CN106944034A - （Si,Y）Codope TiO2The high-efficiency self-cleaning film and preparation method of/redox graphene complex - Google Patents
（Si,Y）Codope TiO2The high-efficiency self-cleaning film and preparation method of/redox graphene complex Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 53
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 52
- 238000004140 cleaning Methods 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 133
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 104
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 91
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 67
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 67
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 67
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 67
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 67
- 239000000243 solution Substances 0.000 claims abstract description 58
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000002994 raw material Substances 0.000 claims abstract description 27
- 239000002243 precursor Substances 0.000 claims abstract description 26
- 235000011187 glycerol Nutrition 0.000 claims abstract description 25
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 20
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- ULWHHBHJGPPBCO-UHFFFAOYSA-N propane-1,1-diol Chemical class CCC(O)O ULWHHBHJGPPBCO-UHFFFAOYSA-N 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical class Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 15
- 239000007864 aqueous solution Substances 0.000 claims abstract description 14
- 235000011167 hydrochloric acid Nutrition 0.000 claims abstract description 13
- 239000003599 detergent Substances 0.000 claims abstract description 9
- 238000003618 dip coating Methods 0.000 claims abstract description 9
- 239000011259 mixed solution Substances 0.000 claims abstract description 9
- 238000004528 spin coating Methods 0.000 claims abstract description 9
- 239000000758 substrate Substances 0.000 claims abstract description 9
- 239000010408 film Substances 0.000 claims description 74
- 150000002500 ions Chemical class 0.000 claims description 14
- 239000010409 thin film Substances 0.000 claims description 11
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- BXJPTTGFESFXJU-UHFFFAOYSA-N yttrium(3+);trinitrate Chemical class [Y+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BXJPTTGFESFXJU-UHFFFAOYSA-N 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 238000007146 photocatalysis Methods 0.000 abstract description 21
- 238000010304 firing Methods 0.000 abstract description 6
- 229910052727 yttrium Inorganic materials 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract 1
- 230000003287 optical effect Effects 0.000 description 16
- 230000010148 water-pollination Effects 0.000 description 10
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- -1 graphite alkene Chemical class 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 6
- 230000002708 enhancing effect Effects 0.000 description 5
- 239000003344 environmental pollutant Substances 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 231100000719 pollutant Toxicity 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000002270 dispersing agent Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 3
- 230000007062 hydrolysis Effects 0.000 description 3
- 238000006460 hydrolysis reaction Methods 0.000 description 3
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 3
- 229940107698 malachite green Drugs 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- PYTMYKVIJXPNBD-UHFFFAOYSA-N clomiphene citrate Chemical compound [H+].[H+].[H+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.C1=CC(OCCN(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C(Cl)C1=CC=CC=C1 PYTMYKVIJXPNBD-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000002079 cooperative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- QBZIEGUIYWGBMY-FUZXWUMZSA-N (5Z)-5-hydroxyimino-6-oxonaphthalene-2-sulfonic acid iron Chemical compound [Fe].O\N=C1/C(=O)C=Cc2cc(ccc12)S(O)(=O)=O.O\N=C1/C(=O)C=Cc2cc(ccc12)S(O)(=O)=O.O\N=C1/C(=O)C=Cc2cc(ccc12)S(O)(=O)=O QBZIEGUIYWGBMY-FUZXWUMZSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000725 suspension Substances 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/58—Fabrics or filaments
- B01J35/59—Membranes
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
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- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Laminated Bodies (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Surface Treatment Of Glass (AREA)
- Catalysts (AREA)
Abstract
（Si,Y）Codope TiO2/ redox graphene complex high-efficiency self-cleaning film, including following components:Y contents are TiO2And SiO20.5~1.5at% of total amount；Si contents are TiO2And SiO2The 30at.% of total amount；Graphene oxide (GO) is TiO2And SiO2The 3wt.% of total amount；The composition film has purer TiO2The notable good conductive of film, photo-induced super-hydrophilicity, light is transparent and the self-cleaning performance performance such as photocatalysis；The Si and Y of appropriate amount doping, can keep and increase the transparent performance of film.The step of preparing film be：1）Raw material butyl titanate, tetraethyl orthosilicate, yttrium nitrate and the GO aqueous solution are added and configure precursor solution into absolute ethyl alcohol, water, ethylene glycol, propane diols, acetylacetone,2,4-pentanedione and glycerine mixed solution；2）The 1.0ml concentrated hydrochloric acids that concentration is 35% are added in precursor solution per 100ml；3）It is stirred until homogeneous transparent；4）The substrate of plated film is needed to be washed with detergent and EtOH Sonicate；5) dip coating or spin coating is used, is dried after applying every time；6）450 DEG C of firings；Preparation method is simple, easy, low cost.
Description
Technical field
The invention belongs to technical field of environmental purification, and in particular to（Si,Y）- codope TiO2/ redox graphene is answered
High-efficiency self-cleaning film of compound and preparation method thereof.
Background technology
Automatically cleaning is a critically important depollution of environment technology.Generally the film with self-cleaning performance is applied and carried out in interior
The surfaces such as External building thing, electrical equipment and Medical Devices, are played to the pernicious gas in environment and the pollutant for being attached to film surface
Photocatalysis Decomposition, sterilizing and reduce pollutant degree of adhesion effect so that play environment purification etc. effect.Therefore, the world
Various countries have extensive research to self-cleaning film and applied.TiO2Film is due to preferable photocatalysis and steady in the environment
The performance such as fixed is self-cleaning film conventional at present.
TiO2Film is that automatically cleaning conventional at present is thin due to the performance such as stablizing with preferable photocatalysis and in the environment
Film.Self-cleaning film is usually required that with good photocatalysis performance（Resolving harmful gas and attachment pollutant and go out
Bacterium）, good electric conductivity（Prevent the Electrostatic Absorption of pollutant）, photo-induced super-hydrophilicity energy（It is difficult some pollutants attached
And carried absorption water cleaning surface）With some applications（Such as glass pane）In necessary optical clarity can [1].Although TiO2Film
With self-cleaning performances such as preferable photocatalysis, but performance is still limited.Pass through ion doping or/and and graphene（rGO）It is multiple
Close enhancing TiO2The photocatalysis performance of powder body material has extensive research and applied, and generally has more significant effect.But from
Son doping or/and and graphene（rGO）It is combined to TiO2The developmental research of film photocatalytic material is seldom.Some usual ions are mixed
Miscellaneous and composite graphite alkene can cause optical clarity to reduce, and study and show that substantial amounts of Si doping can strengthen TiO2The light of material
It is transparent at the same strengthen photocatalysis performance.Therefore, while composite graphite alkene, some ions are selected（Such as Y）Adulterate and the Si that adulterates,
Photopermeability can be enable not reduce enhancing living.But lack Si- doping TiO at present2/ rGO complex thin films are developed, and more lack tool
There are good conductive, photo-induced super-hydrophilicity and optical clarity energy（Si,Y）- codope TiO2/ graphene complex film is opened
Hair.
The content of the invention
For the above-mentioned the deficiencies in the prior art of customer service, it is an object of the invention to provide（Si,Y）- codope TiO2/ redox
High-efficiency self-cleaning film of graphene complex and preparation method thereof, passes through a large amount of silicon and the Yttrium of adulterating（Y）And it is multiple
Close graphene（rGO）, TiO is strengthened using the cooperative effect between three kinds2Every self-cleaning performance of thin-film material, can make light
Through performance does not reduce enhancing living, with good conductive, photo-induced super-hydrophilicity and optical clarity energy.
To achieve the above object, the technical solution adopted by the present invention is：（Si,Y）- codope TiO2/ redox graphite
The high-efficiency self-cleaning film of alkene compound, including following components：
Y contents are TiO2And SiO20.5~1.5at% of total amount；
Si contents are TiO2And SiO2The 30at.% of total amount；
Graphene oxide is TiO2And SiO2The 3wt.% of total amount；
（Si,Y）- codope TiO2The preparation method of the high-efficiency self-cleaning film of/redox graphene complex, including it is following
Step：
1）Raw material butyl titanate, tetraethyl orthosilicate, yttrium nitrate and the GO aqueous solution are added to absolute ethyl alcohol, water, ethylene glycol, third
Precursor solution, absolute ethyl alcohol, water, ethylene glycol, propane diols, levulinic are configured in glycol, acetylacetone,2,4-pentanedione, glycerine mixed solution
Ketone, the volume ratio of glycerine are 4：1：1：3：0.5：1；
Si dopings are TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) mol ratio=0.3；Y dopings are TiO2
And SiO20.5~1.5at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0~0.030, Ti, Si ion concentrations be
0.05mol/l；By this concentration, the addition of raw material is in every 100 ml solution：Butyl titanate 1.702g（For Si doping
Film：Butyl titanate 1.19g, tetraethyl orthosilicate 0.312g）；Six water yttrium nitrate 0.010-0.029g；Graphene oxide is water-soluble
Liquid（1 g/ml）Solution need to be through being sufficiently stirred for 5-30min to homogeneous transparent after 12ml, raw material addition solution.
2）Per 100ml precursor solution in add concentration be 35% 1.0ml concentrated hydrochloric acids, play prevent hydroxide formation and
Redox graphene（GO）Effect；
3）Through being sufficiently stirred for 5-30min to homogeneous transparent；
4）The substrate of plated film is needed to be washed with detergent and EtOH Sonicate, with dip coating or spin coating, 150-200 after applying every timeoC is done
Dry 0.5h, applies 5-15 times, then fires 1.0h for 450 DEG C repeatedly.
The beneficial effects of the invention are as follows：
It is contemplated that passing through a large amount of silicon and the Yttrium of adulterating（Y）And composite graphite alkene（rGO）, between three kinds
Cooperative effect strengthens TiO2Every self-cleaning performance of thin-film material.Specifically include thin film preparation process parameter and optimal Y
Doping and rGO proportionings.(Si, the Y) of exploitation-doping TiO2/ rGO complex thin films have purer TiO2Film, Y doping TiO2
Film,（Si,Y）Codope TiO2Film and TiO2The preferable photocatalysis performance of/rGO complex thin films（Referring to Fig. 1）, preferably
Electric conductivity（Referring to Fig. 2）And hydrophily and photo-induced super-hydrophilicity（Referring to Fig. 3）, close to pure TiO2The light of film is transparent
Performance（Referring to Fig. 4）.
Particularly：Y contents increase to 1.5at% from 0, regardless of whether the photocatalysis of compound rGO films, conductive and hydrophily
Self-cleaning performance strengthens；Y contents have optimal optical clarity energy for 0.5 and 1.0at.%, but during 1.5at.% under optical clarity energy
Drop.RGO quality proportionings increase to 0.03 from 0, regardless of whether the photocatalysis of doping Y films, conductive and hydrophily self-cleaning performance increase
By force, the occasion all required applied to properties, but photopermeability can decline, more than 0.05 every self-cleaning performance enhancing but
Appearance color is more black.Although rGO causes optical clarity to decline, because Si doping is when Y contents are 0.5 and 1.0at.%,
The optical clarity of complex thin film can be still above or equal to pure TiO2Film.
In the precursor solution of film preparation, using absolute ethyl alcohol and a small amount of water as solvent；With concentrated hydrochloric acid（HCl,35%）For oxygen
The reducing agent of graphite alkene；Using the ethylene glycol necessarily matched, propane diols, acetylacetone,2,4-pentanedione and glycerine as dispersant, play simultaneously
Solution viscosity adjusts and kept the scattered effect of the graphene oxide stable and uniform of reduction；Master is prevented by stabilizer of acetylacetone,2,4-pentanedione
Raw material Butyl Phthalate is wanted to hydrolyze.
Firing temperature is too low can not decomposing organic matter completely, too high to cause particle size to increase, properties reduction.Cause
This, 450 DEG C are rational firing temperatures.
Absolute ethyl alcohol, water, ethylene glycol, propane diols, acetylacetone,2,4-pentanedione, the volume ratio of glycerine are 4：1：1：3：0.5：1；This is molten
Liquid is constituted and proportioning can ensure redox graphene dispersed and suspension ~ 20min in precursor solution, it is ensured that film
The uniform stabilization of precursor solution during depositing and drying.
Brief description of the drawings
Fig. 1 for the present invention contain and film without Si and graphene on, photocatalytic degradation（a）Malachite green and（b）Naphthalene
The kinetics constant k1 of the green B aqueous solution of phenol and the graph of a relation of Y mol ratios, k1 is by relational expressionDraw
The slope of curve is provided, wherein, C0With C be before dye solution photocatalysis and photocatalysis t hours after concentration；Fig. 1（a）Urged for light
Change the kinetics constant k1 of the degrading malachite green aqueous solution and the graph of a relation of Y mol ratios；Fig. 1（b）For photocatalytic degradation naphthalene
The kinetics constant k1 of the green B aqueous solution of phenol and the graph of a relation of Y mol ratios.
Fig. 2 for the present invention in contain and the resistivity without Si, rGO film and Y mol ratios graph of a relation.
Fig. 3 is contains and hydrolysis feeler and Y mol ratio of the film without Si, rGO before and after ultraviolet light in the present invention
Graph of a relation.
Fig. 4 for the present invention in contain and the optical spectra figure without Si and rGO and various Y mol ratios films；Wherein Fig. 4
（A) it is light transmission rate spectrogram；Fig. 4（b）For mean transmissivity and the graph of a relation of Y mol ratios.
Embodiment
The present invention is described in further detail with reference to specific embodiments and the drawings.
Embodiment 1
（Si,Y）- codope TiO2The high-efficiency self-cleaning film of/redox graphene complex, graphene is mass ratio, its
He is mol ratio, including following components：
Y contents are TiO2And SiO2The 1.0at% of total amount；
Si contents are TiO2And SiO2The 30at.% of total amount；
Graphene oxide is TiO2And SiO2The 3wt.% of total amount；
Preparing the solvent of the precursor solution of self-cleaning film includes：Absolute ethyl alcohol and water；Also dispersant and stabilizer be：Second
Glycol, propane diols, acetylacetone,2,4-pentanedione and glycerine；Absolute ethyl alcohol, water, ethylene glycol, propane diols, acetylacetone,2,4-pentanedione, the volume of glycerine
Than for 4：1：1：3：0.5:1；Concentration is 35% concentrated hydrochloric acid 1.0vol.%；Ti, Si ion concentration are 0.05mol/l.By this
The addition of raw material is in concentration, every 100ml solution：Butyl titanate 1.19g；Tetraethyl orthosilicate 0.312g；Six water yttrium nitrates
0.020g；Graphene oxide water solution（1 g/ml）12ml, raw material adds solution after solution need to be through being sufficiently stirred for 5-30min to equal
It is even transparent；Apply 10 times repeatedly, 150-200 after applying every timeoC dries 0.5h, then 450 DEG C of firing 1.0h.Preparation method is simple, easy
Row, low cost.
The example films have highest optical clarity energy, photocatalysis, hydrophily and photo-induced super-hydrophilicity, electric conductivity
It is superior to the film without Si and Y.
Embodiment 2
（Si,Y）- codope TiO2The high-efficiency self-cleaning film of/redox graphene complex includes following components：
Y contents are TiO2And SiO2The 0.5at% of total amount；
Si contents are TiO2And SiO2The 30at.% of total amount；
Graphene oxide is TiO2And SiO2The 3wt.% of total amount；
Solvent：Absolute ethyl alcohol and water；
Dispersant and stabilizer are：Ethylene glycol, propane diols, acetylacetone,2,4-pentanedione and glycerine；
Absolute ethyl alcohol, water, ethylene glycol, propane diols, the volume ratio of acetylacetone,2,4-pentanedione and glycerine are 4：1：1：3：0.5:1；
Concentration is 35% concentrated hydrochloric acid 1.0vol.%；
Ti, Si ion concentration are 0.05mol/l.By this concentration, the addition of raw material is in every 100ml solution：The fourth of metatitanic acid four
Ester 1.19g；Tetraethyl orthosilicate 0.312g；Yttrium nitrate 0.010g；Graphene oxide water solution（1 g/ml）12ml, raw material adds molten
Solution need to be through being sufficiently stirred for 5-30min to homogeneous transparent after liquid；
Apply 10 times repeatedly, 150-200 after applying every timeoC dries 0.5h, then 450 DEG C of firing 1.0h.
There is the example films high light catalysis, hydrophily and photo-induced super-hydrophilicity, electric conductivity to be free of stone
All films of black alkene, and with better than TiO2The optical clarity energy of film,
Embodiment 3
（Si,Y）- codope TiO2The high-efficiency self-cleaning film of/redox graphene complex includes following components：
Y contents are TiO2And SiO2The 1.5at% of total amount；
Si contents are TiO2And SiO2The 30at.% of total amount；
Graphene oxide is TiO2And SiO2The 3wt.% of total amount；
Solvent：Absolute ethyl alcohol and water；
Dispersant and stabilizer are：Ethylene glycol, propane diols, acetylacetone,2,4-pentanedione and glycerine；
Absolute ethyl alcohol, water, ethylene glycol, propane diols, the volume ratio of acetylacetone,2,4-pentanedione and glycerine are 4：1：1：3：0.5:1；
Concentration is 35% concentrated hydrochloric acid 1.0vol.%；
Ti, Si ion concentration are 0.05mol/l, by this concentration, and the addition of raw material is in every 100ml solution：The fourth of metatitanic acid four
Ester 1.19g；Tetraethyl orthosilicate 0.312g；Yttrium nitrate 0.029g；Graphene oxide water solution（1g/ml）12 ml, raw material adds molten
Solution need to be through being sufficiently stirred for 5-30min to homogeneous transparent after liquid.
Apply 10 times repeatedly, 150-200 after applying every timeoC dries 0.5h, then 450 DEG C of firing 1.0h.
The example films have best photocatalysis, hydrophily and photo-induced super-hydrophilicity, an electric conductivity, but with compared with
TiO2The low optical clarity energy of film.
Embodiment 4
（Si,Y）- codope TiO2The preparation method of the high-efficiency self-cleaning film of/redox graphene complex, including it is following
Step：
1）Raw material butyl titanate, tetraethyl orthosilicate, yttrium nitrate and the GO aqueous solution are added to absolute ethyl alcohol, water, ethylene glycol, third
Precursor solution, absolute ethyl alcohol, water, ethylene glycol, propane diols, acetyl are configured in glycol, acetylacetone,2,4-pentanedione and glycerine mixed solution
The volume ratio of acetone and glycerine is 4：1：1：3：0.5：1；
Si dopings are TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) mol ratio=0.3；Y dopings are TiO2
And SiO2The 1.0at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0.030, Ti, Si ion concentrations be 0.05mol/l；By this
The addition of raw material is in concentration, every 100ml solution：Butyl titanate 1.19g；Tetraethyl orthosilicate 0.312g；Yttrium nitrate
0.020g；Graphene oxide water solution（1g/ml）12ml；
2）Per 100ml precursor solution in add concentration be 35% 1.0ml concentrated hydrochloric acids, play prevent hydroxide formation and
Redox graphene（GO）Effect；
3）Through being sufficiently stirred for 20min to homogeneous transparent；
4）The substrate of plated film is needed to be washed with detergent and EtOH Sonicate, with dip coating or spin coating, 180 after applying every timeoC is dried
0.5h, applies 10 times, then fires 1.0h for 450 DEG C repeatedly.
The example films have best photocatalysis, hydrophily and photo-induced super-hydrophilicity, electric conductivity and optical clarity
Can, use time is long.
Embodiment 5
（Si,Y）- codope TiO2The preparation method of the high-efficiency self-cleaning film of/redox graphene complex, including it is following
Step：
1）Raw material butyl titanate, tetraethyl orthosilicate, yttrium nitrate and the GO aqueous solution are added to absolute ethyl alcohol, water, ethylene glycol, third
Precursor solution, absolute ethyl alcohol, water, ethylene glycol, propane diols, acetyl are configured in glycol, acetylacetone,2,4-pentanedione and glycerine mixed solution
The volume ratio of acetone and glycerine is 4：1：1：3：0.5：1；
Si dopings are TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) mol ratio=0.3；Y dopings are TiO2
And SiO2The 0.5at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0, Ti, Si ion concentrations be 0.05mol/l；By this concentration,
The addition of raw material is in per 100ml solution：Butyl titanate 1.19g；Tetraethyl orthosilicate 0.312g；Yttrium nitrate 0.010g；
2）Per 100ml precursor solution in add concentration be 35% 1.0ml concentrated hydrochloric acids, play prevent hydroxide formation and
Redox graphene（GO）Effect；
3）Through being sufficiently stirred for 5min to homogeneous transparent；
4）The substrate of plated film is needed to be washed with detergent and EtOH Sonicate, with dip coating or spin coating, 150 after applying every timeoC is dried
0.5h, applies 15 times, then fires 1.0h for 450 DEG C repeatedly.
There is the example films high light catalysis, hydrophily and photo-induced super-hydrophilicity, electric conductivity to be free of stone
All films of black alkene, and with better than TiO2The optical clarity energy of film, use time is long.
Embodiment 6
（Si,Y）- codope TiO2The preparation method of the high-efficiency self-cleaning film of/redox graphene complex, including it is following
Step：
1）Raw material butyl titanate, tetraethyl orthosilicate, yttrium nitrate and the GO aqueous solution are added to absolute ethyl alcohol, water, ethylene glycol, third
Precursor solution, absolute ethyl alcohol, water, ethylene glycol, propane diols, acetyl are configured in glycol, acetylacetone,2,4-pentanedione and glycerine mixed solution
The volume ratio of acetone and glycerine is 4：1：1：3：0.5：1；
Si dopings are TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) mol ratio=0.3；Y dopings are TiO2
And SiO2The 1.5at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0.020, Ti, S ion concentrations be 0.05mol/l；By this
The addition of raw material is in concentration, every 100ml solution：Butyl titanate 1.19g；Tetraethyl orthosilicate 0.312g；Yttrium nitrate
0.029g；Graphene oxide water solution（1 g/ml）12ml；
2）Per 100ml precursor solution in add concentration be 35% 1.0ml concentrated hydrochloric acids, play prevent hydroxide formation and
Redox graphene（GO）Effect；
3）Through being sufficiently stirred for 30min to homogeneous transparent；
4）The substrate of plated film is needed to be washed with detergent and EtOH Sonicate, with dip coating or spin coating, 200 after applying every timeoC is dried
0.5h, applies 5 times, then fires 1.0h for 450 DEG C repeatedly.
The example films have best photocatalysis, hydrophily and photo-induced super-hydrophilicity, electric conductivity, optical clarity energy
Moderate, use time is shorter.
Referring to Fig. 1 for the present invention contain and film without Si and graphene on, photocatalytic degradation（a）Malachite green and
（b）The kinetics constant of the naphthol green B aqueous solutionk 1With the graph of a relation of Y mol ratios.k 1By relational expression（Its
In,C 0WithCIt is before dye solution photocatalysis and photocatalysistConcentration after hour）The slope of curve drawn is provided.Two figures are all
Illustrate that Si doping films have purer TiO2Film has stronger photocatalysis performance, composite graphite alkene（rGO）It is all further with doping Y
Strengthen photocatalysis performance.
Referring to Fig. 2, Fig. 2 for contain in the present invention and the resistivity without Si and rGO films and Y mol ratios graph of a relation.Should
Figure all illustrates that Si doping films have purer TiO2Film has relatively low resistivity, composite graphite alkene（rGO）It is all further with doping Y
Reduce the resistivity of film.
Referring to Fig. 3, Fig. 3 for the present invention in contain and hydrolysis feeler and Y without Si and rGO films before and after ultraviolet light
The graph of a relation of mol ratio.Figure all illustrates that Si doping films have purer TiO2Film has relatively low hydrolysis feeler（I.e. higher is hydrophilic
Property）, composite graphite alkene（rGO）All further reduction hydrolyzes feeler with doping Y（Strengthen hydrophily）.Hydrolyzed after ultraviolet light
Feeler reduces, and illustrates there is photo-induced super-hydrophilicity.Si and Y doping and composite graphite alkene lead to photo-induced super-hydrophilicity
Enhancing.
Referring to Fig. 4, Fig. 4 for the present invention in contain and the optical spectra without Si and rGO and various Y mol ratios films；Its
Middle Fig. 4（A) it is light transmission rate spectrogram；Fig. 4（b）For Fig. 4（a）Mean transmissivity in 200-900nm wave-length coverages rubs with Y
The graph of a relation of your ratio.Fig. 4（A) and（B) explanation Si doping causes light transmission rate to increase, and Y doping causes light transmission rate first to increase Y to contain
The too big light transmission rate of amount reduces again, and graphene causes bare headed rate to reduce, but work as Y contents for 0.5-1.0at.% be still with compared with
TiO2The higher or suitable light transmission rate of film.
Claims (8)
1.（Si,Y）- codope TiO2/ redox graphene complex high-efficiency self-cleaning film, it is characterised in that including following
Component：
Y contents are TiO2And SiO20.5~1.5at% of total amount；
Si contents are TiO2And SiO2The 30at.% of total amount；
Graphene oxide is TiO2And SiO2The 3wt.% of total amount.
2. it is according to claim 1（Si,Y）- codope TiO2The high-efficiency self-cleaning of/redox graphene complex is thin
Film, it is characterised in that including following components：
Y contents are TiO2And SiO2The 1.5at% of total amount；
Si contents are TiO2And SiO2The 30at.% of total amount；
Graphene oxide is TiO2And SiO2The 3wt.% of total amount.
3. it is according to claim 1（Si,Y）- codope TiO2The high-efficiency self-cleaning of/redox graphene complex is thin
Film, including following components：
Y contents are TiO2And SiO2The 0.5at% of total amount；
Si contents are TiO2And SiO2The 30at.% of total amount；
Graphene oxide is TiO2And SiO2The 3wt.% of total amount.
4. it is according to claim 1（Si,Y）- codope TiO2The high-efficiency self-cleaning of/redox graphene complex is thin
Film includes following components：
Y contents are TiO2And SiO2The 1.0at% of total amount；
Si contents are TiO2And SiO2The 30at.% of total amount；
Graphene oxide is TiO2And SiO2The 3wt.% of total amount.
5.（Si,Y）- codope TiO2The preparation method of the high-efficiency self-cleaning film of/redox graphene complex, including with
Lower step：
1）By the GO aqueous solution of raw material butyl titanate, tetraethyl orthosilicate and yttrium nitrate and 1mg/ml add to absolute ethyl alcohol,
Configure precursor solution in water, ethylene glycol, propane diols, acetylacetone,2,4-pentanedione and glycerine mixed solution, absolute ethyl alcohol, water, ethylene glycol,
The volume ratio of propane diols, acetylacetone,2,4-pentanedione and glycerine is 4：1：1：3：0.5：1；
Si dopings are TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) mol ratio=0.3；Y dopings are TiO2
And SiO20.5~1.5at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0~0.030, Ti, Si ion concentrations be
0.05mol/l；By this concentration, the addition of raw material is in every 100ml solution：Butyl titanate 1.702g, adulterates thin for Si
Film：Butyl titanate 1.19 g, tetraethyl orthosilicate 0.312g；Six water yttrium nitrate 0.010-0.029g；1g/ml graphene oxide
Aqueous solution 12ml；Solution need to be through being sufficiently stirred for 5-30min to homogeneous transparent after raw material addition solution；
2）The 1.0ml concentrated hydrochloric acids that concentration is 35% are added in precursor solution per 100ml；
3）By 20:1 volume ratio is toward adding acetylacetone,2,4-pentanedione in precursor solution；
4）Through being sufficiently stirred for 5-30min to homogeneous transparent；
5）The substrate of plated film is needed to be washed with detergent and EtOH Sonicate, with dip coating or spin coating, 150-200 after applying every timeoC is done
Dry 0.5h, applies 5-15 times, then fires 1.0h for 450 DEG C repeatedly.
6. it is according to claim 5（Si,Y）- codope TiO2The high-efficiency self-cleaning of/redox graphene complex is thin
The preparation method of film, comprises the following steps：
1）By the GO aqueous solution of raw material butyl titanate, tetraethyl orthosilicate and yttrium nitrate and 1mg/ml add to absolute ethyl alcohol,
Configure precursor solution in water, ethylene glycol, propane diols, acetylacetone,2,4-pentanedione and glycerine mixed solution, absolute ethyl alcohol, water, ethylene glycol,
The volume ratio of propane diols, acetylacetone,2,4-pentanedione and glycerine is 4：1：1：3：1；
Si dopings are TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) mol ratio=0.3；Y dopings are TiO2
And SiO2The 1.0at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0.030, Ti, Si ion concentrations be 0.05mol/l；By this
The addition of raw material is in concentration, every 100ml solution：Butyl titanate 1.19g；Tetraethyl orthosilicate 0.312g；Six water yttrium nitrates
0.020g；1g/ml graphene oxide water solution 12ml, raw material adds solution after solution need to be through being sufficiently stirred for 5-30min to equal
It is even transparent；
2）The 1.0ml concentrated hydrochloric acids that concentration is 35% are added in precursor solution per 100ml；
3）By 20:1 volume ratio is toward adding acetylacetone,2,4-pentanedione in precursor solution；
4）Through being sufficiently stirred for 20min to homogeneous transparent；
5）The substrate of plated film is needed to be washed with detergent and EtOH Sonicate, with dip coating or spin coating, 180 after applying every timeoC is dried
0.5h, applies 10 times, then fires 1.0h for 450 DEG C repeatedly.
7. it is according to claim 5（Si,Y）- codope TiO2The high-efficiency self-cleaning of/redox graphene complex is thin
The preparation method of film, comprises the following steps：
1）By the GO aqueous solution of raw material butyl titanate, tetraethyl orthosilicate and yttrium nitrate and 1mg/ml add to absolute ethyl alcohol, water,
Precursor solution, absolute ethyl alcohol, water, ethylene glycol, third are configured in ethylene glycol, propane diols, acetylacetone,2,4-pentanedione and glycerine mixed solution
The volume ratio of glycol, acetylacetone,2,4-pentanedione and glycerine is 4：1：1：3：1；
Si dopings are TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) mol ratio=0.3；Y dopings are TiO2
And SiO2The 0.5at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0, Ti, Si ion concentrations be 0.05mol/l；By this concentration,
The addition of raw material is in per 100ml solution：Butyl titanate 1.19g；Tetraethyl orthosilicate 0.312g；Six water yttrium nitrates 0.010
g；
2）The 1.0ml concentrated hydrochloric acids that concentration is 35% are added in precursor solution per 100ml；
3）By 20:1 volume ratio is toward adding acetylacetone,2,4-pentanedione in precursor solution；
4）Through being sufficiently stirred for 5min to homogeneous transparent；
5）The substrate of plated film is needed to be washed with detergent and EtOH Sonicate, with dip coating or spin coating, 150 after applying every timeoC is dried
0.5h, applies 15 times, then fires 1.0h for 450 DEG C repeatedly.
8. it is according to claim 5（Si,Y）- codope TiO2The high-efficiency self-cleaning of/redox graphene complex is thin
The preparation method of film, comprises the following steps：
1）By the GO aqueous solution of raw material butyl titanate, tetraethyl orthosilicate and yttrium nitrate and 1mg/ml add to absolute ethyl alcohol,
Configure precursor solution in water, ethylene glycol, propane diols, acetylacetone,2,4-pentanedione and glycerine mixed solution, absolute ethyl alcohol, water, ethylene glycol,
The volume ratio of propane diols, acetylacetone,2,4-pentanedione and glycerine is 4：1：1：3：1；
Si dopings are TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) mol ratio=0.3；Y dopings are TiO2
And SiO2The 1.5at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0.030, Ti, Si ion concentrations be 0.05mol/l；By this
The addition of raw material is in concentration, every 100 ml solution：Butyl titanate 1.19g；Tetraethyl orthosilicate 0.312g；Six water yttrium nitrates
0.029g；1g/ml graphene oxide water solution 12ml；
2）The 1.0ml concentrated hydrochloric acids that concentration is 35% are added in precursor solution per 100ml；
3）By 20:1 volume ratio is toward adding acetylacetone,2,4-pentanedione in precursor solution；
4）Through being sufficiently stirred for 30min to homogeneous transparent；
5）The substrate of plated film is needed to be washed with detergent and EtOH Sonicate, with dip coating or spin coating, 200 after applying every timeoC is dried
0.5h, applies 5 times, then fires 1.0h for 450 DEG C repeatedly.
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|---|---|---|---|---|
| CN102631910A (en) * | 2012-03-20 | 2012-08-15 | 中国海洋石油总公司 | Stable graphene/titanium oxide composite nanosol and preparation method thereof |
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| CN102631910A (en) * | 2012-03-20 | 2012-08-15 | 中国海洋石油总公司 | Stable graphene/titanium oxide composite nanosol and preparation method thereof |
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| 张金玲: "超亲水性纳米TiO2复合薄膜的制备", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
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| CN111589439A (en) * | 2020-06-02 | 2020-08-28 | 陕西科技大学 | Si and Mo co-doped TiO2Efficient self-cleaning film of/redox graphene compound and preparation method thereof |
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