CN109529954A - One kind having accumulation of energy photoelectrocatalysis type air cleaning laminated film and preparation method - Google Patents
One kind having accumulation of energy photoelectrocatalysis type air cleaning laminated film and preparation method Download PDFInfo
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- 238000009825 accumulation Methods 0.000 title claims abstract description 61
- 238000004140 cleaning Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims description 20
- 230000001699 photocatalysis Effects 0.000 claims abstract description 47
- 238000007146 photocatalysis Methods 0.000 claims abstract description 43
- 239000002245 particle Substances 0.000 claims abstract description 36
- 239000011159 matrix material Substances 0.000 claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 34
- 238000000034 method Methods 0.000 claims description 19
- 239000006210 lotion Substances 0.000 claims description 18
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- 230000003197 catalytic effect Effects 0.000 claims description 15
- 229910052593 corundum Inorganic materials 0.000 claims description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 15
- 239000000463 material Substances 0.000 claims description 14
- 229910052681 coesite Inorganic materials 0.000 claims description 13
- 229910052906 cristobalite Inorganic materials 0.000 claims description 13
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 229910052682 stishovite Inorganic materials 0.000 claims description 13
- 229910052905 tridymite Inorganic materials 0.000 claims description 13
- 229910044991 metal oxide Inorganic materials 0.000 claims description 11
- 150000004706 metal oxides Chemical class 0.000 claims description 11
- 239000004925 Acrylic resin Substances 0.000 claims description 9
- 239000004593 Epoxy Substances 0.000 claims description 9
- 239000011246 composite particle Substances 0.000 claims description 9
- 238000007641 inkjet printing Methods 0.000 claims description 9
- 229920002635 polyurethane Polymers 0.000 claims description 9
- 239000004814 polyurethane Substances 0.000 claims description 9
- 238000007761 roller coating Methods 0.000 claims description 9
- 238000007650 screen-printing Methods 0.000 claims description 9
- 238000005507 spraying Methods 0.000 claims description 9
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 6
- 229910052693 Europium Inorganic materials 0.000 claims description 6
- 229910017623 MgSi2 Inorganic materials 0.000 claims description 6
- 239000005084 Strontium aluminate Substances 0.000 claims description 6
- 229920002050 silicone resin Polymers 0.000 claims description 6
- 239000011258 core-shell material Substances 0.000 claims description 5
- 229910052737 gold Inorganic materials 0.000 claims description 5
- 239000010931 gold Substances 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229920000178 Acrylic resin Polymers 0.000 claims description 3
- 229910004706 CaSi2 Inorganic materials 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052731 fluorine Inorganic materials 0.000 claims description 3
- 229910052839 forsterite Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- -1 siloxanes Chemical class 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 229910001650 dmitryivanovite Inorganic materials 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910001707 krotite Inorganic materials 0.000 claims description 2
- 238000010422 painting Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 3
- 239000002861 polymer material Substances 0.000 abstract description 2
- 230000001681 protective effect Effects 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 124
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 30
- 239000000758 substrate Substances 0.000 description 11
- 239000005416 organic matter Substances 0.000 description 10
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000004659 sterilization and disinfection Methods 0.000 description 6
- 239000011521 glass Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 230000001954 sterilising effect Effects 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000003260 anti-sepsis Effects 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000004745 nonwoven fabric Substances 0.000 description 2
- 210000002381 plasma Anatomy 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 241000208340 Araliaceae Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 description 1
- 235000003140 Panax quinquefolius Nutrition 0.000 description 1
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000008434 ginseng Nutrition 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 229910003471 inorganic composite material Inorganic materials 0.000 description 1
- 230000002147 killing effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 230000004630 mental health Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000002344 surface layer 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B01J35/39—
-
- B01J35/59—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0228—Coating in several steps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
Abstract
The present invention relates to technical field of polymer materials, it is concretely a kind of with accumulation of energy photoelectrocatalysis type air cleaning laminated film, it include: matrix, reflection layer, light accumulation of energy layer and photocatalysis layer, the upper surface of matrix is coated with reflection layer, the upper surface of reflection layer is coated with light accumulation of energy layer, the smooth accumulation of energy layer is the patterned structures of cube, there are non-reflective gaps between each light storage cube, photocatalysis layer is coated in the upper surface of light accumulation of energy layer, the photocatalysis layer is to be piled up to form the film containing hole shape by little particle, the present invention is while keeping frivolous feature, it can use natural light or existing light carry out accumulation of energy, without additional energy consumption, it is environmentally protective, and the utilization rate of light is high, sustainable round-the-clock purification air.
Description
Technical field
The present invention relates to technical field of polymer materials, are concretely a kind of with the type air cleaning of accumulation of energy photoelectrocatalysis
Laminated film and preparation method.
Background technique
With the development of economy, environmental pollution has become the bottleneck problem of social development, and Air Contamination is for example volatilizable
Property organic matter (VOCs) has influenced the physical and mental health of people.If service life is shorter with adsorption technologies such as active carbons, absorption is full
Secondary pollution is also easy to produce with after, it is at high cost；If can only be filtered to grit, be gone to organic gas molecule with technologies such as filterings
Except efficiency is very low；If can decompose VOCs with technologies such as plasmas, but energy consumption is high, the service life is short and at high cost；These technologies are not
It is suitble to low cost large-scale use.
It is a kind of more energy-efficient air cleaning new method that organic molecule is decomposed in the photochemical catalytic oxidation of new development.Photocatalytic method
Generally using nanometer titania as catalyst, the oxidable organic matter decomposed in air under ultraviolet light is
A kind of better simply air purifying process.But because of very low (the ultraviolet light ratio one in such as daylight of the ratio of ultraviolet light in natural light
As < 4%), the utilization rate of light is not high；And ultraviolet source artificial at present is mainly mercury lamp, it has a short service life, and (500 ~ 2000 is small
When), operating power consumption is larger, and it is discarded after mercury easily cause serious environmental pollution.In addition, ultraviolet light easily causes the wound to human body
Evil.Therefore the air evolution technology application of ultraviolet catalytic oxidation decomposing organic matter is very restricted, it is difficult to scale application.
Therefore need development cost lower and efficient catalysis material and technology, and scale application can be practiced, be at present there is an urgent need to
It solves the problems, such as.
Document Chinese patent (CN1699263A) " a kind of composite material with purification and beautifying functions ", mainly uses
Long after glow luminous material, nano-photocatalyst material and antisepsis metallic compound with accumulation of energy function are combined with each other, by accumulation of energy
Luminescent material, antisepsis metallic compound and catalysis material powder are fixed etc. in the form of glaze in substrate surface, have the spy that shines
Property, degradation of contaminant and killing and inhibiting effect to bacterium.The method needs to prepare luminescence glaze at high temperature, can only make pottery
Film is prepared on the substrate resistant to high temperature such as porcelain or glass；In addition surface uses nano-titanium dioxide and silver ion composite catalyzing material
Material, belongs to ultraviolet photocatalytic material, catalytic efficiency is lower under visible light.So method is in practical applications by very big limit
System.
And it needs to carry out photocatalysis to surfaces such as many various types of substrates such as wall, furniture, plastics, metal in practical application thin
The coating of film needs that efficient visible light catalytic film can be coated at room temperature, to there is extensive adaptability.
Therefore design it is a kind of can be coated on a variety of substrates at a lower temperature have accumulation of energy photoelectrocatalysis type air
The laminated film of purification function be very it is necessary to.
Summary of the invention
The present invention breaches the problem of the prior art, devise a kind of organic/inorganic composite material lower temperature (10 ~
150 DEG C) under the laminated film with accumulation of energy photoelectrocatalysis type air-cleaning function that can be coated on a variety of substrates.Feature is
The inorganic nanometer oxide particle of inorganic fluorescent particle and photo-catalysis function with extinction energy-storage function is organised with liquid
The function slurry that object is complex as coatable film forming is closed, function film can be formed by curing under lower temperature (10 ~ 150 DEG C).
In order to achieve the above object, the present invention, which devises one kind, has accumulation of energy photoelectrocatalysis type air cleaning laminated film,
It include: matrix, reflection layer, light accumulation of energy layer and photocatalysis layer, it is characterised in that: the upper surface of matrix is coated with reflection layer,
The upper surface of reflection layer is coated with light accumulation of energy layer, and the smooth accumulation of energy layer is the patterned structures of cube, each light storage cube
There are non-reflective gaps between body, are coated with photocatalysis layer in the upper surface of light accumulation of energy layer, the photocatalysis layer is by little particle heap
It builds and forms the film containing hole shape.
The reflection layer with a thickness of 1 ~ 20 micron, light accumulation of energy layer with a thickness of 1 ~ 60 micron, the thickness of photocatalysis layer
It is 0.1 ~ 2 micron.
Described matrix can be wall, furniture, plastics, metal.
A kind of preparation method with accumulation of energy photoelectrocatalysis type air cleaning laminated film, feature has also been devised in the present invention
It is: is prepared in accordance with the following steps:
Step 1: preparing reflection layer；
Step 2: reflection layer is coated in the upper surface of matrix, room temperature or 10 ~ 150 DEG C at a temperature of dry；
Step 3: preparing light accumulation of energy layer；
Step 4: light accumulation of energy layer is coated in the upper surface of reflection layer, room temperature or 10 ~ 150 DEG C at a temperature of dry；
Step 5: preparing photocatalysis layer；
Step 6: photocatalysis layer is coated in the upper surface of light accumulation of energy layer, room temperature or 10 ~ 150 DEG C at a temperature of dry, obtain
High efficiency photon accumulating type air cleaning laminated film.
The preparation step for preparing reflection layer is as follows:
Using acrylic resin, polyurethane, epoxy, silicone resin as parent, by the TiO of core-shell structure2@SiO2Or TiO2@
Al2O3Parent is added in composite particles, and is uniformly dispersed, the TiO2@SiO2Or TiO2@Al2O3Composite particles and parent mix
Ratio is 5 ~ 30%(wt), thickness is formed at 1 ~ 20 micron using techniques such as spraying, roller coating, blade coating, inkjet printing, silk-screen printings
Film in range, as reflection layer.
The preparation step for preparing light accumulation of energy layer is as follows:
Using polyacrylic resin, polyurethane, epoxy, silicone resin lotion as parent, long-afterglow fluorescent particle is mixed
Lotion is simultaneously uniformly dispersed, and the ratio of mixing of the long-afterglow fluorescent particle and lotion is 5 ~ 50%(wt), using spraying, roller coating, scrape
The techniques such as painting, inkjet printing, silk-screen printing form film of the thickness in 1 ~ 60 micron range, as light accumulation of energy layer.
The preparation step for preparing photocatalysis layer is as follows:
Using polyacrylic resin, polyurethane, epoxy, siloxanes lotion as parent, by the gold with visible light catalytic function
Belong to oxide and mixes nano-TiO2, SnO, at least one of ZnO particle lotion is added, and is uniformly dispersed, it is described have it is visible
The metal oxide of photo-catalysis function mixes nano-TiO2, SnO, ZnO particle and lotion ratio of mixing be 0.1 ~ 5%(wt), adopt
Film of the thickness in 0.1 ~ 2 micron range is formed with techniques such as spraying, roller coating, blade coating, inkjet printing, silk-screen printings, as
Photocatalysis layer.
The TiO of the core-shell structure2@SiO2Or TiO2@Al2O3The size of composite particles is in 200 ~ 400 nanometer ranges
In TiO2One layer of SiO is coated using sol gel process on particle2Or Al2O3Film be formed by, the SiO2Or Al2O3's
Film thickness is 5 ~ 50 nanometers.
The fluorescent material of the long-afterglow fluorescent particle includes at least one of blue, bluish-green, green, yellowish green, orange, red,
The size of the long-afterglow fluorescent particle is CaAl in 1 ~ 30 micron range, the blue2O4:Eu2+, Sr2MgSi2O7,
Sr2MgSi2O7:Eu2+,Dy3+；
Green is SrAl2O4:Eu2+；Sr(Al1-xBx)2O4:Eu2+；(Sr,Eu,Dy)0.95±x(Al,B)2O3.95±x；(Sr,Eu,
Dy)4-x(Al,B)14O25-x；
Yellow green is SrAl2O4:Eu2+,Dy3+, Sr(Al1-xBx)2O4:Eu2+,Dy3+；
Yellow is CaSi2O2N2；
Orange is Sr3Al2O5Cl2；
Red is Y2O3S:Eu3+,Mg2+,Ti4+；Y2O3S:Sm3+；Y2O3:Eu3+,Dy3+; CaO:Eu3+；Mg2SiO4:Dy3+,Mn2+；
Ca2Si5N8:Eu2+, R3+(R3+=Dy3+,Nd3+,Gd3+,Sm3+)；ATiO3:Pr3+, A=Ca,Sr,Ba 。
The metal oxide with visible light catalytic function mixes nano-TiO2, SnO, mixed in ZnO particle
Element is at least one of H, C, N, F, Fe, Cu, Ag, Au, Pt, Ni, W, Mo, Mn, the ginseng of above-mentioned element and metal oxide
Miscellaneous ratio is 0.1 ~ 2%(atm).
Compared with prior art, the present invention the present invention while keeping frivolous feature, can use natural light or
Some light carries out accumulation of energy, environmentally protective without additional energy consumption, and the utilization rate of light is high, sustainable round-the-clock purification
Air.Because the present invention can store luminous energy, the nanoparticle of continuous illumination, the visible light catalytic function on laminated film surface can be to carbon
The organic molecules such as hydrogen carry out catalytic oxidation and generate carbon dioxide and water, thus have disinfection, it is mould proof, sterilize, decompose it is organic
The purification functions such as object.
Detailed description of the invention
Fig. 1 is the structural diagram of the present invention.
Specific embodiment
The present invention is described further in conjunction with attached drawing.
Referring to Fig. 1, the present invention devises a kind of with accumulation of energy photoelectrocatalysis type air cleaning laminated film, comprising: matrix
1, reflection layer 2, light accumulation of energy layer 3 and photocatalysis layer 4, the upper surface of matrix 1 are coated with reflection layer 2, and reflection layer 2 is used as bottom
Layer film can reflect wavelength in the light of 400 ~ 700nm, and 90% or more, the upper surface of reflection layer 2 coats reflectivity
There is a light accumulation of energy layer 3, the smooth accumulation of energy layer 3 is the patterned structures of cube, there are non-reflective gap between each light storage cube,
The light that light storage layer 3 is discharged downwards is reflected into photocatalysis layer 4 again by reflection layer 2 and non-reflective gap, is increased
Strong catalytic action, light accumulation of energy layer 3 are used as intermediate layer film, can wavelength be carried out absorbing storage and be shone in the light of 400 ~ 700nm,
The luminous sunset glow time is coated with photocatalysis layer 4 at 10 hours or more, in the upper surface of light accumulation of energy layer 3, and the photocatalysis layer 4 is
It is piled up by little particle and forms the film containing hole shape, photocatalysis layer 4 is used as surface layer film, can be to wavelength in 400 ~ 700nm
Light carry out absorb generate photoelectrocatalysis function, oxygenolysis can be played to organic molecule.
In the present invention reflection layer 2 with a thickness of 1 ~ 20 micron, light accumulation of energy layer 3 with a thickness of 1 ~ 60 micron, photocatalysis layer 4
With a thickness of 0.1 ~ 2 micron.
Matrix 1 can be plate or film made of a variety of materials such as wall, furniture, plastics, metal in the present invention.
A kind of preparation method with accumulation of energy photoelectrocatalysis type air cleaning laminated film has also been devised in the present invention, according to such as
It is prepared by lower step:
Step 1: preparing reflection layer 2；
Step 2: reflection layer 2 is coated in the upper surface of matrix 1, room temperature or 10 ~ 150 DEG C at a temperature of dry；
Step 3: preparing light accumulation of energy layer 3；
Step 4: light accumulation of energy layer 3 is coated in the upper surface of reflection layer 2, room temperature or 10 ~ 150 DEG C at a temperature of dry；
Step 5: preparing photocatalysis layer 4；
Step 6: photocatalysis layer 4 is coated in the upper surface of light accumulation of energy layer 3, room temperature or 10 ~ 150 DEG C at a temperature of dry, obtain
To high efficiency photon accumulating type air cleaning laminated film.
The preparation step for preparing reflection layer 2 is as follows:
Using acrylic resin, polyurethane, epoxy, silicone resin as parent, by size 200 ~ 400 nanometer ranges nucleocapsid
The TiO of structure2@SiO2Or TiO2@Al2O3Parent is added in composite particles, and is uniformly dispersed, the TiO2@SiO2Or TiO2@Al2O3
The ratio of mixing of composite particles and parent is 5 ~ 30%(wt), using works such as spraying, roller coating, blade coating, inkjet printing, silk-screen printings
Skill forms film of the thickness in 1 ~ 20 micron range, as reflection layer 2.
The preparation step for preparing light accumulation of energy layer 3 is as follows:
Using polyacrylic resin, polyurethane, epoxy, silicone resin lotion as parent, by size in 1 ~ 30 micron range
The incorporation of long-afterglow fluorescent particle lotion and be uniformly dispersed, the ratio of mixing of the long-afterglow fluorescent particle and lotion is 5 ~ 50%
(wt), thin in 1 ~ 60 micron range using the techniques such as spraying, roller coating, blade coating, inkjet printing, silk-screen printing formation thickness
Film, as light accumulation of energy layer 3.
The preparation step for preparing photocatalysis layer 4 is as follows:
Using polyacrylic resin, polyurethane, epoxy, siloxanes lotion as parent, by size 2 ~ 50 nanometer ranges tool
There is the metal oxide of visible light catalytic function to mix nano-TiO2, SnO, at least one of ZnO particle be added lotion, and point
It dissipates uniformly, the metal oxide with visible light catalytic function mixes nano-TiO2, SnO, ZnO particle and lotion mix
Ratio is 0.1 ~ 5%(wt), it is micro- 0.1 ~ 2 that thickness is formed using techniques such as spraying, roller coating, blade coating, inkjet printing, silk-screen printings
Film in rice range, as photocatalysis layer 4.
The TiO of core-shell structure in the present invention2@SiO2Or TiO2@Al2O3The size of composite particles is in 200 ~ 400 nanometer ranges
It is interior, it is in TiO2One layer of SiO is coated using sol gel process on particle2Or Al2O3Film be formed by, the SiO2Or
Al2O3Film thickness be 5 ~ 50 nanometers.
The fluorescent material of long-afterglow fluorescent particle includes at least one in blue, bluish-green, green, yellowish green, orange, red in the present invention
Kind, the size of the long-afterglow fluorescent particle is prepared in 1 ~ 30 micron range using solid-phase sintering method, and the blue is
CaAl2O4:Eu2+, Sr2MgSi2O7, Sr2MgSi2O7:Eu2+,Dy3+；
Green is SrAl2O4:Eu2+；Sr(Al1-xBx)2O4:Eu2+；(Sr,Eu,Dy)0.95±x(Al,B)2O3.95±x；(Sr,Eu,
Dy)4-x(Al,B)14O25-x；
Yellow green is SrAl2O4:Eu2+,Dy3+, Sr(Al1-xBx)2O4:Eu2+,Dy3+；
Yellow is CaSi2O2N2；
Orange is Sr3Al2O5Cl2；
Red is Y2O3S:Eu3+,Mg2+,Ti4+；Y2O3S:Sm3+；Y2O3:Eu3+,Dy3+; CaO:Eu3+；Mg2SiO4:Dy3+,Mn2+；
Ca2Si5N8:Eu2+, R3+(R3+=Dy3+,Nd3+,Gd3+,Sm3+)；ATiO3:Pr3+, A=Ca,Sr,Ba 。
Metal oxide in the present invention with visible light catalytic function mixes nano-TiO2, SnO, joined in ZnO particle
Miscellaneous element is at least one of H, C, N, F, Fe, Cu, Ag, Au, Pt, Ni, W, Mo, Mn, above-mentioned element and metal oxide
Mix ratio be 0.1 ~ 2%(atm), the nanoparticle can be used sol-gal process, hydrothermal synthesis method preparation, it is also possible to vacuum
The preparation such as plasma such as arc process.
The metal oxide nano TiO not mixed2, SnO, ZnO particle have wider semiconductor forbidden bandwidth (>
3.0eV), it mainly absorbs ultraviolet light (wavelength < 400nm) and there is photocatalytic oxidation.Object can be oxidized metal by mixing
The forbidden bandwidth of nanoparticle material becomes smaller (2.0 ~ 3.0eV), 400 ~ 700nm of such visible light absorbing wavelength and urged with light
Change oxidation characteristic, i.e., hydrocarbon equal organic molecules can be carried out under visible light illumination catalytic oxidation generate carbon dioxide and
Water.Therefore using such metal oxide nanoparticles mixed there is disinfection, mould proof, sterilization, decomposition to have under visible light illumination
The purification functions such as machine object.
In specific implementation, first by first layer reflection layer 2 be coated in matrix 1 on, matrix can be used as wall, plank,
Glass, plastic plate or film, metal plate or film, ceramic wafer etc. dry at a temperature of room temperature or 10 ~ 150 DEG C.
Second layer light accumulation of energy layer 3 is coated on 2 surface of first layer reflection layer again, is dried in the air at a temperature of room temperature or 10 ~ 150 DEG C
It is dry.
Last third layer photocatalysis layer 4 is coated on 3 surface of second layer light accumulation of energy layer, dries at room temperature.Work as visible light, wraps
Sunlight, natural light (scattering light), light are included, when being irradiated in the present invention, most photon energy is by second layer light accumulation of energy layer 3
Material is directly absorbed and is stored, and partially can be reflected back the second layer by first layer reflection layer 2 through the light of the second layer and be inhaled again
It receives, the long-afterglow fluorescent particle in second layer light accumulation of energy layer 3 emits the photon of specific wavelength while extinction energy storage.Third
Photocatalytic nanometer particle in layer photocatalysis layer 4 has absorb light photon energy after to the organic matter such as formaldehyde of adsorption
Deng progress catalysis oxidation decomposition reaction, carbon dioxide and water are generated.Nano-catalytic particle can absorb direct irradiation to film surface
Photon and the 3 long-afterglow fluorescent corpuscular emission of photon and second layer light accumulation of energy layer reflected by first layer reflection layer 2 photon
Energy.Can directly organic gas be catalytically decomposed when having light or light-illuminating third layer photocatalysis layer 4 daytime and purify air；
When at night or in dark without light, because the long-afterglow fluorescent particle in second layer light accumulation of energy layer 3 can continue radiating visible light, (wavelength is
450 ~ 700nm) photon, the nano-catalytic particle in third layer photocatalysis layer 4 can absorb the energy of this partial photonic and continues
It carries out catalytic decomposition adsorption organic pollutant and purifies air.
Embodiment:
Example 1:
Using non-woven fabrics as substrate, first layer reflection layer 2 is coated on matrix nonwoven interlining bottom 1, is dried at a temperature of 25 DEG C,
With a thickness of 2 microns；Again by second layer light accumulation of energy layer 3(blue light) it is coated on 2 surface of first layer reflection layer, it dries in the air at a temperature of 25 DEG C
It is dry, with a thickness of 40 microns；Last third layer photocatalysis layer 4 is coated on 3 surface of second layer light accumulation of energy layer, dries at 25 DEG C, thick
Degree is 1 micron.This non-woven fabrics applies laminated film, under natural light or light-illuminating, has after absorbing light photon energy
The sustainable organic matter to adsorption includes that formaldehyde etc. plays photo-catalysis function and the functions such as decomposing organic matter, sterilization.Such as in sky
Concentration of formaldehyde, through light (LED white light, power 10W) irradiation in 2 hours, can remove formaldehyde 70% or so, then through 8 in 5PPM in gas
After hour (no light), 99% or more formaldehyde can remove.
Example 2:
Using polymer P ET as substrate, first layer reflection layer 2 is coated on matrix PET substrate 1, is dried at a temperature of 60 DEG C,
With a thickness of 1 micron；Again by second layer light accumulation of energy layer 3(green light) it is coated on 2 surface of first layer reflection layer, it is dried at a temperature of 60 DEG C
It is dry, with a thickness of 30 microns；Last third layer photocatalysis layer 4 is coated on 3 surface of second layer light accumulation of energy layer, dries at 60 DEG C, thick
Degree is 1 micron.This PET applies laminated film, and under natural light or light-illuminating, having can be held after absorbing light photon energy
Continuous includes that formaldehyde etc. plays photo-catalysis function and the functions such as decomposing organic matter, sterilization to the organic matter of adsorption.As in air
Concentration of formaldehyde, through light (LED white light, power 10W) irradiation in 3 hours, can remove formaldehyde 60% or so, then through 9 hours in 5PPM
After (no light), 96% or more formaldehyde can remove.
Example 3:
Using glass as substrate, first layer reflection layer 2 is coated on substrate glass substrate 1, is dried at a temperature of 120 DEG C, it is thick
Degree is 3 microns；Again by second layer light accumulation of energy layer 3(blue green light) it is coated on 2 surface of first layer reflection layer, at a temperature of 120 DEG C
Drying, with a thickness of 50 microns；Last third layer photocatalysis layer 4 is coated on 3 surface of second layer light accumulation of energy layer, dries at 120 DEG C,
With a thickness of 1 micron.This glass applies laminated film, under natural light or light-illuminating, has after absorbing light photon energy
The sustainable organic matter to adsorption includes that formaldehyde etc. plays photo-catalysis function and the functions such as decomposing organic matter, sterilization.Such as in sky
Concentration of formaldehyde, through light (LED white light, power 20W) irradiation in 1 hour, can remove formaldehyde 80% or so, then pass through in 10PPM in gas
After 5 hours (no lights), 98% or more formaldehyde can remove.
Claims (7)
1. a kind of high efficiency photon accumulating type air cleaning laminated film, comprising: matrix (1), reflection layer (2), light accumulation of energy layer
(3) and photocatalysis layer (4), it is characterised in that: the upper surface of matrix (1) is coated with reflection layer (2), reflection layer (2) it is upper
Surface is coated with light accumulation of energy layer (3), and the smooth accumulation of energy layer (3) is the patterned structures of cube, between each light storage cube
There are non-reflective gaps, are coated with photocatalysis layer (4) in the upper surface of light accumulation of energy layer (3), the photocatalysis layer (4) is by little particle
It piles up to form the film containing hole shape.
2. a kind of high efficiency photon accumulating type air cleaning laminated film according to claim 1, it is characterised in that: described
Reflection layer (2) with a thickness of 1 ~ 20 micron, light accumulation of energy layer (3) with a thickness of 1 ~ 60 micron, photocatalysis layer (4) with a thickness of
0.1 ~ 2 micron.
3. a kind of high efficiency photon accumulating type air cleaning laminated film according to claim 1, it is characterised in that: described
Matrix (1) can be wall, furniture, plastics, metal.
4. the preparation side based on a kind of any high efficiency photon accumulating type air cleaning laminated film of claim 1 ~ 3
Method, it is characterised in that: prepared in accordance with the following steps:
Step 1: preparing reflection layer (2)；
Step 2: reflection layer (2) are coated in the upper surface of matrix (1), room temperature or 10 ~ 150 DEG C at a temperature of dry；
Step 3: preparing light accumulation of energy layer (3)；
Step 4: light accumulation of energy layer (3) is coated in the upper surface of reflection layer (2), room temperature or 10 ~ 50 DEG C at a temperature of dry；
Step 5: preparing photocatalysis layer (4)；
Step 6: photocatalysis layer (4) are coated in the upper surface of light accumulation of energy layer (3), room temperature or 10 ~ 150 DEG C at a temperature of dry in the air
It is dry, obtain high efficiency photon accumulating type air cleaning laminated film；
The preparation step for preparing reflection layer (2) is as follows:
Using acrylic resin, polyurethane, epoxy, silicone resin as parent, by the TiO of core-shell structure2@SiO2Or TiO2@
Al2O3Parent is added in composite particles, and is uniformly dispersed, the TiO2@SiO2Or TiO2@Al2O3 composite particles and parent mix
Ratio is 5 ~ 30%(wt), thickness is formed at 1 ~ 20 micron using techniques such as spraying, roller coating, blade coating, inkjet printing, silk-screen printings
Film in range, as reflection layer (2)；
The preparation step for preparing light accumulation of energy layer (3) is as follows:
Using polyacrylic resin, polyurethane, epoxy, silicone resin lotion as parent, long-afterglow fluorescent particle is mixed
Lotion is simultaneously uniformly dispersed, and the ratio of mixing of the long-afterglow fluorescent particle and lotion is 5 ~ 50%(wt), using spraying, roller coating, scrape
The techniques such as painting, inkjet printing, silk-screen printing form film of the thickness in 1 ~ 60 micron range, as light accumulation of energy layer (3)；
The preparation step for preparing photocatalysis layer (4) is as follows:
Using polyacrylic resin, polyurethane, epoxy, siloxanes lotion as parent, by the gold with visible light catalytic function
Belong to oxide and mixes nano-TiO2, SnO, at least one of ZnO particle lotion is added, and is uniformly dispersed, it is described have it is visible
The metal oxide of photo-catalysis function mixes nano-TiO2, SnO, ZnO particle and lotion ratio of mixing be 0.1 ~ 5%(wt), adopt
Film of the thickness in 0.1 ~ 2 micron range is formed with techniques such as spraying, roller coating, blade coating, inkjet printing, silk-screen printings, as
Photocatalysis layer (4).
5. the preparation method according to claim 4, it is characterised in that: the TiO of the core-shell structure2@SiO2Or TiO2@
Al2O3The size of composite particles is in TiO in 200 ~ 400 nanometer ranges2One layer is coated using sol gel process on particle
SiO2Or Al2O3Film be formed by, the SiO2Or Al2O3Film thickness be 5-50 nanometers.
6. the preparation method according to claim 4, it is characterised in that: the fluorescent material of the long-afterglow fluorescent particle includes
At least one of blue, bluish-green, green, yellowish green, orange, red, the size of the long-afterglow fluorescent particle is in 1-30 micron range, institute
Stating blue is CaAl2O4:Eu2+, Sr2MgSi2O7, Sr2MgSi2O7:Eu2+,Dy3+；
Green is SrAl2O4:Eu2+；Sr(Al1-xBx)2O4:Eu2+；(Sr,Eu,Dy)0.95±x(Al,B)2O3.95±x；(Sr,Eu,
Dy)4-x(Al,B)14O25-x；
Yellow green is SrAl2O4:Eu2+,Dy3+, Sr(Al1-xBx)2O4:Eu2+,Dy3+；
Yellow is CaSi2O2N2；
Orange is Sr3Al2O5Cl2；
Red is Y2O3S:Eu3+,Mg2+,Ti4+；Y2O3S:Sm3+；Y2O3:Eu3+,Dy3+; CaO:Eu3+；Mg2SiO4:Dy3+,Mn2+；
Ca2Si5N8:Eu2+, R3+(R3+=Dy3+,Nd3+,Gd3+,Sm3+)；ATiO3:Pr3+, A=Ca,Sr,Ba 。
7. the preparation method according to claim 4, it is characterised in that: the metal oxidation with visible light catalytic function
Object mixes nano-TiO2, SnO, the element mixed in ZnO particle be in H, C, N, F, Fe, Cu, Ag, Au, Pt, Ni, W, Mo, Mn
At least one, the ratio of mixing of above-mentioned element and metal oxide is 0.1 ~ 2%(atm.).
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