nanotube layer thickness is consistent.Using embodiment 1
Photocatalytic degradation condition, Graphene-TiO2Curve b in the methylene blue solution degradation efficiency curve of nanotube/glass such as Fig. 4
It is shown, degradation rate reduction by 22.1% compared with the sample of embodiment 1 of methylene blue solution.Graphene-TiO2Nanotube/glass
In the fluorescence spectrum such as Fig. 5 of sample shown in curve b, fluorescence intensity shows the graphite in embodiment 1 higher than the sample of embodiment 1
Alkene-TiO2FTO serves the effect for suppressing Carrier recombination in nanotube/FTO two-layer compound membrane samples.
Comparative example 2
Preparing TiO as different from Example 12Graphene, hydro-thermal reaction is not added to obtain during nanotube
Be pure TiO2Nanotube, i.e., condition same as Example 1 is by Graphene-TiO2Nanotube changes TiO into2Nanotube is obtained
TiO2Nanotube/FTO, TiO2Graphene-the TiO of nanotube layer thickness and embodiment 12Nanotube layer thickness is consistent.Using enforcement
The photocatalytic degradation condition of example 1, TiO2In the methylene blue solution degradation efficiency curve of nanotube/FTO double-layered compound films such as Fig. 4
Shown in curve c, degradation rate reduction by 26.6% compared with the sample of embodiment 1 of methylene blue solution.TiO2Nanotube/FTO is double
In the fluorescence spectrum such as Fig. 5 of tunic shown in curve c, fluorescence intensity shows the graphite in embodiment 1 higher than the sample of embodiment 1
Alkene-TiO2Graphene serves the effect for suppressing Carrier recombination in nanotube/FTO two-layer compound membrane samples.
Comparative example 3
Preparing TiO as different from Example 12Graphene, hydro-thermal reaction is not added to obtain during nanotube
Be pure TiO2Nanotube, then using condition same as Example 1 then by TiO2Nanotube powder deposits to common load glass
TiO is obtained on piece2Nanotube/glass, TiO2Graphene-the TiO of nanotube layer thickness and embodiment 12Nanotube layer thickness one
Cause.Using the photocatalytic degradation condition of embodiment 1, TiO2Methylene blue solution degradation efficiency curve such as Fig. 4 of nanotube/glass
Shown in middle curve d, degradation rate reduction by 36.7% compared with the sample of embodiment 1 of methylene blue solution.TiO2Nanotube/glass
In the fluorescence spectrum such as Fig. 5 of sample shown in curve d, fluorescence intensity shows the graphite in embodiment 1 higher than the sample of embodiment 1
Alkene-TiO2In nanotube/FTO two-layer compound membrane samples, Graphene and FTO serve the effect for suppressing Carrier recombination.
Embodiment 2
By 0.01g graphene oxides in 55ml deionized waters ultrasonic disperse 30min, add 1g TiO2(Rutile Type with
The mass ratio of Anatase is 0.11:1) continue ultrasound 30min, add 22g NaOH in above-mentioned solution, make alkali in solution
Concentration reaches 10mol/L, stirs and is then transferred in 100ml teflon-lined reactors, at a temperature of 140 DEG C
Insulation 24 hours.Question response kettle naturally cools to room temperature, and the precipitation that reaction is obtained is 3 to PH with the salt acid elution of 1mol/L,
Then 12h is stirred at room temperature, precipitate with deionized water is continued to wash to neutrality, 60 DEG C of dryings, then the heat under 300 DEG C of air atmospheres
1h is processed, Graphene-TiO is obtained2Nanotube complex powder.Take the above-mentioned powder of 0.3g and be added to 100ml mass fractions for 1%
Polyvinyl alcohol water solution in ultrasonic disperse, Graphene-TiO is obtained2The dispersion liquid of nanotube complex powder is heavy by spraying
By on the FTO glass of dispersion liquid sprayed deposit to 100 DEG C of base reservoir temperatures, spray time 5min obtains graphite to the mode of product film forming
Alkene-TiO2Nanotube/FTO double-layered compound films.Using the photocatalytic degradation condition of embodiment 1, the degradation rate of methylene blue solution
Compare the TiO of individual layer same thickness2Film lifts 15%.
Embodiment 3
By 0.1g graphene oxides in 55ml deionized waters ultrasonic disperse 40min, add 1g TiO2(Rutile Type with
The mass ratio of Anatase is 0.33:1) continue ultrasound 40min, add 2.2g NaOH in above-mentioned solution, make alkali in solution
Concentration reaches 1mol/L and stirs, in being then transferred into 100ml teflon-lined reactors, at a temperature of 180 DEG C
Insulation 12h.Question response kettle naturally cools to room temperature, is 2 to PH by the salt acid elution that the precipitation obtained after reaction uses 0.5mol/L,
Then 12h is stirred at room temperature, precipitate with deionized water is continued to wash to neutrality, 60 DEG C of dryings, then the heat under 500 DEG C of air atmospheres
1h is processed, Graphene-TiO is obtained2Nanotube complex powder.Take the above-mentioned powder of 0.2g and be added to 100ml mass fractions for 2%
Polyvinyl alcohol water solution in ultrasonic disperse, Graphene-TiO is obtained2The dispersion liquid of nanotube complex powder is heavy by spraying
By on the FTO glass of dispersion liquid sprayed deposit to 300 DEG C of base reservoir temperatures, spray time 5min obtains graphite to the mode of product film forming
Alkene-TiO2Nanotube/FTO double-layered compound films.Using the photocatalytic degradation condition of embodiment 1, the degradation rate of methylene blue solution
Compare the TiO of individual layer same thickness2Film lifts 27%.
Embodiment 4
By 0.3g graphene oxides in 55ml deionized waters ultrasonic disperse 50min, add 1g TiO2(100% sharp titanium
Ore deposit) continue ultrasound 50min, add 11g NaOH in above-mentioned solution, the concentration for making alkali in solution reaches 5mol/L, stirs
In being then transferred into 100ml teflon-lined reactors, at a temperature of 110 DEG C 48h is incubated.Question response kettle natural cooling
To room temperature, the precipitation that reaction is obtained is 2 to PH with the salt acid elution of 0.2mol/L, and 12h is then stirred at room temperature, and precipitation is spent
Ionized water continues to wash to neutrality, 60 DEG C of dryings, then is heat-treated 1h under 400 DEG C of air atmospheres, and Graphene-TiO is obtained2Nanometer
Pipe composite powder.Take the above-mentioned powder of 0.5g and be added in the polyvinyl alcohol water solution that 100ml mass fractions are 0.5% and surpassed
Sound disperses, and Graphene-TiO is obtained2The dispersion liquid of nanotube complex powder, by dispersion liquid by way of sprayed deposit film forming
To on the FTO glass of 200 DEG C of base reservoir temperatures, spray time 5min obtains Graphene-TiO to sprayed deposit2Nanotube/FTO is double-deck
Composite membrane.Using the photocatalytic degradation condition of embodiment 1, the degradation rate of methylene blue solution compares the TiO of individual layer same thickness2
Film lifts 18%.
Claims (5)
1. a kind of Graphene-TiO2The preparation method of nanotube/FTO double-layered compound films, it is characterised in that：It comprises the steps：
(1) ratio of 0.18-5.46mg graphene oxides is added in every ml deionized water, 55ml is added graphene oxide into
In deionized water, by it in instrument is cleaned by ultrasonic ultrasound 30-60 minutes, make graphene oxide dispersed, then by graphite oxide
Alkene and TiO2The mass ratio of powder is 0.01-0.3:1 ratio adds TiO2, continue ultrasound 30-60 minutes so that TiO2With oxygen
Graphite alkene is dispersed and anchors together；
(2) NaOH is added in the solution of step (1), makes alkali concn in solution be 1-10mol/L, stirred and be then transferred into
In 100ml teflon-lined reactors, 12～48h is incubated at a temperature of 110～180 DEG C；
(3) question response kettle naturally cools to room temperature, by the salt acid elution that the precipitation reaction thing concentration for obtaining is 0.1～1mol/L
To PH between 2-3,12h is then stirred at room temperature, then precipitate with deionized water is washed to neutrality, be dried at a temperature of 60 DEG C, so
It is heat-treated 1h at a temperature of 300-500 DEG C afterwards, Graphene-TiO is obtained2Nanotube complex powder；The TiO that hydro-thermal reaction is obtained2
Nanotube is unformed shape, and the purpose of heat treatment is by the TiO of unformed shape2Nanotube crystallizes the TiO to form anatase2
Nanotube；
(4) by the Graphene-TiO of step (3)2Nanotube complex powder is added to the polyvinyl alcohol that mass fraction is 0.5-2%
Disperseed in the aqueous solution, by addition Graphene-TiO in every liter of polyvinyl alcohol water solution2Nanotube complex powder 1-5g's
Ratio is obtained Graphene-TiO2The dispersion liquid of nanotube complex powder, by way of sprayed deposit film forming by Graphene-
TiO2The dispersion liquid of nanotube complex powder is deposited on the FTO glass that base reservoir temperature is 100-300 DEG C, and prepared Graphene-
TiO2Nanotube/FTO double-layered compound films.
2. Graphene-TiO according to claim 12The preparation method of nanotube/FTO double-layered compound films, it is characterised in that：
The TiO2Powder is the mixed phase of anatase and rutile, and rutile is 0-0.33 with the mass ratio of anatase:1.
3. Graphene-TiO according to claim 12The preparation method of nanotube/FTO double-layered compound films, it is characterised in that：
The graphene oxide and TiO2The mass ratio of powder is 0.15：1.
4. Graphene-TiO according to claim 12The preparation method of nanotube/FTO double-layered compound films, it is characterised in that：
The step (2) adds NaOH in the solution of step (1), makes alkali concn in solution be 10mol/L.
5. Graphene-TiO according to claim 12The preparation method of nanotube/FTO double-layered compound films, it is characterised in that：
Holding temperature described in the step (2) is 120 DEG C, and the time is 24h.
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| CN109346110A (en) * | 2018-10-29 | 2019-02-15 | 东北师范大学 | Carbon-based nano laminated film and its manufacturing method applied to color hologram storage |
| CN112892536A (en) * | 2021-01-20 | 2021-06-04 | 燕山大学 | Preparation method of composite photocatalyst, composite photocatalyst and degradation method of dye wastewater |
| US11161094B2 (en) * | 2019-05-01 | 2021-11-02 | Imam Abdulrahman Bin Faisal University | Titania-carbon dot-reduced graphene oxide composites, their make, and use |
| US11896956B2 (en) | 2018-01-30 | 2024-02-13 | Anaphite Limited | Process for producing composite material |
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| CN107403938A (en) * | 2017-06-07 | 2017-11-28 | 南昌航空大学 | A kind of preparation method of microbiological fuel cell production hydrogen |
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