CN1186123C - Multi-waveband photocatalytic material, preparation method thereof and air-purifying exposed wall coating composition - Google Patents
Multi-waveband photocatalytic material, preparation method thereof and air-purifying exposed wall coating composition Download PDFInfo
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- CN1186123C CN1186123C CNB021594228A CN02159422A CN1186123C CN 1186123 C CN1186123 C CN 1186123C CN B021594228 A CNB021594228 A CN B021594228A CN 02159422 A CN02159422 A CN 02159422A CN 1186123 C CN1186123 C CN 1186123C
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Abstract
The present invention discloses a multiple wave band light catalyzed material which can be catalyzed by infrared light, ultraviolet light, visual light or a trace amount of natural radiation with greatly improved efficiency of light catalyzing, a method for preparing the multiple wave band light catalyzed material, and an outer wall coating compound which contains the multiple wave band light catalyzed material and can effectively enhance the efficiency of light catalyzing and has the function of air purification. The multiple wave band light catalyzed material is prepared from 100 weight portions of layered substance with nanometer structure and 150 to 400 weight portions of light active substance by the following steps: preparing a solution of rare earth element with varied valency; immersing the laminar substance; replacing interlaminar sodium ions with rare earth ions or rare earth complex ions by an ion exchange method and combining the obtained ions with a mineral with polarity.
Description
Technical field
The invention belongs to building material field, be specifically related to a kind of catalysis material that is used for functional exterior coating, its preparation method, and the exterior wall coating composition that contains this catalysis material.
Background technology
Fujishima in 1972 and Honda find that the phenomenon of optically catalytic TiO 2 decomposition water indicates new era of multiphase photocatalysis, and after this, the conductor photocatalysis technology is widely used in fields such as chemical industry, building materials, weaving, environmental protection, existing 30 years so far.States such as Japan, America and Europe drop into all that huge fund conducts a research and development, and promote its industrialization energetically.Japan is maximum about the patent of photocatalysis technology, focuses on sterilization, air cleaning, from aspects such as cleanings; The America and Europe focuses on that carcinogenic substance is removed in the contaminated underground water, sewage wastewater processing, bay waste oil disposal, atmosphere pollution processing etc.; In China, research mainly concentrates on the aspects such as advanced treating of air cleaning, low concentration high toxicity contaminant water.Also there is research various countries to nano-photo catalytic coating, have had product to be applied to hospital, tunnel, soundproof wall and dwelling house etc., and other products of using photocatalysis technology also have tens of kinds.The relevant patent in the whole world has surpassed more than 1000 at present, but also among increasing.Yet existing technology, photocatalysis efficiency is low under the visible light condition, as " the purification NO of Mitsubishi Material (strain) company exploitation
XThe function road brick " though founded the factory and put into production, its purification efficiency is lower, cost is more expensive, also fails to obtain to promote.
Photocatalysis technology is applied in the coating so that coating has air-cleaning function, two difficult problems are arranged: one, photocatalysis efficiency is low under the visible light condition; Two, if be applied to organic coating,, can react with organic coating film because the hydroxyl radical free radical that catalysis material produces has strong oxidizing property, destroy coating structure, be coated with membrane lifetime thereby reduce, so the exterior coating that purifies air at present is based on inorganic coating.
Summary of the invention
The purpose of this invention is to provide a kind of multiband light catalysis material that photocatalysis effect and photocatalysis efficiency improve greatly that under infrared, ultraviolet, visible light or micro-natural radiation condition, all has.
Another object of the present invention provides a kind of preparation method of above-mentioned multiband light catalysis material.
A further object of the present invention provides and contains above-mentioned multiband light catalysis material, can effectively improve photocatalysis efficiency, has the exterior wall coating composition of air-cleaning function.
For achieving the above object, multiband light catalysis material provided by the invention is assembled by 100 weight portion layered nano-structure materials and 150-～400 weight portion optical active substances.
Above-mentioned multiband light catalysis material, layered nanostructured material are that interlamellar spacing is nano level zeolite or bentonite or its mixing.
Above-mentioned multiband light catalysis material, its for layered nano-structure material and optical active substance assembling back with the polar mineral tourmaline or/and quartz porphyry mix.
Above-mentioned multiband light catalysis material, described optical active substance are the changeable valence rare earth element; Described changeable valence rare earth element is selected from Ce
4+, Ce
3+, Pr
3+, La
3+, Sm
3+, Eu
3+, Nd
3+In rare earth ion or the rare earth complex ion two or more.
Above-mentioned multiband light catalysis material, described optical active substance are the changeable valence rare earth element and further are assembled in nano semi-conductor metal oxide in the nanometer laminated structure material; Described nano semi-conductor metal oxide is one or more in titanium dioxide, zinc oxide, zinc sulphide, tin oxide, di-iron trioxide, the tungsten oxide.
The present invention provides a kind of method for preparing the multiband light catalysis material simultaneously, comprises the steps:
1). described optical active substance changeable valence rare earth element is made solution, soak stratiform nanostructure matter, the interlayer sodium ion is replaced with rare earth ion or rare earth complex ion with ion-exchange;
2). material after the assembling of step 1) is mixed with nano semiconductor material and polar mineral, obtain the multiband light catalysis material.
The present invention also provides the air cleaning that contains multiband light catalysis material exterior wall coating composition, comprises:
Base-material-film forming matter: one or more in polyurethane, acrylate, silicon third, phenylpropyl alcohol, Ludox, the white cement, 30 ~ 65 weight portions;
Filler: at least a in lithopone, superfine talcum powder, ultrafine heavy calcium, diatomite, titanium dioxide, wollastonite in powder, the kaolin, 20 ~ 50 weight portions;
Catalyst: multiband light catalysis material, 1 ~ 15 weight portion;
Auxiliary agent: at least a in dispersant, coalescents, thickener, defoamer, levelling agent, pH value conditioning agent, the anticorrisive agent, 1 ~ 5 weight portion; And
Water: 10 ~ 40 weight portions.
Adopt technique scheme, the multiband light catalysis material that the present invention proposes is characterised in that and adopts multiple powder catalysis material that its energy gap size forms certain distribution, and the multi-wavelength is had absorption.Polar material has bigger absorption to infrared light in addition, and the effect of rare earth oxide or ion pair light is also comparatively responsive.Owing to utilize package technique, assembly multiple optical active substance rare earth element, but and complex group luminous intensity distribution reactive metal oxides, make that material all has the photocatalysis effect under infrared, ultraviolet, visible light or micro-natural radiation condition and photocatalysis efficiency improves greatly.The present invention mixes exterior coating with the multiband light catalysis material, thereby makes exterior coating have preferably air-cleaning function and do not influence its traditional performance.Adopt technique scheme, the multiband light catalysis material that the present invention proposes, owing to utilize package technique, assembly multiple optical active substance rare earth element, but and complex group luminous intensity distribution reactive metal oxides, make that material all has the photocatalysis effect under infrared, ultraviolet, visible light or micro-natural radiation condition and photocatalysis efficiency improves greatly; The present invention mixes exterior coating with the multiband light catalysis material, thereby makes exterior coating have preferably air-cleaning function and do not influence its traditional performance.
Description of drawings
Fig. 1 prepares multiband light catalysis material method schematic diagram for the present invention;
Fig. 2 detects hydroxyl radical free radical testing result figure for multiband light catalysis material of the present invention with electron spin resonance.
The specific embodiment
The present invention's design at first will be in the layered nano-structure material, and assembling has photoactive material.
The selection of optical active substance:
Choosing of rare earth element: the 4f orbital electron of rare earth element is close with the 6s electron energy level, thereby makes the coordination of rare earth element produce changeability, and the electronics of its 4f subgrade can play the effect of " reserve chemical bond " or " residue valence ".The present invention utilizes the electronics that shifts in the rare earth element variation of valence process to activate and participate in photochemical reaction, reduces the hydrone degree of association, promotes hydroxyl radical free radical to produce.Therefore, during design catalyst chemical composition, selecting the changeable valence rare earth element is optical active matter.Consider the photochemistry quantum yield and realize photo-catalysis function in the multiband light scope, rare earth element is preferably Ce
4+, Ce
3+, Pr
3+, La
3+, Sm
3+, Eu
3+, Nd
3+Deng in two or more.
Choosing of Nano semiconductor powder: semi-conducting material when especially reaching nanoscale, can show great photolytic activity under ultra-fine situation.Selecting the bigger nano semiconductor material purpose of photolytic activity for use is in order to increase the absorption photon ability of material, to improve photocatalysis efficiency.Preferred semiconductor powder is one or more of nano titanium oxide, zinc oxide, zinc sulphide, tin oxide, di-iron trioxide, tungsten oxide etc.The energy gap of these materials is incomplete same, is used in combination to increase absorption spectrum ranges.
In addition, the present invention also uses polar mineral, and polar mineral is optional with tourmaline or quartz porphyry.
In the above-mentioned three class materials, can separately rare earth element be assembled in by ion exchange technique becomes the multiband light catalysis material in the layer structure material; Also the layer structure material after the assembling can be mixed into the multiband light catalysis material with polar mineral again; Can also be earlier by ion exchange technique with changeable valence rare earth ion intercalation in layer structure material, mix the Nano semiconductor powder then, mix polar mineral again, assemble out the multiband light catalysis material.
The layered nano-structure material that the present invention selects for use is meant that the interlamellar spacing of material is nano level material, is specifically as follows bentonite, zeolite or its combination.
Concrete assemble method, with compound assembling rare earth element and nano-metal-oxide is that example is done an explanation: referring to Fig. 1, montomorillonite is bentonitic key component, has layered nano-structure, at first rare earth ion is mixed stirring with montmorillonite, guarantee that changeable valence rare earth is in ionic state for a long time, sodium ion between bentonite bed is replaced with rare earth ion or rare earth complex ion (wherein minimum part rare earth becomes oxide, but does not reduce the effect of rare earth itself) with ion-exchange process; Further add metal as the presoma ion, add thermal agitation and drying after, again with in the nano semiconductor photochemical catalyst insert layer; Continue heating, further strengthen the montomorillonite interlamellar spacing, catalyst mixes with montomorillonite to form assembles catalysis material.
Utilize above-mentioned multiband light catalysis material, can prepare air cleaning exterior wall composite dope.The prescription comprise base-material, filler, catalyst, auxiliary agent and water, in the prescription and since admixture the multiband light catalysis material, filler wherein and emulsion will be considered hydrophobicity.Concrete:
Base-material-film forming matter can be selected one or more in polyurethane, acrylate, silicon third, phenylpropyl alcohol, Ludox, the white cement etc. for use;
Filler can select for use lithopone, superfine talcum powder, ultrafine heavy calcium, diatomite, titanium dioxide, wollastonite in powder, kaolin etc. wherein at least a;
Catalyst is a multiband light catalysis material of the present invention;
Auxiliary agent is that dispersant, coalescents, thickener, defoamer, levelling agent, pH value conditioning agent, anticorrisive agent etc. are wherein at least a, and wherein, available material is respectively:
Dispersant: 923, the modest company of Taiwan moral; EFKA-44, Dutch EFKA company; P-19, Shanghai coating research institute etc.;
Coalescents: BK-2 coalescents, Linan, Hangzhou coating additive factory; Texanol ester alcohol, U.S. Eastman company; Propane diols butyl ether etc.;
Thickener: methylcellulose; Hydroxyethylcellulose; VD-S, German Henkel company etc.;
Defoamer: ethanol; Tributyl phosphate; Defoamer T, German Bayer company etc.;
Levelling agent: BYKETOL-OK, German BYK company; Perenol E1, German Henkel company; TegoFlow 300, German Tego company etc.;
PH value conditioning agent: ammoniacal liquor; Sodium hydroxide solution; Glacial acetic acid etc.;
Anticorrisive agent: the sky holds up-601, the Beijing Tianqing Chemical Co., Ltd; DFX, Britain NIPA company; TN-CRL, south, Shaoxin City chemical industry Co., Ltd etc.
Among the present invention, light-catalyzed reaction can take place and produce hydroxyl radical free radical in semiconductor under multiple wave band (from infrared to ultraviolet) light action, hydroxyl radical free radical has strong oxidizing property, can react with nitrogen oxide, sulfur dioxide, hydrogen sulfide, ammonia, most organic pollution, reach the purpose that purifies air.Changeable valence rare earth all has the photocatalysis activation on different wave lengths such as ultraviolet light, visible light, make catalyst all have photocatalysis performance preferably under infrared, ultraviolet, visible light and micro-natural radiation condition, thereby have the multiband light catalysis characteristics.Mixed polar mineral with increase physics adsorbance, and then the catalytic decomposition pollutant.The air cleaning process of air cleaning exterior wall composite dope is first physical absorption pollution gas, again its catalytic oxidation is acid (is nitric acid, sulfuric acid as nitrogen oxide, oxidizing sulfur dioxide) or carbon dioxide and water (as the oxidation of VOC).The not only adsorbable pollution gas of polar mineral.The dust in the absorbed air (being mainly metal oxide or inorganic salts) also, dust forms dirt with the acid effect, is accumulated in the hydrophobic coating surface, can be from clean through rain drop erosion.
Embodiment one: assembling multiband light catalysis material
1). 30 gram bentonites are added in the 100 gram aqueous solution, soaked 12 hours; 2). 40 gram cerous nitrates, 15 gram praseodymium oxides and 25 gram neodymium nitrates are made into the 180 gram aqueous solution; With 1) step and 2) solution mixing and stirring that step obtains, 220 ℃ of oven dry obtain this routine photochemical catalyst.
Embodiment two: assembling multiband light catalysis material
1). 30 gram bentonites are added in the 100 gram aqueous solution, soaked 12 hours; 2). 60 gram cerous nitrates, 20 gram neodymia are made into the aqueous solution with 1) step and 2) the solution mixing and stirring of step acquisition, 220 ℃ of oven dry; 3) preparation 20 gram rutile type nano titanic oxide gels are with step 2) obtain powder and fully mix, obtain this routine catalysis material.
Embodiment three: assembling multiband light catalysis material
1). 30 gram bentonites are added in the 100 gram aqueous solution, soaked 12 hours; 2). 20 gram praseodymium oxides, 60 gram cerous nitrates and 20 gram nano zine oxides are made into the 180 gram aqueous solution; With 1) step and 2) solution mixing and stirring that step obtains, after 220 ℃ of oven dry, mix with 20 gram tourmaline again, obtain this routine catalysis material.
Embodiment four to embodiment eight: assembling multiband light catalysis material.
Adopt following table 1 assembly, according to embodiment one to three method be prepared from.
The component of table 1: embodiment four to embodiment eight
| Component (g) | Embodiment four | Embodiment five | Embodiment six | Embodiment seven | Embodiment eight | |
| Rare earth element | Cerous nitrate | 50 | 50 | |||
| Praseodymium oxide | 100 | 90 | ||||
| Lanthanum chloride | 50 | 70 | 90 | |||
| Samarium oxide | 50 | 20 | ||||
| Europium oxide | 100 | 60 | 50 | |||
| Neodymium nitrate | 120 | |||||
| Metal oxide | Titanium dioxide | 80 | 30 | |||
| Zinc oxide | 90 | |||||
| Zinc sulphide | 20 | |||||
| Tin oxide | 100 | |||||
| Di-iron trioxide | 30 | 50 | ||||
| Tungsten oxide | 120 | 20 | ||||
| Polar mineral | Quartz porphyry | 50 | 30 | |||
| Tourmaline | 60 | 10 | 10 | |||
| Stratified material | Bentonite | 100 | 60 | 30 | ||
| Zeolite | 100 | 100 | 40 | 70 | ||
The product multiband light catalysis material of the foregoing description can all have the photocatalysis effect under infrared, ultraviolet, visible light or micro-natural radiation condition.Detection method is: with the existence of ESR (electron spin resonance) experiment detection hydroxyl radical free radical, testing result as shown in Figure 2.
Testing result shows: the multiband light catalysis material can produce hydroxyl radical free radical under infrared, ultraviolet, visible light or micro-natural radiation condition, promptly all have the photocatalysis effect.
Embodiment nine: assembly air cleaning exterior coating
In 241.3 gram water, add dispersant P-19/10 gram, coalescents Texanol ester alcohol 18 grams, defoamer ethanol 2 grams, dispersed with stirring limit, limit adds titanium dioxide 62.5 grams, superfine talcum powder 160 grams, ultrafine heavy calcium 40 grams, catalyst 100 grams of experimental example five, fully disperse, make white slurry, add pure-acrylic emulsion 350 grams again, defoamer tributyl phosphate 0.2 gram, thickener methylcellulose 6 grams ,-601/10 gram is held up in the anticorrisive agent sky, makes exterior coating 1000 grams.
Embodiment ten embodiment 14: assembly air cleaning exterior coating
Adopt following table 2 assembly, formulated according to embodiment nine same procedure.
Table 2: embodiment ten to embodiment 14 air cleaning exterior coating assembly
| Component (g) | Embodiment ten | Embodiment 11 | Embodiment 12 | Embodiment 13 | Embodiment 14 | |
| Base-material | Polyurethane | 650 | ||||
| Acrylate | 150 | |||||
| Phenylpropyl alcohol | 300 | |||||
| Silicon third | 330 | |||||
| Ludox | 150 | |||||
| White cement | 300 | 200 | ||||
| Filler | Lithopone | 200 | ||||
| Superfine talcum powder | 110 | 60 | 200 | 100 | ||
| Ultrafine heavy calcium | 200 | 180 | ||||
| Titanium dioxide | 50 | 30 | 60 | 50 | 60 | |
| Diatomite | 100 | |||||
| Kaolin | 80 | 50 | ||||
| Wollastonite in powder | 50 | 51.5 | ||||
| Catalyst | Embodiment two | 150 | ||||
| Embodiment four | 10 | 30 | ||||
| Embodiment five | 15 | |||||
| Embodiment eight | 75 | |||||
| Auxiliary agent | Dispersant | P-19 3 | P-19 3.5 | EFKA-44 5 | 923 15.3 | P-19 7.3 |
| Coalescents | BK-2 1.5 | BK-2 4.5 | Texanol 2.2 | BK-2 20 | Propane diols butyl ether 6.4 | |
| Thickener | Hydroxyethylcellulose 2 | VD-S 20 | Methylcellulose 1 | Hydroxyethylcellulose 8 | ||
| Defoamer | Ethanol 3 | Tributyl phosphate 4 | Defoamer T 0.1 | Ethanol 3.6 | ||
| Anticorrisive agent | It holds up-601,1 | DFX，3 | It holds up-601,1 | TN-CRL，1 | It holds up-601,6 | |
| PH value conditioning agent | Ammoniacal liquor, 3 | Ammoniacal liquor, 2 | ||||
| Levelling agent | Perenol E1 2 | Tego Flow 300 2.8 | Perenol E1 2 | |||
| Water | 114.5 | 134 | 400 | 100.6 | 125.2 | |
Experiment one: coating air cleaning test: it is on 0.5 square metre the glass plate that 100 gram air cleaning exterior coatings are evenly coated in area, puts into 1 cubic metre of artificial climate storehouse (20 ℃ of temperature, relative humidity 40%) after 24 hours, and the feeding initial concentration is a
0Pollution gas, record final concentration a after 24 hours
1, in contrast, feeding initial concentration in 1 cubic metre of artificial climate storehouse in (20 ℃ of temperature, relative humidity 40%) is a
0Pollution gas, record final concentration a after 24 hours
2, then coating purifying rate L is:
L＝(a
2-a
1)/a
0
Test result: the NO that in the artificial climate storehouse, adds 2ppm under the natural daylight condition
2, behind the use embodiment of the invention nine coating, NO in the air after 24 hours
2Concentration drops to 0.1ppm; Control experiment is reduced to 1.9ppm from 2ppm.Utilize above-mentioned data computation purifying rate to reach 90%.
Use same procedure to measure the coating of embodiment ten to embodiment 14, purifying rate all can reach 90%.Coating of the present invention is the nitrogen oxide in the absorbed air effectively, has the function that purifies air.
Test two: the illumination of different wave length is penetrated down, the air purification effect of exterior coating
Method: the purifying rate of under infrared ray, ultraviolet ray, no optical condition, surveying coating by test one method;
The result: purifying rate is respectively under infrared ray, ultraviolet ray, no optical condition: 80%, 85%, 73%, prove that coating of the present invention under the illumination of different wave length is penetrated, all has air purification effect.
Claims (8)
1, a kind of multiband light catalysis material is characterized in that: assembled by 100 weight portion layered nano-structure materials and 150～400 weight portion optical active substances; Layered nanostructured material is that interlamellar spacing is nano level zeolite or bentonite or its mixing, and described optical active substance is the changeable valence rare earth element.
2, multiband light catalysis material according to claim 1 is characterized in that: its for layered nano-structure material and optical active substance assembling back with the polar mineral tourmaline or/and quartz porphyry mix.
3, multiband light catalysis material according to claim 1 is characterized in that: described changeable valence rare earth element is selected from Ce
4+, Ce
3+, Pr
3+, La
3+, Sm
3+, Eu
3+, Nd
3+In rare earth ion or the rare earth complex ion two or more.
4, according to the arbitrary described multiband light catalysis material of claim 1 to 3, it is characterized in that: described optical active substance is the changeable valence rare earth element and further is assembled in nano semi-conductor metal oxide in the nanometer laminated structure material.
5, multiband light catalysis material according to claim 4 is characterized in that: described nano semi-conductor metal oxide is one or more in titanium dioxide, zinc oxide, zinc sulphide, tin oxide, di-iron trioxide, the tungsten oxide.
6, multiband light catalysis material according to claim 4 is characterized in that: described changeable valence rare earth element is selected from Ce
4+, Ce
3+, Pr
3+, La
3+, Sm
3+, Eu
3+, Nd
3+In rare earth ion or the rare earth complex ion two or more.
7, a kind of method for preparing the arbitrary described multiband light catalysis material of claim 1 to 6 is characterized in that, comprises the steps:
1). described optical active substance changeable valence rare earth element is made solution, soak stratiform nanostructure matter, the interlayer sodium ion is replaced with rare earth ion or rare earth complex ion with ion-exchange;
2). material after the assembling of step 1) is mixed with nano semiconductor material and polar mineral, obtain the multiband light catalysis material.
8, contain the air cleaning exterior wall coating composition of the arbitrary described multiband light catalysis material of claim 1 to 6, it is characterized in that, comprise following component:
Base-material-film forming matter: one or more in polyurethane, acrylate, silicon third, phenylpropyl alcohol, Ludox, the white cement, 30 ~ 65 weight portions;
Filler: at least a in lithopone, superfine talcum powder, ultrafine heavy calcium, diatomite, titanium dioxide, wollastonite in powder, the kaolin, 20 ~ 50 weight portions;
Catalyst: multiband light catalysis material, 1 ~ 15 weight portion;
Auxiliary agent: at least a in dispersant, coalescents, thickener, defoamer, levelling agent, pH value conditioning agent, the anticorrisive agent, 1 ~ 5 weight portion; And
Water: 10 ~ 40 weight portions.
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| CN100369668C (en) * | 2005-07-06 | 2008-02-20 | 河北工业大学 | Inorganic clay compound material, its preparation and use |
| CN102408755A (en) * | 2011-09-21 | 2012-04-11 | 陈良英 | Method for processing dye |
| CN102658209B (en) * | 2012-05-08 | 2014-03-26 | 上海灏清新能源科技有限公司 | Novel high-activity energy-saving thermal-insulating air purifying nonmaterial and preparation method thereof |
| CN103055914A (en) * | 2012-11-30 | 2013-04-24 | 姜英杰 | Preparation method of composite photocatalytic oxidation nano titanium dioxide preparation |
| CN104629548B (en) * | 2015-02-05 | 2019-08-06 | 洛阳理工学院 | A kind of interior wall coating and preparation method thereof with air-cleaning function |
| CN110343429A (en) * | 2018-11-11 | 2019-10-18 | 广东中盛新型环保科技有限公司 | A kind of nano rare earth dope for inner wall of architecture and preparation method thereof |
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