CN102500366B - Photo-catalytic nanomaterial - Google Patents
Photo-catalytic nanomaterial Download PDFInfo
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- CN102500366B CN102500366B CN 201110343737 CN201110343737A CN102500366B CN 102500366 B CN102500366 B CN 102500366B CN 201110343737 CN201110343737 CN 201110343737 CN 201110343737 A CN201110343737 A CN 201110343737A CN 102500366 B CN102500366 B CN 102500366B
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- photocatalysis
- titanium dioxide
- nano silver
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 35
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 19
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract 8
- 238000007146 photocatalysis Methods 0.000 claims description 30
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 22
- 239000002245 particle Substances 0.000 claims description 21
- 150000001875 compounds Chemical class 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000009413 insulation Methods 0.000 claims description 7
- 241000894006 Bacteria Species 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 21
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 16
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 14
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 12
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229960004643 cupric oxide Drugs 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 239000000395 magnesium oxide Substances 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000009281 ultraviolet germicidal irradiation Methods 0.000 description 1
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- Cold Air Circulating Systems And Constructional Details In Refrigerators (AREA)
Abstract
The invention discloses a photo-catalytic nanomaterial, which is a mixture consisting of nano silver and nano titanium dioxide, wherein the mass ratio of the nano silver to the titanium dioxide is 0.5-10:90-99.5; a preparation method of the mixture comprises the following steps of: mixing the nano silver and the nano titanium dioxide in proportion to prepare solution; performing ultrasonic treatment; reacting in a hydrothermal kettle at 225 DEG C for 2 hours; performing centrifugal washing and separation; and preserving heat at 550 DEG C for 2 hours to obtain the photo-catalytic nanomaterial of the nano silver doped nano titanium dioxide. The mixture provided by the invention can be used in the aspects of bacteria removal and odor removal of a refrigerator, can be coated on the surface of an inner member of the refrigerator, and can also be coated on other substrates to be mounted in a box body.
Description
Technical field:
The present invention relates to a kind of photocatalysis nano material, relate in particular to and a kind ofly can be applicable to refrigerator and have the eliminate the unusual smell photocatalysis nano material of function of degerming.
Background technology:
The peculiar smell that refrigerator is bought the stage can affect the desire that the client buys refrigerator, and the peculiar smell of operational phase and bacterium can affect the freshness date of food in the refrigerator.Therefore, have eliminate the unusual smell refrigerator market prospects of function of degerming very large.
Photocatalysis technology is a kind of emerging, efficient, energy-conservation Modern Green green technology, and photocatalysis technology is under the effect of catalyst, utilizes light radiation that pollutant is decomposed into process nontoxic or the low material of toxicity.
And the catalysis material of usually studying is with TiO
2Be the metal-oxide semiconductor (MOS) of representative, it has extraordinary chemical stability, water insoluble, the advantages such as photostability is high, have strong oxidation-reducing power, cheap, harmless, long service life.TiO
2Be subject to ultraviolet irradiation, when energy during more than or equal to its energy gap, the electronics on the valence band is excited, and crosses the forbidden band and enters conduction band, forms electronegative high activity electronics (e
-), produce corresponding hole (h in valence band simultaneously
+), electronics separates and moves to the diverse location of particle surface with the hole, reduction and oxidation-adsorption H from the teeth outwards
2O and O
2, generate OH and O
2 -Free radical, these free radical decomposing organic matters generate carbon dioxide and water, thereby its surperficial organic pollution gas is degraded, and these free radicals also have bactericidal action simultaneously.Mechanism is as shown in Figure 1:
The A process:
B process: e
-+ Aads → A
-Ads
C process: h+Dads → D
+Ads
D, E process: e
-+ h
+→ △ (heat release)
TiO
2Be a kind of polymorphous compound, it is a kind of common N-shaped semi-conducting material, at nature anatase, rutile and three kinds of crystalline forms of brockite is arranged.The titanium dioxide of Detitanium-ore-type is multiplex in photochemical catalyst, shows very wide application prospect aspect energy-conserving and environment-protective.Usually, TiO
2Particle diameter is less, and its specific area is larger, increases TiO
2Molecule is in the share on surface, produces photoproduction e thereby light-catalyzed reaction occurs
--h
+Right probability increases; On the other hand since with the O of its Surface Contact
2And H
2O content is more, effectively reduces e
--h
+The probability of hole-recombination, thus photocatalysis effect improved.Studies show that the compound raising that more is conducive to photocatalysis effect of a certain proportion of anatase and rutile.
Summary of the invention:
For overcoming the defective of prior art, the object of the present invention is to provide a kind of photocatalysis nano material, be a kind ofly to be applicable to refrigerator and to have the eliminate the unusual smell photocatalysis nano material of function of degerming.
Technical solution problem of the present invention adopts following technical scheme:
A kind of photocatalysis nano material, by the mixture that Nano Silver and nano titanium oxide consist of, the mass ratio of described Nano Silver and described titanium dioxide is 0.5～10: 90～99.5; The preparation method of described mixture is: get in proportion Nano Silver and nano titanium oxide mixing wiring solution-forming, through ultrasonic processing, reaction is 2 hours in 225 ℃ of lower water heating kettles, centrifuge washing, separation, insulation is 2 hours under 550 ℃, obtains the photocatalysis compound of Nano Silver doped nano titanium dioxide.
A kind of photocatalysis nano material, by the mixture that nano cupric oxide, zinc oxide or magnesia and nano titanium oxide consist of, the mass ratio of described nano cupric oxide, zinc oxide or magnesia and nano titanium oxide is 2～12: 88～98; The preparation method of described mixture is: get in proportion nano cupric oxide, zinc oxide or magnesia and nano titanium oxide mixing wiring solution-forming, through ultrasonic processing, reaction is 2 hours in 225 ℃ of lower water heating kettles, centrifuge washing, separation, insulation is 2 hours under 550 ℃, obtains the photocatalysis compound of nano cupric oxide, zinc oxide or magnesia doped nano titanium dioxide.
The nanometer particle size of above-mentioned photocatalysis nano material is at 10～60nm.
Compared with the prior art, beneficial effect of the present invention is embodied in:
Metal ion mixing is to improve TiO
2One of common method of photocatalysis performance, when semiconductor surface and Metal Contact, the carrier redistribution, electronics is transferred to the lower metal of fermi level from the higher N-shaped semiconductor of fermi level, until their fermi level is identical, form Schottky barrier, become effective trap of capturing excitation electron, photo-generated carrier is separated, thereby has suppressed the compound of electronics and hole.
By mixing silver ion is incorporated into TiO
2Lattice structure is inner, introduces new electric charge in lattice, form defective or change lattice types, thereby affect light induced electron and hole moving situation, adjust its distribution or change TiO
2Band structure, finally cause TiO
2Photocatalytic activity in various degree change occurs.
Semiconductor is compound to be that a kind of particle is to the modification of another kind of particle in essence, by the semi-conductive compound separation of charge effect that improves system, be easy to regulate semi-conductive band gap and wide spectrum absorption region, make light absorption be the band edge type, the surface modification by particle can increase its photostability and Superhydrophilic.Adopt zinc oxide, magnesia, cupric oxide semi-conducting material to modify TiO
2, because of Mixed crystal effect, can improve TiO
2Catalytic activity and change crystal structure, thus its photocatalysis performance improved.
The photocatalytic activity of nano material is relevant with the nanometer particle size of material.Particle diameter is little, and light induced electron and hole are from TiO
2The time that is diffused into the surface in the body is short, and they are at TiO
2Recombination probability in the body reduces, and the electronics and the number of cavities that arrive the surface are many, and photocatalytic activity is high.For example at the common powder TiO of 1000nm
2Being diffused into the surface in the body in the particle and approximately needing 100ns, is then only to need 10ps in the 10nm particle at particle diameter.In addition, particle diameter is little, specific area is large, help oxygen and the organic matter that is degraded at TiO
2The in advance absorption on surface, then reaction rate is fast, and photocatalysis efficiency must increase.
When granular size was 1～10nm, quantum size effect appearred.Quantum size effect can cause the forbidden band to broaden, and enables to be with blue shift, and the energy of required exciting light raises, and will cause TiO
2The photoactivate degree dies down.
And at preparation TiO
2Process in, sintering temperature is lower, nano-TiO
2Particle diameter less, but when sintering temperature is lower than 523K, TiO
2Sample is amorphous structure, nano-TiO under this temperature
2Particle diameter be 10.8nm; 523K roasting TiO
2Sample be anatase structured, along with sintering temperature raises, TiO
2The crystal grain of sample grow up gradually; When sintering temperature is 823K, begin to occur crystal transfer, Rutile Type appears; When heat treatment temperature reaches 1073K, TiO
2Sample changes rutile structure fully into, nano-TiO under this temperature
2Particle diameter be 56.3nm.The compound raising that more is conducive to photocatalysis effect of a certain proportion of anatase and rutile, so photocatalysis nano material particle diameter photocatalysis effect between 10～60nm reaches maximum.
Photocatalysis nano material can be applied in a lot of fields, and for example aspect the refrigerator degerming eliminated the unusual smell, it can be coated in refrigerator internals surface, also can be coated on other base material to be installed in the casing.Nano material does not possess the degerming function that eliminates the unusual smell yet when having photocatalysis, and when using UV-irradiation, the degerming of the nano material efficient that eliminates the unusual smell improves.
Description of drawings:
Fig. 1 is OH and O
2 -Free radical has the mechanism figure of bactericidal action.
The specific embodiment:
Embodiment 1: take by weighing the Nano Silver of 0.5 mass parts, the nano titanium oxide of 99.5 mass parts, mix wiring solution-forming, through ultrasonic processing, reaction is 2 hours in 225 ℃ of lower water heating kettles, centrifuge washing, separation, insulation is 2 hours under 550 ℃, obtains the photocatalysis compound of Nano Silver doped nano titanium dioxide, and the particle diameter of compound is between 10～60nm.
Embodiment 2: the preparation method is with embodiment 1, and difference is, Nano Silver is got 1.5 mass parts, and nano titanium oxide is got 98.5 mass parts.
Embodiment 3: the preparation method is with embodiment 1, and difference is, Nano Silver is got 2.5 mass parts, and nano titanium oxide is got 97.5 mass parts.
Embodiment 4: the preparation method is with embodiment 1, and difference is, Nano Silver is got 5 mass parts, and nano titanium oxide is got 95 mass parts.
Embodiment 5: the preparation method is with embodiment 1, and difference is, Nano Silver is got 6 mass parts, and nano titanium oxide is got 94 mass parts.
Embodiment 6: the preparation method is with embodiment 1, and difference is, Nano Silver is got 8 mass parts, and nano titanium oxide is got 92 mass parts.
Embodiment 7: the preparation method is with embodiment 1, and difference is, Nano Silver is got 10 mass parts, and nano titanium oxide is got 90 mass parts.
Embodiment 8: take by weighing the nano zine oxide of 2 mass parts, the nano titanium oxide of 98 mass parts, mix wiring solution-forming, through ultrasonic processing, reaction is 2 hours in 225 ℃ of lower water heating kettles, centrifuge washing, separation, insulation is 2 hours under 550 ℃, obtains the photocatalysis compound of Nano Silver doped nano titanium dioxide, and the particle diameter of compound is between 10～60nm.
Embodiment 9: take by weighing the nano cupric oxide of 4 mass parts, the nano titanium oxide of 96 mass parts, mix wiring solution-forming, through ultrasonic processing, reaction is 2 hours in 225 ℃ of lower water heating kettles, centrifuge washing, separation, insulation is 2 hours under 550 ℃, obtains the photocatalysis compound of Nano Silver doped nano titanium dioxide, and the particle diameter of compound is between 10～60nm.
Embodiment 10: take by weighing the nano magnesia of 12 mass parts, the nano titanium oxide of 88 mass parts, mix wiring solution-forming, through ultrasonic processing, reaction is 2 hours in 225 ℃ of lower water heating kettles, centrifuge washing, separation, insulation is 2 hours under 550 ℃, obtains the photocatalysis compound of Nano Silver doped nano titanium dioxide, and the particle diameter of compound is between 10～60nm.
Embodiment 11: the preparation method is with embodiment 8, and difference is, nano zine oxide is got 6 mass parts, and nano titanium oxide is got 94 mass parts.
Embodiment 12: the preparation method is with embodiment 9, and difference is, nano cupric oxide is got 8 mass parts, and nano titanium oxide is got 92 mass parts.
Claims (2)
1. photocatalysis nano material is characterized in that the mixture that is made of Nano Silver and nano titanium oxide, and the mass parts of Nano Silver described in the mixture is 0.5 ~ 10, and the mass parts of described titanium dioxide is 90 ~ 99.5; The preparation method of described mixture is: get in proportion Nano Silver and nano titanium oxide mixing wiring solution-forming, through ultrasonic processing, reaction is 2 hours in 225 ℃ of lower water heating kettles, centrifuge washing, separation, insulation is 2 hours under 550 ℃, obtains the photocatalysis compound of Nano Silver doped nano titanium dioxide.
2. a kind of photocatalysis nano material according to claim 1 is characterized in that, the nanometer particle size of described photocatalysis nano material is at 10 ~ 60nm.
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| CN102500366B true CN102500366B (en) | 2013-04-17 |
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| CN106076398A (en) * | 2016-06-06 | 2016-11-09 | 同济大学 | A kind of silver TiO2the preparation method of nano cupric oxide modified zeolite composite photo-catalyst |
| CN107514796A (en) * | 2017-08-23 | 2017-12-26 | 洪源 | A kind of air-conditioner air outlet nano material filter bowl |
| CN108190831B (en) * | 2017-11-28 | 2019-06-28 | 郑州大学 | A method of doping regulation hot melt Ag nanoparticle micro-nano interconnection line performance |
| CN109701526A (en) * | 2019-01-07 | 2019-05-03 | 江苏大学 | A kind of hollow B-SiO2@TiO2The purposes of-Ag catalyst degradation green alga |
| CN113145170B (en) * | 2020-12-31 | 2022-05-27 | 东北电力大学 | Preparation method of visible light full-absorption saturated phosphomolybdate composite material with Keggin structure |
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| CN101906662B (en) * | 2010-08-18 | 2012-06-27 | 中国科学院半导体研究所 | Preparation method of TiO2 nanotubes modified by silver nanoparticles with different particle diameters |
| CN102189271B (en) * | 2011-06-18 | 2013-04-17 | 中国科学院合肥物质科学研究院 | Method for preparing Ag/TiO2 nano composite material |
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Address after: 230601 No. 2163 Lianhua Road, Hefei economic and Technological Development Zone, Anhui Patentee after: Changhong MeiLing Limited by Share Ltd Address before: 230061 No. 2163 Lianhua Road, Hefei economic and Technological Development Zone, Anhui Patentee before: Hefei Meiling Co., Ltd. |