CN103007936B - Air purifier material, preparation method and use of air purifier material - Google Patents
Air purifier material, preparation method and use of air purifier material Download PDFInfo
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- CN103007936B CN103007936B CN201210583263.0A CN201210583263A CN103007936B CN 103007936 B CN103007936 B CN 103007936B CN 201210583263 A CN201210583263 A CN 201210583263A CN 103007936 B CN103007936 B CN 103007936B
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Abstract
The invention relates to a TiO2/BaO composite film-type air purifier material doped with A9 ions, a preparation method of the air purifier material and a use of the air purifier material. The composite film-type air purifier material having a photocatalytic performance greatly superior to that of a nanometer TiO2 film under the irradiation of sunlight and ultraviolet can effectively decompose various pollutants in the air and is applicable to indoor air purification.
Description
Technical field
The present invention relates to a kind of air cleaning agent material, relate to especially a kind of taking aluminium oxide as substrate, the nano-TiO of doping Ag ion
2the compound membranous type air purifying preparation of/BaO material, preparation method and its usage, belong to air purification field.
Background technology
Along with the raising day by day of people's living standard, and the interweaving of the factors such as a large amount of discharges of the quickening of urbanization process, motor vehicles tail gas, cause the day by day serious of present air environmental pollution and worsened.Corresponding is, due to the application of a large amount of industrial chemicals, ornament materials, daily chemical products in daily life especially house decoration, cause the severe exacerbation of IAQ, the content of its VOC (VOCs) is far above outdoor, and in these VOCs, contain a large amount of carcinogens, such as the concentration of formaldehyde, benzene,toluene,xylene, ammonia etc. is far above international standard, this physical and mental health to resident has caused serious threat, is also one of key factor of bringing out Several Kinds of Malignancy disease.
And from eighties of last century seventies, scientist finds conductor oxidate TiO
2since cyanide in energy degrading waste water, people are to TiO
2research day by day deep.All research shows, TiO
2especially nano-TiO
2multiple pollutant is had to very strong photocatalytic degradation ability.
Up to now, found that nearly the remaining equal available light catalysis technique such as above pernicious gas, agricultural chemicals, dyestuff, surfactant, stink substance of planting of hundreds of is effectively processed, as sterilization, decolouring, deodorizing etc.And as the most extensive TiO of research
2photochemical catalyst, the organic matter that its degradable is a large amount of, as benzene,toluene,xylene, naphthalene, halogenated aryl hydrocarbon, formaldehyde, NO
x, ammonia, hydrogen sulfide, tetrachloro-ethylene, carbon monoxide etc.
Just because of nano-TiO
2this excellent properties, become at present the study hotspot of photocatalysis field.Its catalytic mechanism is: under illumination, if the energy of photon is greater than semiconductor energy gap, and an electronics (e in its valence band
-) will be excited, cross forbidden band and enter conduction band, in valence band, produce corresponding hole (h simultaneously
+).Photohole has very strong oxidability (its standard hydrogen electrode current potential is at 1.0-3.5V), this hole is oxidation of organic compounds directly or indirectly, but normal conditions, think that hole completes by hydroxyl radical free radical (OH) organic oxidation, and its mechanism is as follows:
TiO
2+hv→e
-+h
+ (1)
h
++OH
-→·OH (2)
e
-+O
2→·O
2 - (3)
·O
2 -+H
+→HO
2· (4)
2HO
2·→O
2+H
2O
2 (5)
Due to TiO
2so strong oxidability, all Organic Pollutants all can be completely oxidized to CO by it
2and H
2o, and can not produce secondary pollution.Before and after this oxidation, TiO
2physical aspect, chemical property all do not change,, in the process of degradation of contaminant, it is photochemical catalyst.
But TiO
2also have some shortcomings, as 1, compared with the physical material of absorbent-type, its absorption property is poor, is difficult to indoor Adsorption of Organic to carry out enrichment to its surface, thereby has affected its photocatalysis efficiency and performance.2, nano-TiO
2particle size is little, surface area is large, surface can be high, in the labile state of energy, surperficial hydrogen bond between nano particle, the effect of chemical bond simultaneously also easily causes particle mutually adsorb and reunite, and how to overcome the particle agglomeration phenomenon causing because of particle diameter miniaturization and is undoubtedly TiO
2performance continues, the key point of stable performance.3, as a kind of inorganic filler, nano-TiO
2only have when good with other component compatibility, its performance is given full play to, but TiO
2this is difficult for disperseing as polar substances in organic media, has greatly limited nano-TiO
2in very many-sided application.
In order to overcome these defects, people have carried out a large amount of research, as membrane wrapping modified: at nano-TiO
2the coating of other material of coated with uniform one deck, changes its surface nature and is stablized.Surface graft modification: macromolecule is connected to nano-TiO by chemical reaction
2surface, to reach coated object.High-energy surface modification: high-energy surface-modification method is to utilize the initiated polymerizations such as high energy corona discharge, ultraviolet ray, plasma or radiation treatment and the method that realizes modification.Utilize precipitation reaction to carry out modification: to utilize organic matter or inorganic matter at nano-TiO
2surface forms one deck coating, to change its surface nature.
In addition, for example, in CN101554583B, disclose use high-speed ion bombardment titanium deoxid film, thereby obtained a large amount of sub-micron spaces, be conducive to absorption and air cleaning.
CN1026558115A discloses and has mixed cerium nano titanium oxide/NACF composite photo-catalyst, and it has good Degradation Formaldehyde ability.
CN1283355C discloses a kind of composite photocatalytic material for air purification, it is to be that raw material makes TiO 2 sol by titanate esters, or disperse to obtain tio_2 suspension with nano titanium dioxide powder ultrasonic wave in water, then add active carbon to carry out hydrothermal treatment consists, obtain the suspension of titanium dioxide/active carbon composite catalyst.Finally be combined with paper technology, be sprayed on paper, obtained the absorbent-type composite photocatalyst material for air purification taking paper as carrier.
CN1150979C discloses a kind of nano compound photocatalyst for cleaning air, is titanium dioxide nano-particle or film are loaded in carrier surface and space and obtain.
CN101081307B disclose a kind of by cyclodextrin material apply or be adsorbed on the material for air purification in photocatalyst surface, the adsoption catalysis clean-up effect of low concentration pollutant is provided.
Though there is certain advantage in above-mentioned disclosed these prior aries, but still has the shortcomings such as degradation efficiency is low, poor stability, though therefore carried out a large amount of effort, has the more nano-TiO of degradation efficiency for acquisition
2still there is demand in air purifying preparation.
Summary of the invention
In order to address the aforementioned drawbacks, the inventor concentrates on studies, and is paying after a large amount of creative works, complete the present invention, and find surprisingly, the present invention is by providing a kind of material for air purification, provide especially a kind of taking aluminium oxide as substrate, the TiO of doping Ag ion
2the compound membranous type material for air purification of/BaO and obtained beyond thought technique effect aspect air cleaning.Described material for air purification of the present invention has very high degradation efficiency for multiple pollutant, and excellent in stability, remarkably productive aspect indoor air purification.In addition, the present invention also provides the preparation method of this material for air purification, and purposes aspect air cleaning.
Particularly, described compound membranous type air purifying preparation material of the present invention comprises:
(1). alumina base counterdie;
(2). the TiO on described alumina base counterdie
2/ BaO composite membrane, in this film doped with Ag ion.
Wherein:
Preferably, described TiO
2the thickness of/BaO composite membrane is 0.1-0.5 with the ratio of described alumina substrate film thickness.
Preferably, described titanium alkoxide and (inorganic barium salt+inorganic silver salt), i.e. TiO
2with the mol ratio of (BaO+Ag) be 5-50.
In order to describe in more detail the present invention, as follows key element and/or feature are wherein explained in further detail, but should be appreciated that this is only non-limiting for the use exemplifying.
[alumina base counterdie]
Described aluminium oxide can be the aluminium oxide of any form, as Alpha-alumina, beta-alumina or gama-alumina, is preferably Woelm Alumina as gama-alumina.
The thickness of described alumina base counterdie there is no special restriction, for example can be 0.1-100 μ m, this scope has comprised any subinterval wherein, as 0.2-90 μ m, 0.4-80 μ m, 0.6-70 μ m, 0.8-60 μ m, 1-50 μ m, 2-40 μ m, 4-30 μ m, 8-20 μ m, 12-15 μ m, also comprise any concrete point value wherein, exemplarily exemplified 0.3 μ m, 0.5 μ m, 0.7 μ m, 0.9 μ m, 1.5 μ m, 3 μ m, 6 μ m, 10 μ m, 25 μ m, 35 μ n, 45 μ m, 55 μ m, 65 μ m, 75 μ m, 85 μ m and 95 μ m.
[TiO
2/ BaO composite membrane]
Wherein, unless otherwise prescribed or be otherwise noted described " TiO
2/ BaO composite membrane " in "/" refer to by TiO
2together with being mutually entrained in BaO and formed this composite membrane, but not the relation of "or".
Described TiO
2particle diameter be not particularly limited, for example its particle diameter degree can be 10-2500nm, this scope has comprised any subinterval wherein, as 50-2000nm, 100-1500nm, 150-1000nm, 200-500nm, also comprise any concrete point value wherein, exemplarily exemplified 20nm, 40nm, 80nm, 160nm, 250nm, 300nm, 400nm, 600nm, 700nm, 800nm, 900nm, 1100nm, 1200nm, 1300nm, 1400nm, 15080nm, 1600nm, 1700nm, 1800nm, 1900nm, 2100nm, 2200nm, 2300nm and 2400nm.
Described TiO
2being 10-100 with the mol ratio of BaO or Ag ion, is exemplarily 10,20,30,40,50,60,70,80,90 and 100.
Described TiO
2the thickness of/BaO composite membrane is 0.1-0.5 with the ratio of described alumina substrate film thickness, this scope has comprised any subinterval wherein, as 0.1-0.4,0.2-0.3, also comprise any concrete point value wherein, exemplarily exemplified 0.11,0.13,0.15,0.17,0.19,0.21,0.23,0.25,0.27,0.29,0.31,0.33,0.35,0.37,0.39,0.41,0.43,0.45,0.47 and 0.49.
The present invention also provides the preparation method of described compound membranous type air purifying preparation material, and it comprises the steps:
(1). the inorganic aluminate aqueous solution is added drop-wise in cetyl benzene sulfonate aqueous solution, then adds solid sulphuric acid hydrogen sodium, stir and obtain colloidal sol;
(2). in titanium alkoxide, add deionized water and absolute ethyl alcohol wiring solution-forming, then add acetylacetone,2,4-pentanedione or diethanol amine, stir and obtain mixed solution; Or
(2 '). by nano-TiO
2powder is placed in absolute ethyl alcohol and carries out ultrasonic wave dispersion, obtains TiO
2suspension;
(3). in the solution of step (2) or (2 '), add inorganic barium salt, pore-foaming agent and inorganic silver salt, ultrasonic concussion, mixes, and forms the colloidal sol of homogeneous transparent;
(4). use simple glass, twin polishing quartz glass, monocrystalline silicon piece or stainless steel substrates as substrate, be impregnated in the colloidal sol of step (1) and obtain gel mould, and dry;
(5). the desiccant gel film immersion obtaining in step (4), in the middle colloidal sol of step (3), is obtained to gel mould, and dry;
(6). the gel mould of step (5) is calcined in Muffle furnace, obtained compound membranous type air purifying preparation material.
Optionally, can by the dipping of step (4), dry repeatedly, as 2-10 time, to obtain the basilar memebrane of desired thickness.
Optionally, can by the dipping of step (5), dry repeatedly, as 2-10 time, to obtain the TiO of desired thickness
2/ BaO composite membrane.
Wherein:
In described step (1): described inorganic aluminate can be the inorganic aluminates such as aluminum nitrate, aluminium carbonate, aluminum sulfate, aluminium chloride, the mass concentration of the inorganic aluminate aqueous solution and cetyl benzene sulfonate aqueous solution all can be 0.5-5mol/l, for example, can be 0.5mol/l, 1mol, 1.5mol/l, 2.0mol/l, 2.5mol/l, 3mol/l, 3.5mol/l, 4mol/l, 4.5mol/l and 5mol/l.
Inorganic aluminate can be 1 with the ratio of the mole of cetyl benzene sulfonic acid sodium salt: 5-5: 1, and for example ratio between two can be 1: 1,1: 2,1: 3,1: 4,1: 5,2: 1,3: 1,4: 1 and 5: 1
.
The mol ratio of described niter cake and inorganic aluminate is 1: 2-5, for example, can be 1: 2,1: 3,1: 4 and 1: 5.
In described step (2): described titanium alkoxide can be is abbreviated as Ti (OEt)
4tetraethyl titanate Ti (OC
2h
5)
4, be abbreviated as Ti (OPr)
4tetraisopropyl titanate Ti (OC
3h
7)
4, be abbreviated as Ti (OBu)
4tetrabutyl titanate Ti (OC
4h
9)
4deng.
The concentration that described titanium alkoxide is dissolved in the solution obtaining in water and absolute ethyl alcohol is 0.5-5mol/l, for example, can be 0.5mol/l, 1mol, 1.5mol/l, 2.0mol/l, 2.5mol/l, 3mol/l, 3.5mol/l, 4mol/l, 4.5mol/l and 5mol/l.The volume ratio of described water and absolute ethyl alcohol is 1: 5-5: 1, be preferably 1: 1.
The mol ratio of the consumption of acetylacetone,2,4-pentanedione or diethanol amine and titanium alkoxide consumption is 1: 1-10, for example, can be 1: 1,1: 2,1: 3,1: 4,1: 5,1: 6,1: 7,1: 8,1: 9 and 1: 10.
In described step (2 '): described nano-TiO
2powder can be anatase titanium dioxide or rutile-type or this mixture of two kinds, its particle diameter is 10-2500nm, this scope has comprised any subinterval wherein, as 50-2000nm, 100-1500nm, 150-1000nm, 200-500nm, also comprised any concrete point value wherein, exemplarily exemplify 20nm, 40nm, 80nm, 160nm, 250nm, 300nm, 400nm, 600nm, 700nm, 800nm, 900nm, 1100nm, 1200nm, 1300nm, 1400nm, 15080nm, 1600nm, 1700nm, 1800nm, 1900nm, 2100nm, 2200nm, 2300nm and 2400nm.
In described step (3): described inorganic barium salt can be the conventional inorganic barium salts such as brium carbonate, barium sulfate, barium nitrate.Described inorganic silver salt can be the conventional inorganic silver salt such as silver carbonate, silver sulfate, silver nitrate.
Described titanium alkoxide is 5-50 with the mol ratio of (inorganic barium salt+inorganic silver salt), i.e. TiO in end product
2with the mol ratio of (BaO+Ag) be 5-50, be exemplarily 5,10,20,30,40,50.Unless otherwise prescribed, " (inorganic barium salt+inorganic silver salt) " or " (BaO+Ag) " here refers to the summation of these two kinds of materials.
The mol ratio of described inorganic barium salt and inorganic silver salt is 1: 5-5: 1, and for example ratio between two can be 1: 1,1: 2,1: 3,1: 4,1: 5,2: 1,3: 1,4: 1 and 5: 1, is preferably 1: 1.
Described pore-foaming agent is polyvinylpyrrolidone, is preferably polyvinylpyrrolidone-k30 (PVP-k30).Its mole dosage is the 10-50% of described titanium alkoxide mole, for example, be 10%, 20%, 30%, 40% and 50%.
In described step (4): adopt czochralski method to obtain gel mould, pull rate is 5-15cm/ minute, for example, can be 5cm/ minute, 7cm/ minute, 9cm/ minute, 11cm/ minute, 13cm/ minute and 15cm/ minute.
Obtain after gel mould, natural drying 5-15 hour, or in the vacuum drying oven of 30-40 DEG C, be dried 2-4 hour, obtain curing gel mould.
In described step (5): adopt czochralski method to obtain gel mould, pull rate is 5-15cm/ minute, for example, can be 5cm/ minute, 7cm/ minute, 9cm/ minute, 11cm/ minute, 13cm/ minute and 15cm/ minute.
Obtain after gel mould, natural drying 8-24 hour, or in the vacuum drying oven of 30-40 DEG C, be dried 3-5 hour, obtain curing gel mould.
In described step (6): the substrate that is covered with curing gel film is put in Muffle furnace, first calcining insulation 1-2 hour in 300-400 DEG C, then with the heating rate rising temperature of 100 DEG C/h, while reaching 700 ± 20 DEG C, stop heating up, and at this temperature, 1-2 hour is calcined in insulation, can obtain composite membrane material for air purification of the present invention.
In the dipping of step (4) and step (5), should control dipping number of times separately, make the TiO in final composite membrane material for air purification
2/ BaO composite membrane thickness is 0.1-0.5 with the ratio of alumina substrate film thickness.
The thickness proportion control of doping, composite membrane and the alumina base counterdie of the organic assembling of the present invention by composite membrane, Ag ion, and the use of specific pore-foaming agent, and make final material for air purification on the basis having a significant improvement with respect to prior art tool and/or improve, further increase the degradation efficiency of organic pollution in air, and had very good stability.Obtaining of all these effects, depends on the enforcement of following technological means and obtains:
1. load TiO on aluminium oxide
2/ BaO composite membrane, thus in the time that pollutants in air concentration is lower, by the high adsorption of aluminium oxide, the pollutant levels on this material are increased, be TiO
2smooth photocatalysis basis and the concentration of being carried out are provided.
2. adulterate by BaO, at TiO
2between particle, evenly mix BaO particle, avoided TiO
2the prolongation in time and agglomeration that occurs has kept long light stable catalytic activity.
3. pass through at TiO
2in/BaO composite membrane, mix Ag ion, make it there is bacteriostasis property.In addition,, when mixing after Ag, it is at TiO
2surface forms the Ag cluster with set electron effect, in the time of UV-irradiation, and TiO
2the photoelectron stream producing, to Ag, has strengthened the right separation in light induced electron-hole, has improved TiO
2photocatalytic activity.
4. by controlling TiO
2the ratio of/BaO composite membrane thickness and alumina substrate film thickness, and obtained best degradation effect and degradation efficiency.
Detailed description of the invention
Below by specific embodiment, the present invention is described in detail, but these exemplary embodiments not form any type of any restriction to real protection scope of the present invention.
Embodiment 1
(1). the aluminum nitrate aqueous solution of 100ml 1mol/l is added drop-wise in the cetyl benzene sulfonate aqueous solution of 100ml 0.5mol/l, then adds 0.025mol solid sulphuric acid hydrogen sodium, continue to stir, until obtain the colloidal sol of clear.
(2). be deionized water and the absolute ethyl alcohol of 1: 1 to adding volume ratio in 0.8mol tetrabutyl titanate, be made into the solution of 1.5mol/l, then add 0.4mol acetylacetone,2,4-pentanedione, strong agitation obtains mixed solution;
(3). in the solution of step (2), add 0.016mol barium nitrate, 0.2mol polyvinylpyrrolidone and 0.016mol silver sulfate, with ultrasonic oscillation, it is mixed completely, until form the colloidal sol of homogeneous transparent;
(4). use the monocrystalline silicon piece of 2cm × 10cm as substrate, be impregnated in step (1) colloidal sol, after 5 minutes, slowly lift, pull rate is 10cm/ minute, obtains gel mould, natural drying 6 hours, obtains curing gel film;
(5). the desiccant gel film immersion obtaining in step (4) is arrived in the colloidal sol of step (3), after 8 minutes, slowly lift, pull rate is 7cm/ minute, obtains gel mould, in the vacuum drying oven of 40 DEG C, be dried 3 hours, obtain curing gel mould;
(6). the substrate that is covered with curing gel film of step (5) is placed in Muffle furnace and is calcined, first in 350 DEG C, calcining is incubated 1.5 hours, then with the heating rate rising temperature of 100 DEG C/h, while reaching 710 DEG C, stop heating up, and at this temperature, insulation is calcined 2 hours, obtains compound membranous type material for air purification of the present invention.
The thickness of wherein said alumina base counterdie is 30 μ m, described TiO
2the thickness of/BaO composite membrane is 12 μ m, described TiO
2the thickness of/BaO composite membrane is 0.400 with the ratio of described alumina substrate film thickness.
Embodiment 2
Removing repetition in step (4) (implements dipping, is dried twice at step (1) colloidal sol by substrate for twice, lower same) outside, to implement the present embodiment with the same way of embodiment 1, the thickness of the alumina base counterdie of final compound membranous type material for air purification is 58 μ m, described TiO
2the thickness of/BaO composite membrane is 12.47 μ m, described TiO
2the thickness of/BaO composite membrane is 0.215 with the ratio of described alumina substrate film thickness.
Embodiment 3
Except repeating in step (4) 4 times, to implement the present embodiment with the same way of embodiment 1, the thickness of the alumina base counterdie of final compound membranous type material for air purification is 125 μ m, described TiO
2the thickness of/BaO composite membrane is 12.5 μ m, described TiO
2the thickness of/BaO composite membrane is 0.100 with the ratio of described alumina substrate film thickness.
Embodiment 4
Except repeating 3 times in step (4), and step (5) repeats outside twice, and to implement the present embodiment with the same way of embodiment 1, the thickness of the alumina base counterdie of final compound membranous type material for air purification is 89.4 μ m, described TiO
2the thickness of/BaO composite membrane is 35.76 μ m, described TiO
2the thickness of/BaO composite membrane is 0.400 with the ratio of described alumina substrate film thickness.
Embodiment 5
Divided by " step (2 '): by the dichloride in anatase type TiO of 0.8mol particle diameter 100nm
2powder adds in absolute ethyl alcohol, ultrasonic wave disperses to form stable suspension " replace outside step (2); to implement the present embodiment with the same way of embodiment 1, the thickness of the alumina base counterdie of final compound membranous type material for air purification is 29 μ m, described TiO
2the thickness of/BaO composite membrane is 14.5 μ m, described TiO
2the thickness of/BaO composite membrane is 0.500 with the ratio of described alumina substrate film thickness.
Embodiment 6
Except using in step (2) 0.4mol polyvinylpyrrolidone, to implement the present embodiment with the same way of embodiment 1, the thickness of the alumina base counterdie of final compound membranous type material for air purification is 28 μ m, described TiO
2the thickness of/BaO composite membrane is 11.48 μ m, described TiO
2the thickness of/BaO composite membrane is 0.410 with the ratio of described alumina substrate film thickness.
Embodiment 7
Except repeating in step (4) 4 times, to implement the present embodiment with the same way of embodiment 6, the thickness of the alumina base counterdie of final compound membranous type material for air purification is 122 μ m, described TiO
2the thickness of/BaO composite membrane is 12.4 μ m, described TiO
2the thickness of/BaO composite membrane is 0.102 with the ratio of described alumina substrate film thickness.
Embodiment 8
Except using in step (2) 0.4mol polyvinylpyrrolidone, to implement the present embodiment with the same way of embodiment 5, the thickness of the alumina base counterdie of final compound membranous type material for air purification is 28.4 μ m, described TiO
2the thickness of/BaO composite membrane is 12.1 μ m, described TiO
2the thickness of/BaO composite membrane is 0.426 with the ratio of described alumina substrate film thickness.
Embodiment 9
Except using in step (3) 0.08mol barium nitrate, to implement the present embodiment with the same way of embodiment 1, the thickness of the alumina base counterdie of final compound membranous type material for air purification is 29 μ m, described TiO
2the thickness of/BaO composite membrane is 12.6 μ m, described TiO
2the thickness of/BaO composite membrane is 0.434 with the ratio of described alumina substrate film thickness.
Embodiment 10
Except using in step (3) 0.008mol barium nitrate, to implement the present embodiment with the same way of embodiment 1, the thickness of the alumina base counterdie of final compound membranous type material for air purification is 28.4 μ m, described TiO
2the thickness of/BaO composite membrane is 12.8 μ m, described TiO
2the thickness of/BaO composite membrane is 0.451 with the ratio of described alumina substrate film thickness.
Embodiment 11-16
Except changing the consumption (but both mol ratios are still 1: 1) of barium nitrate and silver sulfate, so that tetrabutyl titanate (still as 0.8mol) and the mol ratio of (barium nitrate+silver sulfate) are respectively outside 5: 1,10: 1,20: 1,30: 1,40: 1 and 50: 1, to implement the present embodiment, the TiO of final compound membranous type material for air purification with the same way of embodiment 1
2the thickness of/BaO composite membrane is 0.421-0.440 with the ratio of described alumina substrate film thickness.
Embodiment 17
Except repeating in step (4) 5 times, to implement the present embodiment with the same way of embodiment 1, the thickness of the alumina base counterdie of final compound membranous type material for air purification is 156 μ m, described TiO
2the thickness of/BaO composite membrane is 12.2 μ m, described TiO
2the thickness of/BaO composite membrane is 0.078 with the ratio of described alumina substrate film thickness.
Embodiment 18
Except repeating in step (4) 8 times, to implement the present embodiment with the same way of embodiment 1, the thickness of the alumina base counterdie of final compound membranous type material for air purification is 255 μ m, described TiO
2the thickness of/BaO composite membrane is 12.8 μ m, described TiO
2the thickness of/BaO composite membrane is 0.050 with the ratio of described alumina substrate film thickness.
Embodiment 19
Except repeating in step (5) twice, to implement the present embodiment with the same way of embodiment 1, the thickness of the alumina base counterdie of final compound membranous type material for air purification is 29.8 μ m, described TiO
2the thickness of/BaO composite membrane is 25 μ m, described TiO
2the thickness of/BaO composite membrane is 0.838 with the ratio of described alumina substrate film thickness.
Embodiment 20
Except repeating in step (5) 3 times, to implement the present embodiment with the same way of embodiment 1, the thickness of the alumina base counterdie of final compound membranous type material for air purification is 29.5 μ m, described TiO
2the thickness of/BaO composite membrane is 36.8 μ m, described TiO
2the thickness of/BaO composite membrane is 1.247 with the ratio of described alumina substrate film thickness.
Comparative example 1
In step (3), do not add barium nitrate, to implement the present embodiment, described TiO with the same way of embodiment 1
2the thickness of/BaO composite membrane is 0.41 with the ratio of described alumina substrate film thickness.
Comparative example 2
In step (3), do not add polyvinylpyrrolidone, to implement the present embodiment, described TiO with the same way of embodiment 1
2the thickness of/BaO composite membrane is 0.395 with the ratio of described alumina substrate film thickness.
Comparative example 3
In the step of embodiment 1, implementation step (2)-(3), and be impregnated into the monocrystalline silicon piece of the 2cm × 10cm of step (4) as substrate in step (3), after 8 minutes, slowly lift, pull rate is 7cm/ minute, obtain gel mould, in the vacuum drying oven of 40 DEG C, be dried 3 hours, obtain curing gel mould; Then implementation step (7), obtains the TiO of single doping Ag
2/ BaO film, it is monofilm and do not comprise alumina base counterdie
Comparative example 4-7
In step (3), add respectively 0.16mol, 0.8mol barium nitrate and add respectively 0.16mol, 0.8mol silver sulfate, to implement the present embodiment with the same way of embodiment 1, be that described titanium alkoxide is 2.5: 1 and 1: 2 with the mol ratio of (inorganic barium salt+inorganic silver salt), described TiO
2the thickness of/BaO composite membrane is 0.39-0.43 with the ratio of described alumina substrate film thickness.
Comparative example 8-11
In step (3), add respectively 0.0064mol, 0.005mol barium nitrate and 0.0064mol, 0.005mol silver sulfate, to implement the present embodiment with the same way of embodiment 1, be that described titanium alkoxide is 62.5: 1 and 80: 1 with the mol ratio of (inorganic barium salt+inorganic silver salt), described TiO
2the thickness of/BaO composite membrane is 0.38-0.42 with the ratio of described alumina substrate film thickness.
Degradation property test and stability test
Measure as follows degradation property and the stability of material to pollutant in the material for air purification of the present invention of above-described embodiment and comparative example.
Filling respectively in the closed container of benzene, formaldehyde, ammonia, hydrogen sulfide, NO, initial concentration is 100mg/l, tests respectively the above-mentioned various materials that make, and uses gas chromatograph to analyze pollutant residual concentration after 30 minutes, thereby can learn palliating degradation degree, the results are shown in following table.
As seen from the above table: compound membranous type material for air purification of the present invention has excellent contaminant degradation performance, and in the time not comprising alumina base counterdie, BaO or do not use polyvinylpyrrolidone, its degradation property all can sharply reduce.
In addition, also can find out from upper table, in compound membranous type material for air purification of the present invention, described TiO
2the thickness of/BaO composite membrane and described alumina substrate film thickness have significant impact to its degradation property, when being within the scope of 0.1-0.5 time, and degradation property the best, outside this scope, decrease to some degree.And described titanium alkoxide also has significant impact to its degradation property with the mol ratio of (inorganic barium salt+inorganic silver salt), in the time being 5-50, degradation property the best, outside this scope, has the sharply reduction of highly significant.
After 2 months, again measure material for air purification in above-described embodiment and the comparative example degradation property to pollutant, thereby investigate its stability.The results are shown in following table.
As seen from the above table, compound membranous type material for air purification of the present invention has good stability, even if after 2 months, has still kept very high degradation rate.And when not comprising alumina base counterdie, BaO or not using polyvinylpyrrolidone, degradation property significantly reduces.Also can find out, described titanium alkoxide also has significant impact to its stability with the mol ratio of (inorganic barium salt+inorganic silver salt) simultaneously, and in the time being 5-50, degradation property the best, outside this scope, has the sharply reduction of highly significant.
The purposes that should be appreciated that these embodiment only limits the scope of the invention for the present invention being described but not being intended to.In addition; also should understand; after having read technology contents of the present invention, those skilled in the art can make various changes, amendment and/or modification to the present invention, within these all equivalent form of values fall within the protection domain that the application's appended claims limits equally.
Claims (6)
1. the TiO of Ag ion that adulterates
2the compound membranous type air purifying preparation of/BaO material, it comprises:
(1). alumina base counterdie;
(2). the TiO on described alumina base counterdie
2/ BaO composite membrane, in this film doped with Ag ion;
Described TiO
2the thickness of/BaO composite membrane is 0.1-0.5 with the ratio of described alumina substrate film thickness;
TiO
2with the mol ratio of (BaO+Ag) be 5-50;
The TiO of this doping Ag ion
2the preparation method of the compound membranous type air purifying preparation of/BaO material is as follows:
(1). the inorganic aluminate aqueous solution is added drop-wise in cetyl benzene sulfonate aqueous solution, then adds solid sulphuric acid hydrogen sodium, stir and obtain colloidal sol;
(2). in titanium alkoxide, add deionized water and absolute ethyl alcohol wiring solution-forming, then add acetylacetone,2,4-pentanedione or diethanol amine, stir and obtain mixed solution; Or
(2 '). by nano-TiO
2powder is placed in absolute ethyl alcohol and carries out ultrasonic wave dispersion, obtains TiO
2suspension;
(3). in the solution of step (2) or (2 '), add inorganic barium salt, pore-foaming agent polyvinylpyrrolidone and inorganic silver salt, ultrasonic concussion, mixes, and forms the colloidal sol of homogeneous transparent;
(4). use simple glass, twin polishing quartz glass, monocrystalline silicon piece or stainless steel substrates as substrate, be impregnated in the colloidal sol of step (1) and obtain gel mould, and dry;
(5). the desiccant gel film immersion obtaining in step (4), in the middle colloidal sol of step (3), is obtained to gel mould, and dry;
(6). the gel mould of step (5) is calcined in Muffle furnace, obtained compound membranous type air purifying preparation material;
In step (6), the gel mould of step (5) is calcined in Muffle furnace at 300-400 DEG C to insulation 1-2 hour, then with the heating rate rising temperature of 100 DEG C/h, while reaching 700 ± 20 DEG C, stop heating up, and 1-2 hour is calcined in insulation at this temperature.
2. air cleaning agent material as claimed in claim 1, is characterized in that: described aluminium oxide is Alpha-alumina, beta-alumina or gama-alumina.
3. air cleaning agent material as claimed in claim 1, is characterized in that: described alumina substrate film thickness is 0.1-100 μ m.
4. air cleaning agent material as claimed in claim 1, is characterized in that: dipping in step (4) or (5), dry repeatedly.
5. air cleaning agent material as claimed in claim 1, is characterized in that: described inorganic aluminate is aluminum nitrate, aluminium carbonate, aluminum sulfate, aluminium chloride; Described titanium alkoxide is tetraethyl titanate, tetraisopropyl titanate, tetrabutyl titanate; Described inorganic barium salt is brium carbonate, barium sulfate, barium nitrate; Described inorganic silver salt is silver carbonate, silver sulfate, silver nitrate.
6. the purposes of air cleaning agent material for purifying air described in claim 1.
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