CN108970601A - A kind of photocatalysis coating and its preparation method and application with Zinc oxide/titanium dioxide heterojunction structure - Google Patents
A kind of photocatalysis coating and its preparation method and application with Zinc oxide/titanium dioxide heterojunction structure Download PDFInfo
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- 239000011248 coating agent Substances 0.000 title claims abstract description 103
- 238000000576 coating method Methods 0.000 title claims abstract description 103
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 50
- 238000007146 photocatalysis Methods 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 30
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title description 128
- 239000011787 zinc oxide Substances 0.000 title description 64
- 239000004408 titanium dioxide Substances 0.000 title description 19
- 238000005507 spraying Methods 0.000 claims abstract description 47
- 238000000034 method Methods 0.000 claims abstract description 39
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000011159 matrix material Substances 0.000 claims abstract description 19
- 239000002245 particle Substances 0.000 claims abstract description 13
- 239000013078 crystal Substances 0.000 claims abstract description 8
- 238000009825 accumulation Methods 0.000 claims abstract description 4
- 238000003780 insertion Methods 0.000 claims abstract description 3
- 230000037431 insertion Effects 0.000 claims abstract description 3
- 239000011344 liquid material Substances 0.000 claims description 35
- 239000011701 zinc Substances 0.000 claims description 22
- 239000002994 raw material Substances 0.000 claims description 19
- 230000008569 process Effects 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000007921 spray Substances 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 13
- 229910052725 zinc Inorganic materials 0.000 claims description 13
- 239000004094 surface-active agent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 150000003751 zinc Chemical class 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 9
- 229910001220 stainless steel Inorganic materials 0.000 claims description 9
- 239000010935 stainless steel Substances 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 8
- 238000007751 thermal spraying Methods 0.000 claims description 8
- 239000004246 zinc acetate Substances 0.000 claims description 8
- 235000007164 Oryza sativa Nutrition 0.000 claims description 7
- 235000009566 rice Nutrition 0.000 claims description 7
- 238000000889 atomisation Methods 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 4
- 238000007750 plasma spraying Methods 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920002125 Sokalan® Polymers 0.000 claims description 2
- 229910000831 Steel Inorganic materials 0.000 claims description 2
- 239000011521 glass Substances 0.000 claims description 2
- 239000004584 polyacrylic acid Substances 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 239000010959 steel Substances 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 claims 1
- 239000000356 contaminant Substances 0.000 claims 1
- 238000006731 degradation reaction Methods 0.000 claims 1
- 238000010521 absorption reaction Methods 0.000 abstract description 10
- 230000003595 spectral effect Effects 0.000 abstract description 6
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 29
- 239000002105 nanoparticle Substances 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- 239000012071 phase Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 12
- 239000000843 powder Substances 0.000 description 12
- 239000000725 suspension Substances 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 235000013339 cereals Nutrition 0.000 description 7
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- 241000209094 Oryza Species 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000008187 granular material Substances 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000002127 nanobelt Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
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- 230000008018 melting Effects 0.000 description 4
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- 239000002086 nanomaterial Substances 0.000 description 4
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- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
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- 239000004698 Polyethylene Substances 0.000 description 3
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 229960000583 acetic acid Drugs 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 238000013019 agitation Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
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- 238000006555 catalytic reaction Methods 0.000 description 3
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- 238000005859 coupling reaction Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000012362 glacial acetic acid Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- JLFNLZLINWHATN-UHFFFAOYSA-N pentaethylene glycol Chemical compound OCCOCCOCCOCCOCCO JLFNLZLINWHATN-UHFFFAOYSA-N 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
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- 230000008023 solidification Effects 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 235000011299 Brassica oleracea var botrytis Nutrition 0.000 description 2
- 240000003259 Brassica oleracea var. botrytis Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000005352 clarification Methods 0.000 description 2
- 230000001808 coupling effect Effects 0.000 description 2
- 238000001523 electrospinning Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 241000721047 Danaus plexippus Species 0.000 description 1
- 241000790917 Dioxys <bee> Species 0.000 description 1
- 241001282153 Scopelogadus mizolepis Species 0.000 description 1
- 229910008595 TiZn2O4 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- HGWOWDFNMKCVLG-UHFFFAOYSA-N [O--].[O--].[Ti+4].[Ti+4] Chemical compound [O--].[O--].[Ti+4].[Ti+4] HGWOWDFNMKCVLG-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001566 austenite Inorganic materials 0.000 description 1
- TZCXTZWJZNENPQ-UHFFFAOYSA-L barium sulfate Inorganic materials [Ba+2].[O-]S([O-])(=O)=O TZCXTZWJZNENPQ-UHFFFAOYSA-L 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 229910000238 buergerite Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
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- 230000008025 crystallization Effects 0.000 description 1
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- 230000008021 deposition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
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- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002057 nanoflower Substances 0.000 description 1
- 239000011858 nanopowder Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006862 quantum yield reaction Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
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- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 150000003608 titanium Chemical class 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses one kind to have ZnO/TiO2Photocatalysis coating of heterojunction structure and preparation method thereof, the photocatalysis coating include the nano-TiO in ZnO heap cluster, and the insertion ZnO heap cluster as made of the nano-ZnO crystal grain accumulation that diameter is 10~50nm2Particle；The ZnO heap cluster is in bulk structure, has loose and porous structure, and diameter is 3~30 μm.The present invention uses hot-spraying technique, and the photocatalysis coating is prepared in a step, and product morphology and microscopic dimensions are controllable.Photocatalysis coating disclosed by the invention, it is strong with the binding force of matrix, and there is bigger spectral absorption range, significantly improve the efficiency of the pollutants such as photocatalytically degradating organic dye.
Description
Technical field
The present invention relates to the technical fields of catalysis material, and in particular to one kind has Zinc oxide/titanium dioxide hetero-junctions
Photocatalysis coating of structure and its preparation method and application.
Background technique
Although being covered with nearly 70% water on earth surface, wherein freshwater resources only account for 2.8%, remove and are stored in the middle
Polar glacier etc. be difficult to be utilized 75%, the mankind can be using the 1% of the still insufficient earth total Water of fresh water amount, and these precious water
The resource threat with waste contaminated always for a long time, many drink water purifying technologies and sewage disposal technology are developed in succession
Out.In all kinds of purification method, photocatalysis technology as one kind can use Driven by Solar Energy catalysis reaction, have efficiently,
Low energy consumption, method applied widely and with deep oxidation ability, it is with important application prospects.
Wherein, titanium dioxide (TiO2) be the wide bandgap semiconductor being most widely used, have it is nontoxic, catalytic activity is high,
The advantages that oxidability is strong, cheap and easy to get, but titanium dioxide band gap relatively wide (Eg=3.2eV) is only in response to ultraviolet wavelength
Light irradiation, and the electron-hole pair generated is easy compound, influences its catalytic activity, limits its practical application.
Zinc oxide (ZnO) is a kind of direct semiconductor material (3.37eV) of band gap close to titanium dioxide, with higher
Exciton binding energy is common to do photoelectrocatalysimaterial material.ZnO has and TiO2Similar band structure and physical property, but simultaneously
With the unexistent characteristic of some titanium dioxide, such as higher quantum yield and higher electron mobility, this is advantageous to
Improve its photocatalytic activity.ZnO and TiO2Between energy level it is close, if in interface zone there are the contact of quantum size, can
Nanometer schottky junction is formed, can effectively increase the separative efficiency of photo-generated carrier, inhibit the compound of photo-generated carrier, and improve
The stability of catalysis material, coupling and synergistic effect can expand spectral absorption range, to increase the utilization to visible light
Rate.
(Wang Nuanxia, Sun Chenghua, Hu Xiujie, Chen Ping, Zhou Shuyun, two-step method synthesize ZnO/TiO to Wang Nuanxia etc.2Hetero-junctions
Structure, material engineering, 10 phases in 2008.) electrospinning and hydro-thermal two-step method is used to be prepared for ZnO/TiO2Heterojunction structure uses electrospinning first
Method is prepared for TiO2Film-based fibre, then with hydro-thermal method in TiO2ZnO structure is grown on film-based fibre.The preparation method needs more
Process, complex process, and the high requirements on the equipment are walked, should not be formed a film on a large scale.
(stifled monarch, Wang Yanmin, Hu Peiguang, Liu Hong, Liu Duo, the Wang Jiyang, ZnO TiO such as stifled monarch2Nanobelt surface heterogeneous medium
The preparation and characterization of structure, rare metal, in December, 2009) use hydro-thermal method and subsequent heat treatment method to prepare nano titania
Then band is prepared for ZnO@TiO in nanobelt surface-assembled nano structure of zinc oxide by liquid phase synthesizing method2Nanobelt table
Face heterojunction structure.Through characterizing, products therefrom is TiO2Nanobelt surface-assembled ZnO nano flower, TiO2The width of nanobelt is 50
~200nm, length reaches tens microns, and ZnO nano spends the petal on the bone bud of a length of 500nm with 200nm or so.The system
Although Preparation Method has obtained the TiO of self assembly2ZnO nano-structure, but it is only suitable for small range preparation, and reaction condition is controllable
Property is poor.
Therefore, it to realize with ZnO/TiO2The large-scale production and application of the photocatalysis coating of heterojunction structure, it would be highly desirable to develop
A kind of photocatalysis performance is more excellent, has new structural photocatalysis coating, and has low cost, quality of forming film high, big
Scale, the coat preparing technology for being suitble to industrialized production.
Summary of the invention
The invention discloses a kind of new structural with ZnO/TiO2The photocatalysis coating of heterojunction structure, the knot with matrix
Resultant force is strong, and has bigger spectral absorption range, significantly improves the efficiency of the pollutants such as photocatalytically degradating organic dye.This
Invention also discloses the preparation process of the photocatalysis coating, and using hot-spraying technique, the photocatalysis coating is prepared in a step, produces
Object pattern and microscopic dimensions are controllable.
Specific technical solution is as follows:
One kind having ZnO/TiO2The photocatalysis coating of heterojunction structure, including brilliant for the nano-ZnO of 10~50nm by diameter
Nano-TiO in ZnO heap cluster made of grain accumulation, and the insertion ZnO heap cluster2Particle；
The ZnO heap cluster is in bulk structure, has loose and porous structure, and diameter is 3~30 μm.
In the photocatalysis coating, ZnO and TiO2Mass ratio be 5~20:1；The TiO2It is received including at least Detitanium-ore-type
Rice TiO2。
The photocatalysis coating with a thickness of 1~20 μm, surface roughness is Ra0.2~2 μm.
Further, it being calculated through Tauc models fitting, the approximate band gap width of the photocatalysis coating is 2.80~
3.01eV。
By comparing pure ZnO sample (3.11eV) and pure TiO2(P25) the approximate band gap width number of sample (3.15eV)
According to it is found that the approximate band gap width of photocatalysis coating prepared by the present invention obviously becomes smaller, it was demonstrated that formd in photocatalysis coating
ZnO/TiO2Heterojunction structure.
The invention also discloses described to have ZnO/TiO2The preparation method of the photocatalysis coating of heterojunction structure, step packet
It includes:
(1) using dehydrated alcohol-water as solvent, zinc solution is prepared, and adjusts the pH value of the zinc solution to 4~6,
Surfactant and titanium dioxide nanoparticle are added, spraying raw material is obtained；
(2) through liquid material thermal spraying, the spraying raw material is deposited into matrix surface, is obtained described with ZnO/TiO2It is heterogeneous
The photocatalysis coating of structure.
The present invention passes through hot-spraying technique, it is preferred to use plasma spray coating process, with nano-TiO2The zinc salt of particle mixing
Forerunner's liquid suspension of solution as spraying raw material, using raw material in spraying process chemical reaction and deposit on matrix, it is real
Showed one-step method be prepared product morphology and microscopic dimensions it is controllable there is ZnO/TiO2The photocatalysis coating of heterojunction structure.
Under normal conditions, nanometer powder cannot directly carry out coating spraying preparation, and this is mainly due to nano particle diameters
Small, light weight, it is easy to reunite in spraying process and block powder feeding pipe, and accelerate kinetic energy small, it is difficult in deposited on substrates into coating；This
Outside, nanometer powder large specific surface area, powder active are high, easily make grain Size growth in spraying process and lose original receive
Rice characteristic.To overcome above-mentioned difficulties, the present invention, which is used, is configured to the traditional feeding manner progress liquid of suspension replacement for nanometer powder
Phase thermal spraying, it is small to avoid nano particle diameter in traditional hot-spraying technique, light weight, easy to reunite in spraying process and block and send
The problems such as tube cell.Meanwhile solvent its good protective effect to nano particle in the spraying process of liquid-phase thermal spray technique, it avoids
The crystallite dimension of nano particle grow up under high temperature the problems such as phase transformation.
Specifically, coating preparation is carried out using zinc solution as raw material, by nanometer powder preparation and coating preparation process one
Body had both avoided process cumbersome in nanometer powder preparation process, nano-powder in traditional hot-spraying technique will not occurs
Crystal grain is grown up and is lost.It is directly compound in the form of a solution to be difficult to realize since selectivity of the titanium salt to solvent is different from zinc salt, and
Interphase easy to form.In order to further obtain that there is the ZnO/TiO of micro-nano structure2Heterojunction structure, the present invention are further led to
The direct doping titanium dioxide nano particle in zinc solution is crossed, liquid material atomization process is improved, improves coating and matrix
Bond strength, while melting or fritting titanium dioxide granule are evenly coated in ZnO nano particle, effectively realize two kinds of wide taboos
Carrying semiconductor material it is compound, in the photocatalysis coating of preparation for porous structure and have certain hetero-junctions, to generate coupling
Synergistic effect is closed, the photocatalytic activity of composite coating is expected to obviously improve.Further, pass through titanium dioxide in control spraying raw material
The parameters such as the solid content of titanium nano particle, the mass ratio of zinc solution concentration and surfactant, spray power effectively control most
The characteristic parameters such as the pattern and phase composition score of whole coating.In step (1),
Preferably:
In the solvent, the volume ratio of dehydrated alcohol and water is 1~4:1；
Zinc salt in the zinc solution is selected from least one of zinc nitrate, zinc acetate, zinc chloride；
The concentration of the zinc solution is 0.1~1mol/L.
Preferably:
The surfactant is selected from least one of polyethylene glycol, polyethyleneimine, ammonium citrate, polyacrylic acid；
In terms of nano-titanium dioxide quality in the spraying raw material, the mass percentage of the surfactant is 5~
20%.
The mass ratio of the zinc salt and titanium dioxide nanoparticle is 5~100:1.
Further preferably, the concentration of the zinc solution is 0.5mol/L, the zinc salt and titanium dioxide nanoparticle
Mass ratio is 13.75~55.75:1.
In step (2):
Preferably:
Described matrix is selected from aluminium oxide, 45 steel, 316L stainless steel, polished silicon slice or glass slide, and described matrix is using preceding needing
By pretreatment；
The liquid material thermal spraying includes liquid material atomization and thermal spraying.
In liquid material thermal spray process, spraying raw material, i.e. liquid material are atomized into via the atomizer on spray gun tiny first
Droplet carries out thermal spraying, by the volatilization and burning of the solvent in droplet and the precipitation of solute subsequently into high temperature and high speed flame stream
With decomposing etc. tiny solids particles precipitate is formed after a series of physical, chemical reaction form coating in matrix surface.
Preferably, the process conditions of liquid material atomization are as follows: liquid material nozzle diameter isLiquid material flow is
50~150mL/min, liquid material and flame stream angulation are 90 °.
In the present invention, liquid material flow plays a key effect for the formation of hetero-junctions in the photocatalysis film that finally prepares,
It is found through experiment that will be unable to obtain heterojunction structure, lesser flow can weaken liquid when liquid material flow exceeds above-mentioned optimization range
Expect the secondary-atomizing and heating process with flame stream, influences ZnO and generate and crystallize.
Preferably, the thermal jet is painted with plasma spraying, the Lacking oxygen defect formed under the conditions of plasma high-temperature quenching
And ZnO-TiO2Heterojunction structure makes band gap narrow, and reduction photo-generated carrier is compound while expanding spectral absorption range, to make
The ability for obtaining the pollutants such as coating photocatalytically degradating organic dye gets a promotion.
The technological parameter of the plasma spraying are as follows:
Electric current is 500~700A, and voltage is 45~60V, and spray distance is 60~100mm, plasma gun movement speed
For 200~600mm/s, coating spraying pass is 1~10 time.
Further preferably, the liquid material flow is 100~120mL/min, in the liquid material range of flow, in conjunction with above-mentioned excellent
The raw material proportioning and plasma spray coating process of change, the ZnO/TiO being prepared2The approximate band gap of the photocatalysis coating of heterojunction structure
Width is 2.88~2.93eV.
The invention also discloses described to have ZnO/TiO2The photocatalysis coating of heterojunction structure is organic in photocatalytic degradation
Application in pollutant field.
Compared with prior art, the present invention has the advantage that
The present invention uses hot-spraying technique, prepares spraying raw material using nano titanium dioxide powder and zinc solution as raw material,
By strict control liquid material flow, the other hot-spraying technique parameters of re-optimization are prepared through one-step method with micro-nano structure
ZnO/TiO2The photocatalysis coating of heterojunction structure, the photocatalysis coating effectively realize ZnO and TiO2Two kinds of wide bandgap semiconductors
The coupling and synergistic effect of material have bigger spectral absorption range, significantly improve the dirts such as photocatalytically degradating organic dye
Contaminate the efficiency of object.Further, by the accuracy controlling to hot-spraying technique parameter, the pattern to photocatalysis coating may be implemented
And the Effective Regulation of microscopic dimensions.
Detailed description of the invention
Fig. 1 is that the present invention has ZnO/TiO2The preparation flow figure of the photocatalysis coating of heterojunction structure；
Fig. 2 is the XRD spectrum of the photocatalysis coating prepared respectively in Examples 1 to 5, and provides the difference of comparative example 1~3
The XRD spectrum of prepares coating is as a comparison；
Fig. 3 is that low power (5000 times) SEM of the photocatalysis coating prepared respectively in Examples 1 to 5 and comparative example 3 is microcosmic
Shape appearance figure is corresponding in turn to (a)~(f)；
Fig. 4 is high power (100000 times) the SEM microscopic appearance figure (a) and section of photocatalysis coating prepared by embodiment 3
SEM microscopic appearance figure (b)；
Fig. 5 is that the diffusing reflection of the photocatalysis coating for preparing respectively in UV-visible range absorbs in Examples 1 to 5
The curve of spectrum, and provide comparative example 1~3 and distinguish the diffusing reflection absorption spectrum curve of prepares coating as a comparison；
Fig. 6 is the Tauc model curve of the diffusing reflection absorption spectrum of the photocatalysis coating prepared respectively in Examples 1 to 5,
And it provides comparative example 1~3 and distinguishes the curve of prepares coating as a comparison.
Specific embodiment
Present invention is further described in detail with reference to the accompanying drawings and embodiments, it should be pointed out that following embodiment
It is intended to convenient for the understanding of the present invention, and does not play any restriction effect to it.
Embodiment 1
In the present embodiment, the 316L stainless steel substrates that basis material is about 2mm for thickness, ZnO/TiO on the matrix are selected2It is multiple
Closing coating layer thickness is about 5 μm, wherein TiO2With ZnO mass ratio be 1:20, coating be ZnO crystal grain and P25 particle stacking cladding and
At the loose surface, be in bulk structure, diameter be 3~30 μm, wherein ZnO grain size range be 10~50nm.The present embodiment
In, using P25 as raw material, after plasma spray coating process, titanium dioxide granule is in evenly dispersed nano particle in the coating,
With the particle for the submicron-scale that a small amount of melted by heating is sintered.The ZnO/TiO of the composite micro-nano rice structure2The system of coating
Standby process as shown in Figure 1, it is specific the preparation method is as follows:
1, first by commercially available Zn (CH3COO)2·2H2O is added to dehydrated alcohol and deionized water in equal volume than in solvent,
It stirs evenly, is made into the zinc acetate solution of 0.5mol/L, the pH value of above-mentioned zinc acetate solution is adjusted to 6 or so with glacial acetic acid,
After solution clarification, the surfactant polyethylene (PEG400) for accounting for zinc salt quality 0.09wt% is added to zinc acetate solution
In, it stirs evenly, obtains mixed solution, it will be with Zn (CH3COO)2·2H2O mass ratio is the nanometer titanium dioxide titanium valve of 1.8wt%
Last (P25) is added in mixed solution, and ultrasonic disperse 5min, magnetic agitation 0.5h obtain suspension, as spraying raw material；
2, stainless steel base is successively cleaned with acetone, dehydrated alcohol, deionized water, with 60 mesh Brown Alundum sand blastings
Sand processing, coarse surface, compressed air pressure is about 0.7MPa, finally blows off matrix surface with compressed air；
3, using feeding style outside plasma gun, under wriggling pumping action, a certain amount of liquid material passes throughNozzle,
It is vertical to be sent into flame stream root.Liquid material be atomized under the effect of plasma flame flow high temperature and high speed broken, evaporation, concentration, precipitating, sintering,
Melting, solidification form the coating that thickness is about 5 μm in matrix surface.Wherein, the spray parameters of plasma spray gun are as follows: electric current
500A, voltage 50V, spray coating liquor stream amount 100mL/min, spray distance 80mm, plasma gun lateral velocity 400mm/s are applied
Layer spraying number 3 times.
Comparative example 1
Titania nanoparticles and surfactant are not added when preparing spraying raw material for this comparative example, i.e., only with
Zn (the CH of 0.5mol/L3COO)2Solution is sprayed as raw material, and step 2~3 are identical with embodiment 1.
Embodiment 2
In the present embodiment, the 316L stainless steel substrates that basis material is about 2mm for thickness, ZnO/TiO on the matrix are selected2It is multiple
Closing coating layer thickness is about 5 μm, wherein TiO2With ZnO mass ratio be 1:10, coating be ZnO crystal grain and P25 particle stacking cladding and
At the loose surface, wherein ZnO grain size range be 10~50nm.The ZnO/TiO of the composite micro-nano rice structure2Specific preparation
Method is as follows:
1, first by commercially available Zn (CH3COO)2·2H2O is added to dehydrated alcohol and deionized water in equal volume than in solvent,
It stirs evenly, is made into the zinc acetate solution of 0.5mol/L, the pH value of above-mentioned solution is adjusted to 6 or so with glacial acetic acid, solution is clear
After clear, the surfactant polyethylene (PEG400) for accounting for zinc salt quality 0.18wt% is added in solution, is stirred evenly, it will
With Zn (CH3COO)2·2H2O mass ratio is that the nano titanium dioxide powder (P25) of 3.6wt% is added to Zn (CH3COO)2·
2H2In O solution, ultrasonic disperse 5min, magnetic agitation 0.5h obtain suspension, as spraying raw material；
2, stainless steel base is successively cleaned with acetone, dehydrated alcohol, deionized water, with 60 mesh Brown Alundum sand blastings
Sand processing, coarse surface, compressed air pressure is about 0.7MPa, finally blows off matrix surface with compressed air；
3, using feeding style outside plasma gun, under wriggling pumping action, a certain amount of liquid material passes throughNozzle,
It is vertical to be sent into flame stream root.Liquid material be atomized under the effect of plasma flame flow high temperature and high speed broken, evaporation, concentration, precipitating, sintering,
Melting, solidification form the coating that thickness is about 5 μm in matrix surface.Wherein, the spray parameters of plasma spray gun are as follows: electric current
500A, voltage 50V, spray coating liquor stream amount 120mL/min, spray distance 80mm, plasma gun lateral velocity 400mm/s are applied
Layer spraying number 3 times.
Embodiment 3:
In the present embodiment, the 316L stainless steel substrates that basis material is about 2mm for thickness, ZnO/TiO on the body are selected2It is multiple
Closing coating layer thickness is about 5 μm, wherein TiO2It is 1:5 with ZnO mass ratio, coating is that ZnO crystal grain and P25 particle stacking coat
The loose surface, wherein ZnO grain size range be 10~50nm.The ZnO/TiO of the composite micro-nano rice structure2Specific preparation side
Method is as follows:
1, first by commercially available Zn (CH3COO)2·2H2O is added to dehydrated alcohol and deionized water in equal volume than in solvent,
It stirs evenly, is made into the zinc acetate solution of 0.5mol/L, the pH value of above-mentioned solution is adjusted to 6, after solution clarification with glacial acetic acid,
The surfactant polyethylene (PEG400) for accounting for zinc salt quality 0.36wt% is added in solution, is stirred evenly, it will be with Zn
(CH3COO)2·2H2O mass ratio is that the nano titanium dioxide powder (P25) of 7.2wt% is added to Zn (CH3COO)2·2H2O
In solution, ultrasonic disperse 5min, magnetic agitation 0.5h obtain suspension；
2, stainless steel base is successively cleaned with acetone, dehydrated alcohol, deionized water, with 60 mesh Brown Alundum sand blastings
Sand processing, coarse surface, compressed air pressure is about 0.7MPa, finally blows off matrix surface with compressed air；
3, using feeding style outside plasma gun, under wriggling pumping action, a certain amount of liquid material passes throughNozzle,
It is vertical to be sent into flame stream root.Liquid material be atomized under the effect of plasma flame flow high temperature and high speed broken, evaporation, concentration, precipitating, sintering,
Melting, solidification form the coating that thickness is about 5 μm in matrix surface.Wherein, the spray parameters of plasma spray gun are as follows: electric current
500A, voltage 50V, spray coating liquor stream amount 100mL/min, spray distance 80mm, plasma gun lateral velocity 400mm/s are applied
Layer spraying number 3 times.
Comparative example 2
This comparative example in step 1, prepares dehydrated alcohol and deionized water in equal volume than mixed solvent, but only no longer add
Zinc acetate is equipped with nano titanium dioxide powder (P25) suspension of identical solid content as liquid material.Step 2~3 and embodiment
It is identical in 3.
Comparative example 3
This comparative example in step 1, prepares dehydrated alcohol and deionized water in equal volume than mixed solvent, the mass ratioes such as is equipped with
Nano-zinc oxide powder (30 ± 10nm of particle diameter) and nano titanium dioxide powder (P25) suspension be used as liquid material, suspension
Solid content is 40g/L in liquid.Step 2~3 are identical with embodiment 3.
Embodiment 4
Preparation process flow is identical with embodiment 3, and difference, which is only that, replaces with spray coating liquor stream amount in step 3
50mL/min。
Embodiment 5
Preparation process flow is identical with embodiment 3, and difference, which is only that, replaces with spray coating liquor stream amount in step 3
150mL/min。
Material phase analysis, microscopic appearance observation and coating surface Elemental redistribution is carried out to the product of the above various embodiments preparation to survey
Examination, test method and result are as follows:
1, material phase analysis: coating sample is laid flat to concordant with sample stage, using X-ray diffractometer to its crystal structure into
Row detection.
Embodiment 1,2,3,4,5 compares, and the product prepared after spraying mainly contains Anatase and Rutile Type
TiO2There is the austenite phase of stainless steel base since coating layer thickness is smaller with the ZnO of buergerite phase.With directly suspended by P25
The coating of liquid spraying (comparative example 2) preparation is compared, and the ratio of anatase and Rutile Type has different degrees of raising.With dioxy
Change the increase of Ti content, the ratio of Anatase gradually first increases in coating subtracts afterwards.For direct spraying zinc oxide and titanium dioxide
, there is new TiZn in suspension mixed coating (comparative example 3)2O4Phase.Also occurs new TiZn in embodiment 42O4Phase,
And titanium dioxide crystal degree is smaller in coating.In embodiment 5, although there is not TiZn2O4Phase, but titanium dioxide in coating
Crystallization degree is equally smaller, and the ratio of Anatase is reduced sharply compared to embodiment 1,2,3.As shown in Fig. 2, by Scherrer formula
It can be calculated, significant change does not occur for the size of ZnO particle in each coating, and average grain size is in 20nm or so.
2, Micro-Structure Analysis: taking coating sample, is fixed on sample stage with conducting resinl, after spraying Au, is swept using Flied emission
Retouch its coating surface of electron microscope observation or section heterogeneous microstructure.
As it can be seen that coating morphology is in the typical cauliflower structure of solution spraying coating, i.e. nanometer from Fig. 3 (a)~(e)
ZnO heap cluster is in bulk structure, has certain loose hole, but contains a small amount of TiO in " cauliflower "2Spherical particle, coating portion
Visible unmelted TiO in subregion2Reunite, and as content of titanium dioxide increases, spheric granules ratio increases.(a) figure from Fig. 4
High power image in it is known that nano zine oxide diameter is very small, about 10~50nm, and among ZnO particle is mixed with few
Measure TiO2Spheric granules.For the vertical structure of coating, can from find out in (b) figure in Fig. 4 coating by nano particle accumulation and
At interlayer has certain hole.
From in Fig. 3 (f) as it can be seen that in coating, TiO2Spheric granules is in the aggregating state of bulky grain, fails to be dispersed in and receive
Between rice ZnO heap cluster.
3, coating spectral absorption curve: taking coating sample, is fixed on specimen holder, with BaSO4For blank, testing coating wave
The absorbance within the scope of 200-800nm is grown, and is calculated according to Tauc models fitting, obtains the approximate band gap width of coating.
It is known that being less than the ultraviolet light wave band of 400nm, ZnO/TiO in wavelength from Fig. 52Composite coating (embodiment 1
~5) absorption curve and the ZnO coating of solution presoma spraying are close, and are higher than P25 coating sample；In wavelength greater than 400nm's
Visible light wave range, ZnO/TiO2Composite coating absorption curve is higher than ZnO coating sample close to P25 coating sample.ZnO/
TiO2For composite coating absorption line compared to one-component sample, ABSORPTION EDGE is in red shift trend.Further from Fig. 6 and the following table 1
It is found that ZnO/TiO2Composite coating samples band-gap width is within the scope of 2.88~3.01eV, hence it is evident that less than the ZnO sample of one-component
Product (3.11eV), P25 sample (3.15eV) and ZnO and TiO2Mixing suspension sample (3.17eV).To 4 coating of embodiment, compared with
On the one hand low liquid material flow is unfavorable for coating deposition, on the other hand higher unit heat input is also easy to produce second-phase reaction, no
Conducive to ZnO/TiO2The formation of heterojunction structure, this is also the higher reason of its band gap magnitude (3.01eV).To 5 coating of embodiment, compared with
High liquid material flow makes liquid stream in spraying process inject upset plasma arc flame, on the one hand reduces the homogeneity of coating, separately
On the one hand there is the liquid material of large scale to be directly mixed in coating without Source, influence coating overall structure.Comparative example 3 is biggish
Band gap magnitude illustrates ZnO and TiO2The mechanical mixture of nano particle cannot form being uniformly distributed for nano particle, the TiO of incorporation2Nanometer
There is (in such as Fig. 3 (f)) easily in suspension with the aggregated form of submicron order in particle, be also easy to happen sintering reaction generation
Second phase less has the formation of hetero-junctions.
The following table 1 is the band gap magnitude being calculated according to the Tauc model curve of the diffusing reflection absorption spectrum of coating each in Fig. 6.
Table 1
Claims (10)
1. one kind has ZnO/TiO2The photocatalysis coating of heterojunction structure, which is characterized in that including being receiving for 10~50nm by diameter
Nano-TiO in ZnO heap cluster, and the insertion ZnO heap cluster made of rice ZnO crystal grain accumulation2Particle；
The ZnO heap cluster is in bulk structure, has loose and porous structure, and diameter is 3~30 μm.
2. according to claim 1 have ZnO/TiO2The photocatalysis coating of heterojunction structure, which is characterized in that the light is urged
Change in coating, ZnO and TiO2Mass ratio be 5~20:1.
3. according to claim 1 have ZnO/TiO2The photocatalysis coating of heterojunction structure, which is characterized in that through Tauc mould
Type the Fitting Calculation, the approximate band gap width of the photocatalysis coating are 2.88~3.01eV.
4. there is ZnO/TiO described in a kind of any claim according to claim 1~32The photocatalysis coating of heterojunction structure
Preparation method, which is characterized in that step includes:
(1) using dehydrated alcohol-water as solvent, zinc solution is prepared, and the pH value for adjusting the zinc solution is added to 4~6
Surfactant and nano-titanium dioxide, obtain spraying raw material；
(2) through liquid material thermal spraying, the spraying raw material is deposited into matrix surface, is obtained described with ZnO/TiO2Heterojunction structure
Photocatalysis coating.
5. according to claim 4 have ZnO/TiO2The preparation method of the photocatalysis coating of heterojunction structure, feature exist
In in step (1):
In the solvent, the volume ratio of dehydrated alcohol and water is 1~4:1；
Zinc salt in the zinc solution is selected from least one of zinc nitrate, zinc acetate, zinc chloride；
The concentration of the zinc solution is 0.1~1mol/L.
6. according to claim 4 have ZnO/TiO2The preparation method of the photocatalysis coating of heterojunction structure, feature exist
In in step (1):
The surfactant is selected from least one of polyethylene glycol, polyethyleneimine, ammonium citrate, polyacrylic acid；
In terms of the quality of nano-titanium dioxide in the spraying raw material, the mass percentage of the surfactant is 5~
20%；
The mass ratio of the zinc salt and nano-titanium dioxide is 5~100:1.
7. according to claim 4 have ZnO/TiO2The preparation method of the photocatalysis coating of heterojunction structure, feature exist
In in step (2):
Described matrix be selected from aluminium oxide, 45 steel, 316L stainless steel, polished silicon slice or glass slide, described matrix using preceding need by
Pretreatment；
The liquid material thermal spraying includes liquid material atomization and thermal spraying.
8. according to claim 7 have ZnO/TiO2The preparation method of the photocatalysis coating of heterojunction structure, feature exist
In the process conditions of liquid material atomization are as follows: liquid material nozzle diameter isLiquid material flow is 50~150mL/
Min, liquid material and flame stream angulation are 90 °；
The thermal jet is painted with plasma spraying, technological parameter are as follows:
Electric current is 500~700A, and voltage is 45~60V, and spray distance is 60~100mm, and plasma gun movement speed is 200
~600mm/s, coating spraying pass are 1~10 time.
9. according to claim 7 have ZnO/TiO2The preparation method of the photocatalysis coating of heterojunction structure, feature exist
In in the liquid material atomization process, liquid material flow is 100~120mL/min.
10. there is ZnO/TiO described in a kind of any claim according to claim 1~32The photocatalysis coating of heterojunction structure
Application in photocatalysis degradation organic contaminant field.
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