CN102284289B - Tin dioxide load-type nanometer cold catalyst for purifying air - Google Patents
Tin dioxide load-type nanometer cold catalyst for purifying air Download PDFInfo
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Abstract
The invention relates to a tin dioxide load-type nanometer cold catalyst which is used for thoroughly removing formaldehyde of air inside a car at a room temperature and has high-efficient sterilization performance, which relates to the field of catalysis, microorganism and environment protection. The tin dioxide load-type nanometer cold catalyst is characterized in that: honeycomb ceramic is adopted as a carrier, previous channel silver-doped hollandite crystal structural tin oxide (SnO2) is adopted as a basic body, and back-loading silver-golden system (Ag-Au) is adopted as an active constituent. The weight ratio of the Ag-Au system and the doped SnO2 is 0 to 10 percent, and the weight ratio of the Ag in the Ag-Au system is 0 to 100 percent. The tin dioxide nanometer cold catalyst can high efficiently, stably and thoroughly eliminate the formaldehyde in the air in a real environment of normal temperature and normal humidify, also has long validity, high efficiency and stable wide antibacterial function, has no side effect on the human body, and can be widely used for preparing different air purifiers and different microorganism processing devices to eliminate formaldehyde and to kill the bacteria.
Description
Technical field
The present invention a kind ofly can thoroughly remove airborne formaldehyde in chamber/car and have the cold catalyst of stannic oxide nanometer of high-efficiency antimicrobial performance for room temperature, relates to catalysis, microorganism and field of environment protection.The cold catalyst of stannic oxide nanometer of the present invention can be removed up hill and dale airborne formaldehyde by efficient stable in the true environment of ambient temperature and moisture, has long-acting, efficient and stable broad-spectrum antiseptic ability simultaneously, and to human body without any adverse side effect
The invention still further relates to above-mentioned nanometer cold catalyst preparation method.
The invention still further relates to that above-mentioned nanometer cold catalyst is applied to prepare various air purifiers and microbial treatment device is removed formaldehyde and killing pathogenic bacteria simultaneously, be particularly useful for automobile-used air purifier.
Background technology
Formaldehyde is a kind of main indoor air pollutants, and its harm has been subject to people and has paid close attention to widely.The sanitary standard (maximum permissible concentration) of China's regulation formaldehyde in indoor air in the < < IAQ standard > > (GB/T18883-2002) promulgating for 2002 is respectively 0.10mg/m
3.Therefore the formaldehyde of, removing in room air has important meaning.Purification method can be divided into absorption method, chemical reaction method, plasma technique, photocatalytic method and catalysis method roughly, and wherein catalysis method is a kind of long-acting method.US Patent No. 5585083 has been invented a kind of Au/SnO
2catalyst is removed the method for formaldehyde in air, and catalyst is not having under extra energy input and-5～25 ℃ of conditions, and the airborne oxygen of take is completely oxidized to carbon dioxide and water by formaldehyde as oxidant.But the Au content (12wt%) that catalyst is high causes the expensive of catalyst.Rare earth oxide or the metal composite oxide catalyst of gold-supported for Chinese patent CN1698932, at 80～100 ℃ of temperature, PARA FORMALDEHYDE PRILLS(91,95) can obtain good effect.
The cold catalyst of nano-antibacterial because antimicrobial efficiency is high, the advantage such as good stability, nonpoisonous and tasteless and broad spectrum activity has wide market.Being usually used in the cold catalyst of nano-antibacterial is mainly loaded Ag (Ag
2o), the serial inorganic matter such as CuO or ZnO, because it is stronger that silver is antibacterial ability, Grain-positive, negative bacterium and mould and saccharomycete are had to good effect, and security is good, human body is not produced to toxic action, so current business-like antiseptic is mainly silver is antibacterial cold catalyst, and be widely used in the Related products such as coating, plastics, rubber and fabric.
Think that at present silver is that antibacterial cold catalyst mainly contains two kinds of mechanism: silver ion oozes out mechanism and catalytic activation oxygen mechanism.It is to be that antibacterial cold catalyst oozes out silver ion Ag by silver that silver ion oozes out mechanism
+with microorganism combination, destroy cell synzyme, electric transmission system, respiratory system or material transfer system etc., cause microbial death.The cold catalyst of current most inorganic antibacterial is all to adopt silver ion to ooze out mechanism.As the SnAgZn compound system of CN1568704A invention, the nano SnO of CN1742583A invention
2, ZnO and Ag
2the silver-colored aluminum sulfate system of O system and US20090047311 invention etc.Mechanism is because need constantly to consume Ag like this
+so the service life of antiseptic, (durability) was decided by the content of antibacterial cold catalyst silver, finally because causing anti-microbial property, exhausting of silver lost efficacy.So ooze out the Ag of mechanism
+antiseptic, in service life and existing problems economically, can not adapt to the economic strategy of sustainable development.
Catalytic activation oxygen mechanism is mainly that silver atoms (comprising band portion positive charge Ag ion) can become active oxygen species (as O airborne oxygen activation in air
-, O
2 -or O
2 2-deng), or in liquid, activating solvent can be become to living radical (HO or RO, R represents organic matter etc.), these active oxygen species or the nonselective destroy microorganisms matrix of living radical energy, cause the death of microorganism.Such antiseptic is not selective to microorganism, thus there is broad-spectrum sterilization performance, because the mechanism based on catalysis, so bactericidal action does not consume noble silver, has long-lasting and stability.Therefore, the antibacterial cold catalyst of catalytic activation oxygen formula has the advantage that the antibacterial cold catalyst of silver ion permeable cannot be unrealistically compared.As carried metal silver on CN101187018A aluminium flake has regular structure; CN1857309A utilizes silver powder to make the spray that women uses has good effect to various bacterium fungies etc.; US20090130181 with UV by Ag
+on multiple natural with synthetic cold catalyst, in-situ reducing becomes metal A g, has efficient and long-acting anti-microbial property etc.
The object of this invention is to provide a kind of have efficient room temperature removal formaldehyde and antibacterial monolithic devices nanometer cold catalyst and the preparation method and application of broad-spectrum long-acting simultaneously.
Summary of the invention
Object 1 of the present invention: provide a kind of while efficient room temperature to remove formaldehyde and the antibacterial monolithic devices nanometer cold catalyst of broad-spectrum long-acting.
Object 2 of the present invention: the preparation method that the antibacterial monolithic devices nanometer cold catalyst of preparation while efficient room temperature removal formaldehyde and broad-spectrum long-acting is provided.
Object 3 of the present invention: relate to above-mentioned nanometer cold catalyst and be applied to prepare the products such as various environmental protection, air pollutants improvement, medical treatment and health defence and coating, plastics, rubber and fabric.
The object of the invention is to be achieved through the following technical solutions:
Efficient room temperature provided by the invention is removed formaldehyde and the antibacterial monolithic devices nanometer cold catalyst of broad-spectrum long-acting, adopts following methods synthetic:
1. skeleton doping hollandite type SnO
2two kinds of preparation methods
(1) roasting method key step: by powder SnO
2or solubility pink salt, M salt (M=Zn
2+or Mg
2+), template and organic solvent be according to a certain amount of mixing, vigorous stirring mixes, at 100～150 ℃ of dry 1～24h, then at 800～1300 ℃ of roasting 1～36h, cooling rear washing, is dried and obtains skeleton doping hollandite type SnO at 200～500 ℃ of roasting 1～36h
2matrix.
(2) ion-exchange key step: by the skeleton doping hollandite type SnO of above-mentioned preparation
2matrix adds a certain amount of red fuming nitric acid (RFNA) ammonium (NH
4nO
3) forming suspension in the aqueous solution, ion-exchange 1～48h, filters, and at 100～150 ℃ of dry 1～24h, then at 200～400 ℃ of roasting 1～36h, as required, ion exchange procedure can repeat, and obtains part K in duct
+by H
+the skeleton doping hollandite type SnO replacing
2matrix.
2. duct Ag doping hollandite type SnO
2the preparation method of matrix.
(1) by the hollandite type SnO of skeleton doping
2matrix adds in a certain amount of aqueous solution and forms suspension.
(2) ammoniacal liquor of finite concentration (≤25wt.%) is added to liquor argenti nitratis ophthalmicus (AgNO
3) the middle silver-colored ammonia (Ag (NH that forms
3)
2 +) solution.
(3) under fierce stirring, by the hydrogen peroxide (H of finite concentration (≤30wt.%)
2o
2) and Ag (NH
3)
2 +solution is added dropwise to respectively above-mentioned skeleton doping hollandite type SnO simultaneously
2matrix suspension, aging 1～12h, then filters, washs, and at 100～150 ℃ of dry 1～24h, then at 200～800 ℃ of roasting 1～36h, obtains duct containing monatomic silver doping hollandite type SnO
2matrix.
3. honeycomb ceramic carrier loaded Ag
x(A)
y[M
zsn
8-z] O
16preparation method
(1) take the Ag of a certain amount of doping
x(A)
y[M
zsn
8-z] O
16matrix, adds a certain proportion of deionized water and adhesive.According to the requirement of viscosity and particle diameter, by the Ag of adhesive and doping
x(A)
y[M
zsn
8-z] O
16matrix mixing suspended emulsion high-speed stirred 1～24h, obtains the Ag of certain density doping
x(A)
y[M
zsn
8-z] O
16matrix slurries.
(2) adopt vacuum-negative pressure extraction technique by the Ag of above-mentioned doping
x(A)
y[M
zsn
8-z] O
16matrix slurries are coated on the ceramic honey comb of anticipating, and at 200～800 ℃ of roasting 1～36h, obtain carried with doped Ag
x(A)
y[M
zsn
8-z] O
16the cold catalyst of matrix.
4. Ag adulterates
x(A)
y[M
zsn
8-z] O
16the method of matrix loaded Ag-Au system, is characterized in that adopting gas phase reduction process or liquid phase reduction preparation:
(1) gas phase reduction process: by above-mentioned loaded Ag
x(A)
y[M
zsn
8-z] O
16the cold catalyst of monolithic devices (claim 6 preparation) is immersed in AgNO
3with nitroso diamines alloy (Au (NH
3)
2(NO
2)
2) or gold chloride (H
2auCl
6) in mixed solution, dry after at 200～400 ℃ of roasting 1～36h, then at H
2in atmosphere, at 200～400 ℃ of reduction 1～36h, or adopt the UV of certain wavelength and light intensity to irradiate 1～72h.
(2) liquid phase reduction: by loaded Ag
x(A)
y[M
zsn
8-z] O
16the cold catalyst of monolithic devices is immersed in finite concentration AgNO
3and Au (NH
3)
2(NO
2)
2or H
2auCl
6in mixed solution, then add reducing agent, as NaBH
4, formaldehyde, ethylene glycol, glucose or there is the organic matter of reducing property, react at a certain temperature 1～6h, dry after at 200～400 ℃ of roasting 1～36h.
The technology of the present invention effect
Technique effect of the present invention is that a kind of room temperature can thoroughly be removed airborne formaldehyde and have the feature of the monolithic devices nanometer cold catalyst of high-efficiency antimicrobial performance simultaneously: under unglazed existence, room temperature is often 0.010～50mg/m by concentration in oxidation air under wet condition
3formaldehyde change into nontoxic carbon dioxide and water; Mainly adopt the sterilization mechanism of catalytic activation oxygen formula, have the feature of efficiency height and good stability, can suppress and kill various germs, as Grain-positive and gram-negative bacteria etc., bacteriostasis (MIC) is in 1～600 μ g/mL scope.。
Advantage of the present invention
1. high efficiency and broad spectrum activity
Efficient room temperature of the present invention is removed formaldehyde and the antibacterial monolithic devices nanometer cold catalyst of broad-spectrum long-acting, adopts the method for catalysis, make cold catalyst not only PARA FORMALDEHYDE PRILLS(91,95) have outstanding removal ability but also have extremely strong anti-microbial property.
2. high stability and long-lasting
Antibacterial cold catalyst of the present invention has been abandoned the sterilization mechanism of adsorption technology and traditional silver ion permeable, adopt catalytic activation oxygen mechanism, formaldehyde remove and when antibacterial catalyst do not consume, have well long-lasting, very high stability and good economy, and to human body without any adverse side effect.
3. non-toxic and have no side effect
Efficient room temperature of the present invention is removed formaldehyde and the antibacterial monolithic devices nanometer cold catalyst of broad-spectrum long-acting, and when being applied to air cleaning or antimicrobial product, nontoxicity, does not have accessory substance carbon monoxide and formic acid and produce, rat half lethal dose LD
50> 2000mg/kg.
The specific embodiment
Embodiment mono-
The hollandite type SnO of duct argentiferous
2matrix (Ag
x(A)
y[M
zsn
8-z] O
16, A=K
+, M=Zn
2+or Mg
2+) preparation.
By powder SnO
2(P25), M salt (Zn (NO
3)
2or Mg (NO
3)
2), template potassium nitrate (KNO
3) and organic matter P123 according to a certain amount of mixing, vigorous stirring mixes, at 100～150 ℃ of dry 1～24h, then at 900 ℃ of roasting 36h, cooling rear washing, dry and obtain skeleton doping hollandite type SnO at 500 ℃ of roasting 24h
2matrix.
By above-mentioned hollandite type SnO
2matrix adds in a certain amount of aqueous solution and forms suspension.The ammoniacal liquor of finite concentration (≤25wt.%) is added to liquor argenti nitratis ophthalmicus (AgNO
3) the middle silver-colored ammonia (Ag (NH that forms
3)
2 +) solution.Under fierce stirring, by the hydrogen peroxide (H of finite concentration (≤30wt.%)
2o
2) and silver-colored ammonia (Ag (NH
3)
2 +) solution is added dropwise to respectively above-mentioned hollandite type SnO simultaneously
2matrix suspension, stirs aging 12h, then filters, washs, and at 110 ℃ of dry 24h, at 500 ℃ of roasting 6h, obtains Ag
x(A)
y[M
zsn
8-z] O
16 (x≤2; Y≤2; Z≤3).
XRD and HRTEM analytical proof Ag enter Hollandite type SnO
2the duct of matrix.
The performance test of catalyst is carried out on the fixed bed reactors of continuous-flow.Before catalyst performance test, catalyst is not done to any processing, fine catalyst, through compressing tablet, is pulverized the granular of making 0.25～0.50mm, then 0.5g granular is loaded in a glass tube, under the condition that is 50% in room temperature (20 ℃) and relative humidity, pass into containing 5.0mg/m
3the air of formaldehyde, wind speed is 1.5m/s.Reactor outlet gas detects with FSNR infrared spectrum analyser, trace gas analysis mass spectrograph and Aglient7890A gas chromatographicanalyzer simultaneously simultaneously.The results are shown in Table 1.
Anti-microbial property test is according to the JIS Z2801:2000 of Japanese Industrial Standards, and AnSnmicrobial products-Test for anSnmicrobial acSnvity and efficacy and the cold catalyst anti-microbial property of State Standard of the People's Republic of China GB/T21510-2008 < < nano inorganic method of testing > > carry out.Test result is as shown in table 1.
Embodiment bis-
Ag (K)
0.3[Zn
2sn
6] O
16the preparation of the cold catalyst of monolithic devices catalysis.Take a certain amount of Ag (K)
0.3[Zn
2sn
6] O
16, adding a certain proportion of deionized water and 30% silica adhesive, high-speed stirred 10h, obtains the Ag (K) of certain density doping
0.3[Zn
2sn
6] O
16slurries.Adopt vacuum-negative pressure extraction technique by the Ag (K) of doping
0.3[Zn
2sn
6] O
16slurries are coated on the ceramic honey comb of anticipating, and at 500 ℃ of roasting 12h, Ag (K) obtains adulterating
0.3[Zn
2sn
6] O
16the cold catalyst of monolithic devices catalysis.Be designated as " monolithic devices Ag (K)
0.3[Zn
2sn
6] O
16".
The formaldehyde performance test of the cold catalyst of monolithic devices catalysis is carried out on fixed bed.The three-dimensional of integral catalyst is 150*150*40mm
3, then pack in glass tube, under the condition that is 50% in room temperature (20 ℃) and relative humidity, pass into containing 5.0mg/m
3the air of formaldehyde, wind speed is 1.5m/s.Air purifier detects the concentration of exit gas simultaneously simultaneously with FSNR infrared spectrum analyser, trace gas analysis mass spectrograph and Aglient7890A gas chromatographicanalyzer.The results are shown in Table 1.
Anti-microbial property test is according to the JIS Z2801:2000 of Japanese Industrial Standards, and AnSnmicrobial products-Test for anSnmicrobial acSnvity and efficacy and the cold catalyst anti-microbial property of State Standard of the People's Republic of China GB/T21510-2008 < < nano inorganic method of testing > > carry out.Test result is as shown in table 1.
Table 1. duct is containing the Hollandite type SnO of Ag
2matrix (Ag
x(A)
y[M
zsn
8-z] O
16) test result.
athis value is the logarithm value of antibacterial activity (with reference to the JIS Z2801:2000 of Japanese Industrial Standards, AnSnmicrobial products-Test for anSnmicrobial acSnvity and efficacy)
Embodiment tri-
Doping Ag (K)
0.3[Zn
2sn
6] O
16matrix loaded Ag-Au system is prepared by gas phase reduction process: by above-mentioned loaded Ag (K)
0.3[Zn
2sn
6] O
16the cold catalyst of monolithic devices (claim 6 preparation) is immersed in AgNO
3and gold chloride (HAuCl
4) in mixed solution, dry after at 300 ℃ of roasting 4h, then at H
2in atmosphere, at 300 ℃ of reduction 4h, or adopt the UV of certain 254nm to irradiate 36h.By liquid phase reduction, prepared: by loaded Ag (K)
0.3[Zn
2sn
6] O
16the cold catalyst of monolithic devices is immersed in finite concentration AgNO
3and Au (NH
3)
2(NO
2)
2or H
2auCl
6in mixed solution, then add reducing agent NaBH
4, at room temperature react 4h, after being dried, at 300 ℃ of roasting 4h, remembering " Ag-Au/Ag (K)
0.3[Zn
2sn
6] O
16".The content process icp analysis of metal, wherein Ag-Au and doping Ag (K)
0.3[Zn
2sn
6] O
16matrix ratio is 0～10%, and the content of gold accounts for 0～100% of Ag-Au weight ratio.
The formaldehyde performance test of the cold catalyst of monolithic devices catalysis and antibacterial experiment are with embodiment bis-.Result shows, preparation method is little on experimental result impact, in Table 2.
Table 2.Ag-Au/Ag (K)
0.3[Zn
2sn
6] O
16test result.
athis value is the logarithm value of antibacterial activity (with reference to the JIS Z2801:2000 of Japanese Industrial Standards, AnSnmicrobial products-Test for anSnmicrobial acSnvity and efficacy)
Embodiment tetra-
Ag-Au/Ag (K)
0.3[Zn
2sn
6] O
16the preparation of the cold catalyst of catalysis (Au/Ag=3/7) is identical with embodiment tri-.
The performance test of catalyst stability experiment is with embodiment bis-, follow-on test time 120d, and the formaldehyde of entrance is 50mg/m
3, formaldehyde exit concentration is respectively 0.003mg/m
3.Anti-microbial property stability (life-span) test is according to the JIS Z2801:2000 of Japanese Industrial Standards, and AnSnmicrobial products-Test for anSnmicrobial acSnvity and efficacy and the cold catalyst anti-microbial property of State Standard of the People's Republic of China GB/T21510-2008 < < nano inorganic method of testing > > carry out.Antibacterial activity logarithm value: being 4.8 to Escherichia coli, is 4.1 to Staphylococcus auresu.
Claims (10)
1. the cold catalyst of stannic oxide nanometer, it is characterized in that adopting ceramic honey comb is carrier, the hollandite type crystal structure tin ash (SnO of first load duct silver-doped
2) matrix, back loading Yin-Jin system (Ag-Au); Doping hollandite type SnO
2the chemical general formula of matrix is expressed as Ag
x(A)
y[M
zsn
8-z] O
16, M=Zn
2+, Mg
2+; A=K
+, H
+; X≤2; Y≤2; Z≤3, [M
zsn
8-2] O
16represent hollandite type SnO
2skeleton form, Ag
x(A)
yrepresent SnO
2duct form; Ag-Au system and doping hollandite type SnO
2matrix weight ratio is 0～10%, does not wherein comprise 0; The weight ratio that Ag accounts for Ag-Au system is 0～100%, wherein 0 and 100% all except.
2. the cold catalyst of stannic oxide nanometer as described in claim 1, is characterized in that its preparation method is as follows:
(1) skeleton doping hollandite type SnO
2matrix preparation;
(2) at skeleton doping hollandite type SnO
2matrix carries out duct silver doping, obtains Ag
x(A)
y[M
zsn
8-z] O
16;
(3) by Ag
x(A)
y[M
zsn
8-z] O
16be coated on honeycomb ceramic carrier 80～150 ℃ of oven dry, 200～800 ℃ of roasting 1～36h;
(4) prepared by above-mentioned (3) to the hollandite type SnO of the duct silver doping of Supported Honeycomb Ceramics
2the outer surface of matrix is loaded Ag-Au cluster or nano particle again.
3. the cold catalyst of stannic oxide nanometer as described in claim 2, is characterized in that skeleton doping hollandite type SnO
2adopt the preparation of roasting-ion-exchange:
(1) roasting method key step: by powder SnO
2or solubility pink salt, zinc salt or magnesium salts, template and organic solvent are according to a certain amount of mixing, vigorous stirring mixes, at 100～150 ℃ of dry 1～24h, then at 800～1300 ℃ of roasting 1～36h, cooling rear washing, is dried and obtains hollandite type SnO at 200～500 ℃ of roasting 1～36h
2;
(2) ion-exchange key step: by the hollandite type SnO of above-mentioned preparation
2matrix adds a certain amount of red fuming nitric acid (RFNA) ammonium (NH
4nO
3) forming suspension in the aqueous solution, ion-exchange 1～48h, filters, and at 100～150 ℃ of dry 1～24h, then at 200～400 ℃ of roasting 1～36h, as required, ion exchange procedure can repeat, and obtains part K in duct
+by H
+the hollandite type SnO replacing
2.
4. the cold catalyst of stannic oxide nanometer as described in claim 3, is characterized in that skeleton doping hollandite type SnO
2preparation condition:
(1) powder SnO
2snO for tetragonal
2powder, solubility pink salt is butter of tin (SnCl
4), tin trichloride (SnCl
3), tin tetrafluoride (SnF
4), ethanol tin, stannic acid four butyl esters (Sn (OCH
2cH
2cH
2cH
3)
4) in one or more;
(2) concentration of zinc salt or magnesium salts is 0.1～5.0mol/L, it is characterized in that soluble zinc salt is zinc nitrate (Zn (NO
3)
2), zinc chloride (ZnCl
2) and zinc acetate (Zn (CH
3cOO)
2) in one or more; Solubility magnesium salts is magnesium nitrate (Mg (NO
3)
2), magnesium chloride (MgCl
2) and magnesium acetate (Mg (CH
3cOO)
2) in one or more, wherein the mol ratio of M salt and tin ion is between 0～0.4, and does not get 0;
(3) template is sylvite, and the mol ratio of template and total metal ion is between 1: 1 to 20: 1.
5. the cold catalyst of stannic oxide nanometer as described in claim 1, is characterized in that duct silver doping hollandite type SnO
2the preparation method of matrix is as follows:
(1) skeleton is adulterated hollandite type SnO
2add in a certain amount of aqueous solution and form suspension;
(2) ammoniacal liquor that is 25wt.% by concentration adds liquor argenti nitratis ophthalmicus (AgNO
3) the middle silver-colored ammonia (Ag (NH that forms
3)
2 +) solution;
(3) under fierce stirring, the hydrogen peroxide (H that is 30wt.% by concentration
2o
2) and Ag (NH
3)
2 +solution is added dropwise to respectively above-mentioned hollandite type SnO simultaneously
2suspension, aging 1～12h, then filters, washs, and at 100～150 ℃ of dry 1～24h, then at 200～800 ℃ of roasting 1～36h, obtains duct silver doping hollandite type SnO
2matrix.
6. the cold catalyst of stannic oxide nanometer as described in claim 1, is characterized in that honeycomb ceramic carrier loaded Ag
x(A)
y[M
zsn
8-z] O
16preparation method be:
(1) take the Ag of a certain amount of doping
x(A)
y[M
zsn
8-z] O
16matrix, adds a certain proportion of deionized water and adhesive, according to the requirement of viscosity and particle diameter, by the Ag of adhesive and doping
x(A)
y[M
zsn
8-z] O
16matrix mixing suspended emulsion high-speed stirred 1～24h, obtains the Ag that finite concentration adulterates
x(A)
y[M
zsn
8-z] O
16matrix slurries;
(2) adopt vacuum-negative pressure extraction technique by the Ag of above-mentioned doping
x(A)
y[M
zsn
8-z] O
16matrix slurries are coated on the ceramic honey comb of anticipating, and at 200～800 ℃ of roasting 1～36h, obtain Supported Honeycomb Ceramics type Ag
x(A)
y[M
zsn
8-z] O
16material.
7. the cold catalyst of stannic oxide nanometer as described in claim 6, is characterized in that the carrying method of Ag-Au system adopts gas phase reduction process or liquid phase reduction:
(1) gas phase reduction process: by above-mentioned loaded Ag
x(A)
y[M
zsn
8-z] O
16the cold catalyst of monolithic devices is immersed in AgNO
3and gold chloride (HAuCl
4) in mixed solution, dry after at 200～400 ℃ of roasting 1～36h, then at H
2in atmosphere 200～400 ℃ reduction 1～36h;
(2) liquid phase reduction: by loaded Ag
x(A)
y[M
zsn
8-z] O
16the cold catalyst of monolithic devices is immersed in finite concentration AgNO
3and HAuCl
4in mixed solution, then add NaBH
4, formaldehyde, ethylene glycol or glucose, react at a certain temperature 1～6h, dry after at 200～400 ℃ of roasting 1～36h.
8. the cold catalyst of stannic oxide nanometer as described in claim 6, the adhesive using while it is characterized in that preparing is silicate, aluminium oxide or zirconium carbonate ammonium, adhesive and the duct silver hollandite type SnO that adulterates
2the weight ratio of matrix is between 1～50%.
9. the cold catalyst of stannic oxide nanometer as described in claim 1, is characterized in that Hollandite duct contains monatomic nano silver wire, is mainly Ag
0; The Ag of doping
x(A)
y[M
zsn
8-z] O
16the Ag-Au cluster of outer surface of matrix or nano particle are mainly Ag-Au alloys.
10. the cold catalyst of stannic oxide nanometer as described in claim 1, is characterized in that having the feature that room temperature can thoroughly be removed airborne formaldehyde and have the monolithic devices nanometer cold catalyst of high-efficiency antimicrobial performance simultaneously: in unglazed, room temperature be often 0.010～50mg/m by concentration in air under wet condition
3formaldehyde through catalytic oxidation become nontoxic carbon dioxide and water; And can suppress and kill various germs, minimum inhibitory concentration (MIC) is in 1～600 μ g/mL scope.
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|---|---|---|---|
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Citations (3)
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