CN106944034B - (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
- Publication number
- CN106944034B CN106944034B CN201710271376.XA CN201710271376A CN106944034B CN 106944034 B CN106944034 B CN 106944034B CN 201710271376 A CN201710271376 A CN 201710271376A CN 106944034 B CN106944034 B CN 106944034B
- Authority
- CN
- China
- Prior art keywords
- tio
- sio
- solution
- film
- total amount
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 49
- 229910052710 silicon Inorganic materials 0.000 title claims abstract description 35
- 238000004140 cleaning Methods 0.000 title claims abstract description 33
- 229910052727 yttrium Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 111
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 108
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 82
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 60
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 60
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 60
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 60
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 60
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000000243 solution Substances 0.000 claims abstract description 57
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 46
- 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 33
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002994 raw material Substances 0.000 claims abstract description 25
- 229960000935 dehydrated alcohol Drugs 0.000 claims abstract description 23
- 235000011187 glycerol Nutrition 0.000 claims abstract description 23
- 239000002243 precursor Substances 0.000 claims abstract description 23
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-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 17
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000010304 firing Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 12
- 239000003599 detergent Substances 0.000 claims abstract description 8
- 238000003618 dip coating Methods 0.000 claims abstract description 8
- 239000011259 mixed solution Substances 0.000 claims abstract description 8
- 238000004528 spin coating Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 8
- 239000010408 film Substances 0.000 claims description 72
- -1 graphene compound Chemical class 0.000 claims description 14
- 150000002500 ions Chemical class 0.000 claims description 13
- 239000010409 thin film Substances 0.000 claims description 10
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 3
- 150000002148 esters Chemical class 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 21
- 238000007146 photocatalysis Methods 0.000 abstract description 21
- 239000000203 mixture Substances 0.000 abstract description 2
- 230000003287 optical effect Effects 0.000 description 16
- 230000010148 water-pollination Effects 0.000 description 10
- 230000002708 enhancing effect Effects 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 9
- 239000010439 graphite Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000002131 composite material Substances 0.000 description 7
- 230000005540 biological transmission Effects 0.000 description 6
- 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
- 239000002270 dispersing agent Substances 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 238000006460 hydrolysis reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- 230000007423 decrease Effects 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
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 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
- 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
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- DCKVNWZUADLDEH-UHFFFAOYSA-N sec-butyl acetate Chemical compound CCC(C)OC(C)=O DCKVNWZUADLDEH-UHFFFAOYSA-N 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
- 230000002195 synergetic effect Effects 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
- 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
- 230000008021 deposition Effects 0.000 description 1
- 229960002380 dibutyl phthalate Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000034 method Methods 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
- 238000010422 painting Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 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
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- 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 content is TiO2And SiO20.5~1.5at% of total amount；Si content is TiO2And SiO2The 30at.% of total amount；Graphene oxide (GO) is TiO2And SiO2The 3wt.% of total amount；The composition film has purer TiO2The significant good conductive of film, photo-induced super-hydrophilicity, light is transparent and the self-cleaning performances performance such as photocatalysis；The doping of the Si and Y of appropriate amount can keep and increase the transparent performance of film.The step of preparing film are as follows: 1) raw material butyl titanate, ethyl orthosilicate, yttrium nitrate and GO aqueous solution are added and configure precursor solution into dehydrated alcohol, water, ethylene glycol, propylene glycol, acetylacetone,2,4-pentanedione and glycerine mixed solution；2) the 1.0ml concentrated hydrochloric acid that concentration is 35% is added in the precursor solution of every 100ml；3) it is stirred until homogeneous transparent；4) substrate of plated film is needed to be washed with detergent and EtOH Sonicate；5) dip coating or spin coating is used, it is dry after applying every time；6) 450 DEG C of firings；Preparation method is simple, easy, at 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 multiple
Close the high-efficiency self-cleaning film and preparation method thereof of object.
Background technique
Automatically cleaning is a critically important depollution of environment technology.Usually the film with self-cleaning performance is applied and is carried out in interior
The pollutant of film surface is played to the pernicious gas in environment and is attached on the surfaces such as External building object, electric appliance and Medical Devices
Photocatalysis Decomposition, sterilizing and reduce pollutant degree of adhesion effect, thus the effects of playing environment purification.Therefore, the world
There are extensive research and application in various countries to self-cleaning film.TiO2Film is due to preferable photocatalysis and steady in the environment
The performances such as fixed are currently used self-cleaning films.
TiO2Film is since the performances such as stable are that currently used automatically cleaning is thin with preferable photocatalysis and in the environment
Film.Self-cleaning film is usually required that (pollutant of resolving harmful gas and attachment and to go out with good photocatalysis performance
Bacterium), good electric conductivity (Electrostatic Absorption for preventing pollutant), photo-induced super-hydrophilicity can (so that some pollutants is not easy attached
And proposed absorption water clean the surface) and 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.Again by ion doping or/and with graphene (rGO)
Close enhancing TiO2The photocatalysis performance of powder body material has extensive research and application, and usually has more significant effect.But from
Son doping or/and it is compound to TiO with graphene (rGO)2The developmental research of film photocatalytic material is seldom.Usual some ions are mixed
Miscellaneous and composite graphite alkene, which will lead to optical clarity, to be reduced, and research shows that TiO can be enhanced in a large amount of Si doping2The light of material
It is transparent while enhancing photocatalysis performance.Therefore, it while composite graphite alkene, selects some ions (such as Y) to adulterate and adulterates Si,
Can enable photopermeability not reduces enhancing living.But lacks Si- at present and adulterate TiO2The exploitation of/rGO complex thin film, more lacks tool
There is (Si, Y)-codope TiO of good conductive, photo-induced super-hydrophilicity and optical clarity energy2/ graphene complex film is opened
Hair.
Summary of the invention
For the above-mentioned the deficiencies in the prior art of customer service, the object of the present invention is to provide (Si, Y)-codope TiO2/ redox
High-efficiency self-cleaning film of graphene complex and preparation method thereof, by a large amount of silicon of doping and Yttrium (Y) and again
It closes graphene (rGO), enhances TiO using the synergistic effect between three kinds2Every self-cleaning performance of thin-film material, can make light
Through performance does not reduce enhancing living, has good conductive, photo-induced super-hydrophilicity and optical clarity energy.
To achieve the above object, the technical solution adopted by the present invention is that: (Si, Y)-codope TiO2/ redox graphite
The high-efficiency self-cleaning film of alkene compound, including following components:
Y content is TiO2And SiO20.5~1.5at% of total amount；
Si content is 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
Following steps:
1) raw material butyl titanate, ethyl orthosilicate, yttrium nitrate and GO aqueous solution are added to dehydrated alcohol, water, second two
Alcohol, acetylacetone,2,4-pentanedione, configures precursor solution in glycerine mixed solution at propylene glycol, dehydrated alcohol, water, ethylene glycol, propylene glycol,
Acetylacetone,2,4-pentanedione, glycerine volume ratio be 4:1:1:3:0.5:1；
Si doping is TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) molar ratio=0.3；Y doping is
TiO2And SiO20.5~1.5at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0~0.030, Ti, Si ion concentration be
0.05mol/l；By this concentration, the additional amount of raw material in every 100 ml solution are as follows: butyl titanate 1.702g (adulterates Si
Film: butyl titanate 1.19g, ethyl orthosilicate 0.312g)；Yttrium nitrate hexahydrate 0.010-0.029g；Graphene oxide is water-soluble
Liquid (1 g/ml) 12ml, 5-30min need to be sufficiently stirred to homogeneous transparent in solution after solution is added in raw material.
2) the 1.0ml concentrated hydrochloric acid that concentration is 35% is added in the precursor solution of every 100ml, playing prevents hydroxide shape
At the effect with redox graphene (GO)；
3) through 5-30min is sufficiently stirred to homogeneous transparent；
4) substrate of plated film is needed to be washed with detergent and EtOH Sonicate, with dip coating or spin coating, 150- after applying every time
200oC dries 0.5h, repeatedly painting 5-15 times, then 450 DEG C of firing 1.0h.
The beneficial effects of the present invention are:
The present invention is directed to by adulterating a large amount of silicon and Yttrium (Y) and composite graphite alkene (rGO), using three kinds it
Between synergistic effect enhance TiO2Every self-cleaning performance of thin-film material.Specifically include thin film preparation process parameter and optimal
Y doping and rGO proportion.(Si, the Y)-of exploitation adulterates TiO2/ rGO complex thin film has purer TiO2Film, Y doping
TiO2Film, (Si, Y) codope TiO2Film and TiO2The preferable photocatalysis performance of/rGO complex thin film (referring to Fig. 1), compared with
Good electric conductivity (referring to fig. 2) and hydrophily and photo-induced super-hydrophilicity (referring to Fig. 3), close to pure TiO2The light of film
Transparent performance (referring to fig. 4).
Particularly: Y content increases to 1.5at% from 0, regardless of whether photocatalysis, conduction and the hydrophily of compound rGO film
Self-cleaning performance enhancing；Y content has optimal optical clarity energy for 0.5 and 1.0at.%, but when 1.5at.% under optical clarity energy
Drop.RGO quality proportioning increases to 0.03 from 0, regardless of whether photocatalysis, conduction and the hydrophily self-cleaning performance of doping Y film 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 that can decline, since the doping of Si is when Y content is 0.5 and 1.0at.%,
The optical clarity of complex thin film can be still greater than or be equal to pure TiO2Film.
In the precursor solution of film preparation, using dehydrated alcohol and a small amount of water as solvent；With concentrated hydrochloric acid (HCl, 35%) for oxygen
The reducing agent of graphite alkene；Using ethylene glycol, propylene glycol, acetylacetone,2,4-pentanedione and the glycerine centainly matched as dispersing agent, play simultaneously
Solution viscosity adjusts and keeps the effect of the graphene oxide stable and uniform dispersion of reduction；It prevents from leading using acetylacetone,2,4-pentanedione as stabilizer
Raw material Butyl Phthalate is wanted to hydrolyze.
Firing temperature too it is low cannot complete decomposing organic matter, it is too high that particle size is caused to increase, properties reduce.Cause
This, 450 DEG C are reasonable firing temperatures.
Dehydrated alcohol, water, ethylene glycol, propylene glycol, acetylacetone,2,4-pentanedione, glycerine volume ratio be 4:1:1:3:0.5:1；This is molten
Liquid composition and proportion can guarantee redox graphene evenly dispersed and suspension ~ 20min in precursor solution, guarantee film
The uniform stabilization of precursor solution during deposition and drying.
Detailed description of the invention
Fig. 1 be 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 relational graph of Y molar ratio, k1 is by relational expressionIt obtains
The slope of curve provides, wherein C0With the concentration that C is before dye solution photocatalysis and after photocatalysis t hours；Fig. 1 (a) urges for light
Change the kinetics constant k1 of degrading malachite green aqueous solution and the relational graph of Y molar ratio；Fig. 1 (b) is photocatalytic degradation naphthalene
The kinetics constant k1 of the green B aqueous solution of phenol and the relational graph of Y molar ratio.
Fig. 2 is to contain and the relational graph of the resistivity without Si, rGO film and Y molar ratio in the present invention.
Fig. 3 is to contain in the present invention and hydrolysis feeler and Y molar ratio of the film without Si, rGO before and after ultraviolet light
Relational graph.
Fig. 4 is to contain and the optical spectra figure without Si and rGO and various Y molar ratio films in the present invention；Wherein Fig. 4
It (a) is light transmission rate spectrogram；Fig. 4 (b) is the relational graph of mean transmissivity and Y molar ratio.
Specific embodiment
Invention is further described in detail with attached drawing combined with specific embodiments below.
Embodiment 1
(Si, Y)-codope TiO2The high-efficiency self-cleaning film of/redox graphene complex, graphene are quality
Than other are molar ratio, including following components:
Y content is TiO2And SiO2The 1.0at% of total amount；
Si content is TiO2And SiO2The 30at.% of total amount；
Graphene oxide is TiO2And SiO2The 3wt.% of total amount；
The solvent for preparing the precursor solution of self-cleaning film includes: dehydrated alcohol and water；There are also dispersing agents and stabilizer
Are as follows: ethylene glycol, propylene glycol, acetylacetone,2,4-pentanedione and glycerine；Dehydrated alcohol, water, ethylene glycol, propylene glycol, acetylacetone,2,4-pentanedione, glycerine
Volume ratio is 4:1:1:3:0.5:1；The concentrated hydrochloric acid 1.0vol.% that concentration is 35%；The ion concentration of Ti, Si are 0.05mol/l.
By this concentration, the additional amount of raw material in every 100ml solution are as follows: butyl titanate 1.19g；Ethyl orthosilicate 0.312g；Six water nitre
Sour yttrium 0.020g；Graphene oxide water solution (1 g/ml) 12ml, solution need to be through being sufficiently stirred 5-30min after solution is added in raw material
To homogeneous transparent；It applies 10 times repeatedly, 150-200 after applying every timeoC dries 0.5h, then 450 DEG C of firing 1.0h.Preparation method letter
It is single, easy, at 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 content is TiO2And SiO2The 0.5at% of total amount；
Si content is TiO2And SiO2The 30at.% of total amount；
Graphene oxide is TiO2And SiO2The 3wt.% of total amount；
Solvent: dehydrated alcohol and water；
Dispersing agent and stabilizer are as follows: ethylene glycol, propylene glycol, acetylacetone,2,4-pentanedione and glycerine；
Dehydrated alcohol, water, ethylene glycol, propylene glycol, the volume ratio of acetylacetone,2,4-pentanedione and glycerine are 4:1:1:3:0.5:1；
The concentrated hydrochloric acid 1.0vol.% that concentration is 35%；
The ion concentration of Ti, Si are 0.05mol/l.By this concentration, the additional amount of raw material in every 100ml solution are as follows: metatitanic acid
Four butyl ester 1.19g；Ethyl orthosilicate 0.312g；Yttrium nitrate 0.010g；Graphene oxide water solution (1 g/ml) 12ml, raw material add
5-30min need to be sufficiently stirred to homogeneous transparent in solution after entering solution；
It applies 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 have and be 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 content is TiO2And SiO2The 1.5at% of total amount；
Si content is TiO2And SiO2The 30at.% of total amount；
Graphene oxide is TiO2And SiO2The 3wt.% of total amount；
Solvent: dehydrated alcohol and water；
Dispersing agent and stabilizer are as follows: ethylene glycol, propylene glycol, acetylacetone,2,4-pentanedione and glycerine；
Dehydrated alcohol, water, ethylene glycol, propylene glycol, the volume ratio of acetylacetone,2,4-pentanedione and glycerine are 4:1:1:3:0.5:1；
The concentrated hydrochloric acid 1.0vol.% that concentration is 35%；
The ion concentration of Ti, Si are 0.05mol/l, by this concentration, the additional amount of raw material in every 100ml solution are as follows: metatitanic acid
Four butyl ester 1.19g；Ethyl orthosilicate 0.312g；Yttrium nitrate 0.029g；12 ml of graphene oxide water solution (1g/ml), raw material add
5-30min need to be sufficiently stirred to homogeneous transparent in solution after entering solution.
It applies 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, electric conductivity, but have 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
Following steps:
1) raw material butyl titanate, ethyl orthosilicate, yttrium nitrate and GO aqueous solution are added to dehydrated alcohol, water, second two
Configure precursor solution in alcohol, propylene glycol, acetylacetone,2,4-pentanedione and glycerine mixed solution, dehydrated alcohol, water, ethylene glycol, propylene glycol,
The volume ratio of acetylacetone,2,4-pentanedione and glycerine is 4:1:1:3:0.5:1；
Si doping is TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) molar ratio=0.3；Y doping is
TiO2And SiO2The 1.0at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0.030, Ti, Si ion concentration be 0.05mol/l；
By this concentration, the additional amount of raw material in every 100ml solution are as follows: butyl titanate 1.19g；Ethyl orthosilicate 0.312g；Yttrium nitrate
0.020g；Graphene oxide water solution (1g/ml) 12ml；
2) the 1.0ml concentrated hydrochloric acid that concentration is 35% is added in the precursor solution of every 100ml, playing prevents hydroxide shape
At the effect with redox graphene (GO)；
3) through 20min is sufficiently stirred to homogeneous transparent；
4) 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 dry
Dry 0.5h is applied 10 times, then 450 DEG C of firing 1.0h repeatedly.
The example films have best photocatalysis, hydrophily and photo-induced super-hydrophilicity, electric conductivity and optical clarity
Can, it is long using the time.
Embodiment 5
(Si, Y)-codope TiO2The preparation method of the high-efficiency self-cleaning film of/redox graphene complex, including
Following steps:
1) raw material butyl titanate, ethyl orthosilicate, yttrium nitrate and GO aqueous solution are added to dehydrated alcohol, water, second two
Configure precursor solution in alcohol, propylene glycol, acetylacetone,2,4-pentanedione and glycerine mixed solution, dehydrated alcohol, water, ethylene glycol, propylene glycol,
The volume ratio of acetylacetone,2,4-pentanedione and glycerine is 4:1:1:3:0.5:1；
Si doping is TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) molar ratio=0.3；Y doping is
TiO2And SiO2The 0.5at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0, Ti, Si ion concentration be 0.05mol/l；By this
Concentration, the additional amount of raw material in every 100ml solution are as follows: butyl titanate 1.19g；Ethyl orthosilicate 0.312g；Yttrium nitrate
0.010g；
2) the 1.0ml concentrated hydrochloric acid that concentration is 35% is added in the precursor solution of every 100ml, playing prevents hydroxide shape
At the effect with redox graphene (GO)；
3) through 5min is sufficiently stirred to homogeneous transparent；
4) 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 dry
Dry 0.5h is applied 15 times, then 450 DEG C of firing 1.0h 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 have and be better than TiO2The optical clarity energy of film, it is long using the time.
Embodiment 6
(Si, Y)-codope TiO2The preparation method of the high-efficiency self-cleaning film of/redox graphene complex, including
Following steps:
1) raw material butyl titanate, ethyl orthosilicate, yttrium nitrate and GO aqueous solution are added to dehydrated alcohol, water, second two
Configure precursor solution in alcohol, propylene glycol, acetylacetone,2,4-pentanedione and glycerine mixed solution, dehydrated alcohol, water, ethylene glycol, propylene glycol,
The volume ratio of acetylacetone,2,4-pentanedione and glycerine is 4:1:1:3:0.5:1；
Si doping is TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) molar ratio=0.3；Y doping is
TiO2And SiO2The 1.5at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0.020, Ti, S ion concentration be 0.05mol/l；
By this concentration, the additional amount of raw material in every 100ml solution are as follows: butyl titanate 1.19g；Ethyl orthosilicate 0.312g；Yttrium nitrate
0.029g；Graphene oxide water solution (1 g/ml) 12ml；
2) the 1.0ml concentrated hydrochloric acid that concentration is 35% is added in the precursor solution of every 100ml, playing prevents hydroxide shape
At the effect with redox graphene (GO)；
3) through 30min is sufficiently stirred to homogeneous transparent；
4) 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 dry
Dry 0.5h is applied 5 times, then 450 DEG C of firing 1.0h repeatedly.
The example films have best photocatalysis, hydrophily and photo-induced super-hydrophilicity, electric conductivity, optical clarity energy
It is moderate, it is shorter using the time.
Referring to Fig. 1 be the present invention contain and film without Si and graphene on, photocatalytic degradation (a) malachite green
(b) the kinetics constant of naphthol green B aqueous solutionk 1With the relational graph of Y molar ratio.k 1By relational expression
(wherein,C 0WithCIt is before dye solution photocatalysis and photocatalysistConcentration after hour) slope of curve that obtains provides.Two figures
All illustrate that Si doping film has purer TiO2Film has stronger photocatalysis performance, and composite graphite alkene (rGO) and doping Y are into one
Step enhancing photocatalysis performance.
Referring to fig. 2, Fig. 2 is to contain and the relational graph of the resistivity without Si and rGO film and Y molar ratio in the present invention.It should
Figure all illustrates that Si doping film has purer TiO2Film has lower resistivity, and composite graphite alkene (rGO) and doping Y are further
Reduce the resistivity of film.
Referring to Fig. 3, Fig. 3 is to contain and hydrolysis feeler and Y without Si and rGO film before and after ultraviolet light in the present invention
The relational graph of molar ratio.Figure all illustrates that Si doping film has purer TiO2Film has lower hydrolysis feeler (i.e. higher hydrophilic
Property), composite graphite alkene (rGO) and doping Y further decrease hydrolysis feeler (i.e. enhancing hydrophily).It is hydrolyzed after ultraviolet light
Feeler reduces, and illustrates that there are photo-induced super-hydrophilicities.Si and Y doping and composite graphite alkene lead to photo-induced super-hydrophilicity
Enhancing.
Referring to fig. 4, Fig. 4 is to contain and the optical spectra without Si and rGO and various Y molar ratio films in the present invention；Its
Middle Fig. 4 (a) is light transmission rate spectrogram；Fig. 4 (b) is that mean transmissivity of the Fig. 4 (a) in 200-900nm wave-length coverage rubs with Y
The relational graph of your ratio.Fig. 4 (a) and (b) illustrate that Si doping causes light transmission rate to increase, and Y doping causes light transmission rate first to increase Y to contain
Too big light transmission rate is measured to reduce again, graphene causes bare headed rate to reduce, but when Y content for 0.5-1.0at.% be still with compared with
TiO2Film is higher or comparable light transmission rate.
Claims (6)
1.(Si, Y)-codope TiO2/ redox graphene compound high-efficiency self-cleaning film, it is characterised in that including following
Component:
Y content is TiO2And SiO20.5~1.0 at% of total amount；
Si content is TiO2And SiO2The 30at.% of total amount；
Redox graphene is TiO2And SiO2The 3wt.% of total amount.
2. (Si, Y)-codope TiO according to claim 12The high-efficiency self-cleaning of/redox graphene compound is thin
Film, which is characterized in that including following components:
Y content is TiO2And SiO2The 0.5at% of total amount；
Si content is TiO2And SiO2The 30at.% of total amount；
Redox graphene is TiO2And SiO2The 3wt.% of total amount.
3. (Si, Y)-codope TiO according to claim 12The high-efficiency self-cleaning of/redox graphene compound is thin
Film, which is characterized in that including following components:
Y content is TiO2And SiO2The 1.0at% of total amount；
Si content is TiO2And SiO2The 30at.% of total amount；
Redox graphene is TiO2And SiO2The 3wt.% of total amount.
4.(Si, Y)-codope TiO2The preparation method of the high-efficiency self-cleaning film of/redox graphene compound, feature
It is, comprising the following steps:
1) by the GO aqueous solution of raw material butyl titanate, ethyl orthosilicate and yttrium nitrate and 1mg/ml be added to dehydrated alcohol,
Configure precursor solution in water, ethylene glycol, propylene glycol, acetylacetone,2,4-pentanedione and glycerine mixed solution, dehydrated alcohol, water, ethylene glycol,
The volume ratio of propylene glycol, acetylacetone,2,4-pentanedione and glycerine is 4:1:1:3:0.5:1；
Si doping is TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) molar ratio=0.3；Y doping is TiO2
And SiO20.5~1.5at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0~0.030, rGO/ (TiO2+SiO2) mass ratio is not
Including 0, Ti, Si ion concentration are 0.05mol/l；By this concentration, the additional amount of raw material in every 100ml solution are as follows: four fourth of metatitanic acid
Ester 1.702g, for Si doping film: butyl titanate 1.19 g, ethyl orthosilicate 0.312g；Yttrium nitrate hexahydrate 0.010-
0.029g；The graphene oxide water solution 12ml of 1g/ml；5-30min need to be sufficiently stirred to equal in solution after solution is added in raw material
It is even transparent；
2) the 1.0ml concentrated hydrochloric acid that concentration is 35% is added in the precursor solution of every 100ml；
3) acetylacetone,2,4-pentanedione is added into precursor solution by the volume ratio of 20:1；
4) through 5-30min is sufficiently stirred to homogeneous transparent；
5) 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 dry
Dry 0.5h is applied 5-15 times, then 450 DEG C of firing 1.0h repeatedly.
5. (Si, Y)-codope TiO according to claim 42The high-efficiency self-cleaning of/redox graphene complex is thin
The preparation method of film, comprising the following steps:
1) by the GO aqueous solution of raw material butyl titanate, ethyl orthosilicate and yttrium nitrate and 1mg/ml be added to dehydrated alcohol,
Configure precursor solution in water, ethylene glycol, propylene glycol, acetylacetone,2,4-pentanedione and glycerine mixed solution, dehydrated alcohol, water, ethylene glycol,
The volume ratio of propylene glycol, acetylacetone,2,4-pentanedione and glycerine is 4:1:1:3:0.5:1；
Si doping is TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) molar ratio=0.3；Y doping is TiO2
And SiO2The 1.0at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0.030, Ti, Si ion concentration be 0.05mol/l；By this
Concentration, the additional amount of raw material in every 100ml solution are as follows: butyl titanate 1.19g；Ethyl orthosilicate 0.312g；Yttrium nitrate hexahydrate
0.020g；The graphene oxide water solution 12ml of 1g/ml, 5-30min need to be sufficiently stirred to equal in solution after solution is added in raw material
It is even transparent；
2) the 1.0ml concentrated hydrochloric acid that concentration is 35% is added in the precursor solution of every 100ml；
3) acetylacetone,2,4-pentanedione is added into precursor solution by the volume ratio of 20:1；
4) through 20min is sufficiently stirred to homogeneous transparent；
5) 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 dry
0.5h is applied 10 times, then 450 DEG C of firing 1.0h repeatedly.
6. (Si, Y)-codope TiO according to claim 42The high-efficiency self-cleaning of/redox graphene compound is thin
The preparation method of film, comprising the following steps:
1) by the GO aqueous solution of raw material butyl titanate, ethyl orthosilicate and yttrium nitrate and 1mg/ml be added to dehydrated alcohol,
Configure precursor solution in water, ethylene glycol, propylene glycol, acetylacetone,2,4-pentanedione and glycerine mixed solution, dehydrated alcohol, water, ethylene glycol,
The volume ratio of propylene glycol, acetylacetone,2,4-pentanedione and glycerine is 4:1:1:3:0.5:1；
Si doping is TiO2And SiO2The 30at.% of total amount, i.e. SiO2/(TiO2+SiO2) molar ratio=0.3；Y doping is TiO2
And SiO2The 1.5at.% of total amount, rGO/ (TiO2+SiO2) mass ratio=0.030, Ti, Si ion concentration be 0.05mol/l；By this
Concentration, the additional amount of raw material in every 100 ml solution are as follows: butyl titanate 1.19g；Ethyl orthosilicate 0.312g；Yttrium nitrate hexahydrate
0.029g；The graphene oxide water solution 12ml of 1g/ml；
2) the 1.0ml concentrated hydrochloric acid that concentration is 35% is added in the precursor solution of every 100ml；
3) acetylacetone,2,4-pentanedione is added into precursor solution by the volume ratio of 20:1；
4) through 30min is sufficiently stirred to homogeneous transparent；
5) 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 dry
0.5h is applied 5 times, then 450 DEG C of firing 1.0h repeatedly.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710271376.XA CN106944034B (en) | 2017-04-24 | 2017-04-24 | (Si, Y)-codope TiO2The high-efficiency self-cleaning film and preparation method of/redox graphene complex |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710271376.XA CN106944034B (en) | 2017-04-24 | 2017-04-24 | (Si, Y)-codope TiO2The high-efficiency self-cleaning film and preparation method of/redox graphene complex |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106944034A CN106944034A (en) | 2017-07-14 |
| CN106944034B true CN106944034B (en) | 2019-09-24 |
Family
ID=59476600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710271376.XA Active CN106944034B (en) | 2017-04-24 | 2017-04-24 | (Si, Y)-codope TiO2The high-efficiency self-cleaning film and preparation method of/redox graphene complex |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106944034B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
-
2017
- 2017-04-24 CN CN201710271376.XA patent/CN106944034B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| 超亲水性纳米TiO2复合薄膜的制备;张金玲;《中国优秀硕士学位论文全文数据库 工程科技I辑》;20081115(第11期);第B020-213页 * |
| 钇离子掺杂对二氧化钛纳米薄膜光诱导超亲水性能的影响及其机理;曾人杰等;《无机化学学报》;20030731;第19卷(第7期);第678-684页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106944034A (en) | 2017-07-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5784481B2 (en) | Coating composition and use thereof | |
| CN101333075B (en) | Method for preparing self-cleaning toughened glass | |
| CN103102791B (en) | Preparation method of nano TiO2 self-cleaning transparent coating | |
| CN110183880B (en) | Photocatalytic super-amphiphobic coating and preparation method and application thereof | |
| CN101525504A (en) | Photocatalytic self-cleaning film coating agent with self-layered isolation effect and preparation method thereof | |
| CN104085165B (en) | A kind of preparation method of photocatalyst of titanium dioxide coating | |
| CN107141992A (en) | A kind of super-hydrophobic transparent coating liquid and preparation method thereof | |
| CN104745052B (en) | A kind of preparation method of the Nano self-cleaning coating material of high adhesion force | |
| JP6266230B2 (en) | Surface-modified metal oxide fine particles, coating liquid for thin film formation, substrate with thin film, photoelectric cell, and method for producing surface-modified metal oxide fine particles | |
| CN104261695A (en) | Preparation method of transparent super-hydrophobic zinc oxide coating | |
| CN101570401B (en) | Method for preparing self-cleaning glass | |
| Lv et al. | Robust, infrared-reflective, superhydrophobic and breathable coatings on polyester fabrics | |
| CN104692671A (en) | Preparation method of super-hydrophobic self-cleaning glass based on ZnO nano array coating | |
| CN103922802A (en) | Antireflection type super-hydrophilic zinc oxide/titanium dioxide composite nanometer structure self-cleaning coating and preparation method thereof | |
| JP3755852B2 (en) | Coating liquid for forming transparent film having photocatalytic activity and substrate with transparent film | |
| CN106944034B (en) | (Si, Y)-codope TiO2The high-efficiency self-cleaning film and preparation method of/redox graphene complex | |
| CN113462207A (en) | Photocatalytic self-cleaning composite coating and preparation method thereof | |
| CN110372226B (en) | Nano-silver coated strandy zinc oxide photocatalytic film and preparation method thereof | |
| CN104071988B (en) | Preparation method of wear-resistant long-acting self-cleaning anti-reflection coating and wear-resistant long-acting self-cleaning anti-reflection coating | |
| CN109385122A (en) | A kind of preparation method of graphene doping self-cleaning glass coating liquid | |
| CN103280281A (en) | Method for preparing anti-pollution flashover insulators | |
| CN107382092A (en) | TiO with Nanoparticles Embedded structure2 /WO3Compound electrochromic membrane and preparation method thereof | |
| EP3162773B1 (en) | Substrate provided with low-reflection coating, method for its production and photoelectric conversion device containing it. | |
| CN111589439A (en) | Si and Mo co-doped TiO2Efficient self-cleaning film of/redox graphene compound and preparation method thereof | |
| JP5434778B2 (en) | Cage-type silsesquioxane-peroxotitanium composite photocatalyst aqueous coating liquid and coating film for hydrophilic film formation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |