CN108295853A - Catalysis material, preparation method with antibacterial effect and photocatalytic elements - Google Patents
Catalysis material, preparation method with antibacterial effect and photocatalytic elements Download PDFInfo
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- CN108295853A CN108295853A CN201710780595.0A CN201710780595A CN108295853A CN 108295853 A CN108295853 A CN 108295853A CN 201710780595 A CN201710780595 A CN 201710780595A CN 108295853 A CN108295853 A CN 108295853A
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- antibacterial effect
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 56
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 52
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 84
- 239000004408 titanium dioxide Substances 0.000 claims abstract description 39
- 239000002245 particle Substances 0.000 claims abstract description 34
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 27
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 27
- 229910052709 silver Inorganic materials 0.000 claims abstract description 16
- 239000004332 silver Substances 0.000 claims abstract description 16
- 238000007146 photocatalysis Methods 0.000 claims description 28
- 239000000084 colloidal system Substances 0.000 claims description 23
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 21
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 9
- 229910001868 water Inorganic materials 0.000 claims description 9
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 claims description 7
- 239000000908 ammonium hydroxide Substances 0.000 claims description 6
- 229940044927 ceric oxide Drugs 0.000 claims description 6
- 230000008859 change Effects 0.000 claims description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 241000790917 Dioxys <bee> Species 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- -1 hydrogen Titanium oxide Chemical class 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 2
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 238000012360 testing method Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 241000588724 Escherichia coli Species 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 230000003385 bacteriostatic effect Effects 0.000 description 5
- 238000005202 decontamination Methods 0.000 description 5
- 230000003588 decontaminative effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 229910001923 silver oxide Inorganic materials 0.000 description 5
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 5
- 230000003115 biocidal effect Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 241000894006 Bacteria Species 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003599 detergent Substances 0.000 description 2
- 230000008034 disappearance Effects 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 241001614291 Anoplistes Species 0.000 description 1
- 241000370738 Chlorion Species 0.000 description 1
- 241001062009 Indigofera Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000000845 anti-microbial effect Effects 0.000 description 1
- 230000002155 anti-virotic effect Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 230000003389 potentiating effect Effects 0.000 description 1
- DTPQZKZONQKKSU-UHFFFAOYSA-N silver azanide silver Chemical compound [NH2-].[Ag].[Ag].[Ag+] DTPQZKZONQKKSU-UHFFFAOYSA-N 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or gold
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
-
- B01J35/39—
-
- B01J35/393—
-
- B01J35/396—
Abstract
The invention discloses a kind of catalysis materials with antibacterial effect, including multiple photocatalytic particles, each photocatalytic particle includes a core body and one is formed in outer covering layer on the surface of core body, wherein core body is made of titanium dioxide, outer covering layer is made of ceria and silver, and core body and the weight ratio of outer covering layer are between 1:1 to 1:Between 2, and the weight in outer covering layer shared by ceria is more than the weight shared by silver.The invention also discloses the photocatalytic elements of the preparation method of above-mentioned catalysis material and the above-mentioned catalysis material of application.
Description
Technical field
The present invention relates to a kind of photocatalysis, preparation method and applications, more particularly to a kind of light with antibacterial effect
Catalysis material, preparation method and photocatalytic elements.
Background technology
Photocatalysis is exactly the irradiation by light, can promote the substance of chemical reaction.Photocatalysis, which is good at, is used in photocatalysis
The harmful chemical of low concentration in air is handled, and itself will not disengage harmful substance, therefore is also that extremely excellent environment is net
Change catalyst.Being often used as light-catalysed substance at present has metal oxide, wherein titanium dioxide (TiO2) because with strong
Big oxidability, high chemically stability and the characteristics such as nontoxic and be most often used.
The photodegradation mechanism of so-called photocatalysis treatment program refers to being catalyzed by ultraviolet light or sun phot-luminescence, make
Photocatalysis generates electronics and hole, will adsorb substance oxidation on the surface thereof, and be decomposed into small molecule.It is with titanium dioxide
Example starts reaction (because the energy level difference of titanium dioxide is about 3.1eV, and wavelength 400nm under the light irradiation of wavelength 400nm
Light energy be about 3.1eV), Titanium dioxide absorption light energy simultaneously generates electronics and hole, hole therein have it is great
Oxidizing force can decompose the contaminant molecule direct oxidation on surface, or by the water-molecule dissociation on surface be hydrogen-oxygen from
By base.The macromolecule contaminant of script is cracked into smaller pollution-free substance by light-catalyzed reaction, that is, reaches removing pollution
The purpose of object.
Titanium dioxide can generally be equipped on carrier and use, to increase the irradiated area of light.However, titanium dioxide must be
300 DEG C to 500 DEG C of temperature is calcined, and the beginning can form anatase crystallization (anatase), and the crystallization of such kenel just has light
Catalytic effect.But some carriers are such as cloth, leather, and it can not be resistant to high temperature, once and it is unable to get in use environment
Sufficient light irradiation will so that titanium dioxide itself is difficult to reach good anti-bacteria and anti-virus efficiency, thus in application by
Certain limitation.In order to solve the problems, such as this, the practice more typical at present is that titanium dioxide is compound with silver, but it is only capable of promotion one
Partial anti-microbial property, though there is excellent antibacterial to imitate general common strain (such as Escherichia coli, staphylococcus aureus)
Fruit, but to more indomitable strain (such as mycobacteria etc.) if can not effectively inhibit growth, cause antibacterial effect bad；And pass through one
After the use of section time, nano silver material surface has the attachment of biomembrane, thus reduces antibacterial efficacy.
Invention content
Technical problem to be solved by the present invention lies in provide a kind of with antibacterial effect in view of the deficiencies of the prior art
Catalysis material, especially can have potent lasting antibacterial ability in irradiation and not irradiation under the conditions of.The present invention also provides
The preparation method of above-mentioned catalysis material with use the photocatalytic elements of above-mentioned catalysis material.
In order to solve the above technical problems, a technical solution provided by the present invention is：It is a kind of with antibacterial effect
Catalysis material, including multiple photocatalytic particles, wherein each described photocatalytic particle include that a core body and one are formed
Outer covering layer on the surface of the core body.The core body is made of titanium dioxide, and the outer covering layer is ceria
It is constituted with silver, and the core body and the weight ratio of the outer covering layer are between 1:1 to 1:Between 2, and in the outer covering layer
Weight shared by ceria is more than the weight shared by silver.
The core body of an embodiment according to the present invention, each photocatalytic particle is in needle-shaped, and has one
Draw ratio between 1 to 40.
An embodiment according to the present invention, the outer covering layer include multiple nano ceric oxide particles and multiple nano silvers
Particle, the average grain diameter of the plurality of nano ceric oxide particle is between 5 to 20 nanometers, multiple nano silvers
The average grain diameter of grain is between 1 to 10 nanometer.
An embodiment according to the present invention, multiple nano ceric oxide particles account for the 50% of the outer covering layer total weight
To 75%, multiple nano-Ag particles account for the 25% to 50% of the outer covering layer total weight.
An embodiment according to the present invention, the outer covering layer are formed in a continuous fashion on the surface of the core body.
An embodiment according to the present invention, the outer covering layer are formed in the surface of the core body in the form of discrete
On.
An other technical solution provided by the present invention is：A kind of preparation of the above-mentioned catalysis material with antibacterial effect
Method includes the following steps：Titanium hydroxide colloid is prepared, hydrogen peroxide is then added, to form titanium dioxide colloid solution；And
At a temperature of 60 DEG C to 100 DEG C, ceria and silver nitrate is added to the titanium dioxide colloid solution, then heated at constant temperature
It disappears until colloid hydrolyzes, to form the catalysis material with antibacterial effect, wherein titanium dioxide, ceria, silver
Weight ratio with water is 0.01%-2%：0.01%-1%：0.001%-1%：96%-96.979%.
An embodiment according to the present invention, the titanium hydroxide colloid are first at a temperature of 0 DEG C to 15 DEG C, by four chlorinations
Titanium and combined are made then at addition ammonium hydroxide in mixture is formed by.
An embodiment according to the present invention, the molar ratio of hydrogen peroxide and titanium dioxide is situated between in the titanium dioxide colloid solution
In 2:1 to 5:Between 1, and the solid content of titanium dioxide is between 0.01% to 2%.
An embodiment according to the present invention, the catalysis material with antibacterial effect with one between 6.5 to 10 it
Between pH value.
Other yet another aspect provided by the present invention is：A kind of photocatalytic elements, including a carrier and a use
The above-mentioned catalysis material with antibacterial effect is coated on the carrier and the photocatalysis layer of formation.
The beneficial effects of the present invention are, the catalysis material with antibacterial effect that technical solution of the present invention is provided,
It is by the way that " each photocatalytic particle includes a core body and one is formed in outer covering layer on the surface of core body, center
Heart body is made of titanium dioxide, and outer covering layer is made of ceria and silver, and core body and the weight ratio of outer covering layer between
1:1 to 1:Between 2, and the weight in outer covering layer shared by ceria be more than silver shared by weight " technical characteristic, visible
Good antibacterial effect can be kept under light for a long time, and when photocatalysis layer is by ultraviolet light or daylight light irradiation, can generated quite
High catalytic activity, and have the function of decontamination, self-cleaning and antibacterial.
For the enabled feature and technology contents for being further understood that the present invention, please refer to below in connection with the present invention specifically
Bright and attached drawing, however the attached drawing provided is merely provided for reference and description, is not intended to limit the present invention.
Description of the drawings
Fig. 1 is the step flow chart of the preparation method of the catalysis material with antibacterial effect of the present invention.
Fig. 2 is the structural schematic diagram (one) of the catalysis material with antibacterial effect of the present invention.
Fig. 3 is the structural schematic diagram (two) of the catalysis material with antibacterial effect of the present invention.
Fig. 4 is the structural schematic diagram of the photocatalytic elements of the present invention.
Fig. 5 is the partial schematic diagram of the parts V in Fig. 4.
Specific implementation mode
Due to titanium dioxide (TiO2) it is used as photocatalysis, itself do not have the ability of antibacterial bacteriostatic and makes application range
Limited, the present invention proposes a kind of new catalysis material, by by titanium dioxide and ceria (CeO2) and silver-colored (Ag) is again
It closes, irradiation and good antibacterial bacteriostatic ability under the conditions of not irradiation can be obtained.And in order to realize a large amount of lifes of this catalysis material
Production and extensive use, the present invention also propose a kind of low temperature process of innovation, do not need 300 DEG C or more of high-temperature calcination, and institute
The suspension of manufactured photocatalytic particle is very stable, even if photocatalytic particle will not assemble more than 3 years, generate precipitation.
Be below illustrated by particular specific embodiment it is presently disclosed in relation to " with antibacterial effect photocatalysis
The embodiment of material, preparation method and photocatalytic elements ", those skilled in the art can be by contents disclosed in this specification
Understand advantages of the present invention and effect.The present invention can be implemented or applied, this explanation by other different specific embodiments
Every details in book may be based on different viewpoints and application, in the lower various modifications of progress without departing from the spirit and change
More.In addition, the attached drawing of the present invention is only simple schematically illustrate, not according to the description of actual size, state in advance.Implementation below
The relevant technologies content of the present invention will be explained in further detail in mode, but disclosure of that is not to limit the guarantor of the present invention
Protect range.
Refering to Figure 1, the preparation method of the catalysis material with antibacterial effect for first embodiment of the invention
Step flow chart.As shown in Figure 1, preparation method S100 includes the following steps：Step S102 prepares titanium hydroxide colloid, so
After hydrogen peroxide is added, to form titanium dioxide colloid solution；And step S104, at a temperature of 60 DEG C to 100 DEG C, to dioxy
Change titanium colloidal solution and ceria and silver nitrate is added, then heated at constant temperature disappears until colloid hydrolyzes, and has antibacterial to be formed
The catalysis material of effect.
In step S102, titanium hydroxide colloid is first at a temperature of 0 DEG C to 15 DEG C, by titanium tetrachloride and aqueous hydrochloric acid solution
Mixing is made then at addition ammonium hydroxide in mixture is formed by.It is first by the titanium tetrachloride as titanium source when actual implementation
It is slowly added in aqueous hydrochloric acid solution, forms titanium tetrachloride dispersion liquid, add 30wt% ammonium hydroxide (NH4OH pH value) is adjusted to 6-
12, the dirty solution containing titanium hydroxide colloid is formed, is then filtered dirty solution, and washed several times with water, until not having chlorion to be
Only (can be using silver nitrate titration until not having white silver nitride precipitation as basis for estimation) be to get to the higher titanium hydroxide glue of purity
Body.Hydrogen peroxide is added later to be reacted, titanium dioxide colloid solution is formed.
It is the temperature that the titanium dioxide colloid solution formed in step S102 is first placed in 60 DEG C to 100 DEG C in step S104
Degree lower heating a period of time (such as 1-10 hours), then ceria and silver nitrate is added to the titanium dioxide colloid solution after heating
(AgNO3) solution, then heated at constant temperature disappear to get to ceria-silver/bis- as catalysis material until colloid hydrolysis
Titanium oxide complex sol solution；Preferably, complex sol solution has a pH value between 6.5 to 10, and complex sol
Titanium dioxide, ceria, the silver-colored weight ratio with water are 0.01%-2% in solution：0.01%-1%：0.001%-1%：
96.9%-96.979%.
Please refer to shown in Fig. 2 and Fig. 3, the catalysis material M made of preparation method S100, including multiple stable suspersions in
Photocatalytic particle 10 in water, each photocatalytic particle 10 include the surface that a core body 11 and one is formed in core body 11
On outer covering layer 12.Wherein core body 11 is made of titanium dioxide, and is a Detitanium-ore-type crystalline solid, and outer covering layer 12 is dioxy
Change cerium to be constituted with silver.When actual implementation, outer covering layer 12 can be in a continuous fashion formed on the surface of core body 11 (as schemed
Shown in 2), can also discrete form be formed on the surface of core body 11 (as shown in Figure 3).
It is worth noting that, the core body 11 of each photocatalytic particle 10 and the weight ratio of outer covering layer 12 are between 1:1 to
1:Between 2, and the weight in outer covering layer 12 shared by ceria is more than the weight shared by silver.Whereby, electron hole pair transfer is multiple
The time of conjunction is effectively extended, this phenomenon not only increases light-catalysed activity, moreover it is possible to will excite the wavelength of photocatalytic activity
From ultraviolet light wave band toward visible light wave range displacement so that catalysis material M can keep good antibacterial to imitate for a long time under visible light
Fruit.
Preferably, core body 11 is in needle-shaped, and there is a draw ratio between 1 to 40.Outer covering layer 12 includes multiple
Nano ceric oxide particle 121 and multiple nano-Ag particles 122, wherein the average grain diameter of cerium oxide particle 121 is between 5 to 20
Between nanometer, and cerium oxide particles 121 account for the 50-75% of 12 total weight of outer covering layer, and the average grain diameter of nano-Ag particles 122 is situated between
Between 1 to 10 nanometer, and nano-Ag particles 122 account for the 25-50% of 12 total weight of outer covering layer.
Please refer to shown in Fig. 4, in order to increase the utilization rate of visible light, can by catalysis material M (i.e. ceria-silver/
Titanium dioxide composite collosol solution) transparent membrane is made, and be applied on a carrier 2, to increase exposed area, to increase light
Catalytic efficiency；Carrier 2 can be glass, ceramics or plastics material, and but not limited thereto.When actual implementation, catalysis material M
It can be formed on 2 surface of carrier by immersion plating or spraying plating mode, and form photocatalysis layer 1；Catalysis material M is in neutrality, no
Carrier 2 can be caused to corrode.When photocatalysis layer 1 is by ultraviolet light or daylight light irradiation, quite high catalytic activity can be generated,
And have the function of decontamination, self-cleaning and antibacterial.
It is worth noting that, the core body 11 of photocatalytic particle 10 has a draw ratio between 1 to 40, so its
With quite high adhesion and storehouse, so as to form the photocatalysis layer 1 with high attachment degree and consistency.Experiment is aobvious
Show, the attachment degree of photocatalysis layer 1 can reach the standard of 5B in the test of hundred lattice, and can also reach in the test of soaked hundred lattice
The standard of 5B；Furthermore photocatalysis layer 1 has high-compactness, and according to 10757 standards of CNS, friction durability of photocatalysis layer 1 can be with
Reach about 3000 times.
Referring back to Fig. 2 to Fig. 4, further, may be constructed one by carrier 2 and photocatalysis layer 1 has extensively in fact
The photocatalytic elements Z of border application, production process are as follows：
One, carrier is cleaned
It is to allow catalysis material M to be more securely attached on carrier 2 to clean carrier 2.Once there is oiliness on 2 surface of carrier
Substance or other filths exist, and plated film will be caused uneven and peeled off.The step of cleaning carrier 2 is as follows：
1. carrier 2 is statically placed in mild detergent, cleaned one hour with ultrasonic vibrating；
2. cleaning the detergent of 2 remained on surface of carrier with deionized water, and cleaned one hour with ultrasonic vibrating；
3. carrier 2 is placed in sodium hydroxide solution, cleaned one hour with ultrasonic vibrating；
4. remaining on the sodium hydroxide solution on 2 surface of carrier with deionized water cleaning, and one is cleaned with ultrasonic vibrating
Hour；And
It dries and preserves 5. carrier 2 is placed in baking oven, in case plated film is used.
Two, film plating process
Photocatalysis layer 1 is formed using dipping coating method, the step of plated film is as follows：
It is drawn high on board 1. the overlay film liquid of catalysis material M is placed in；
2. carrier 2 is fixed on the machine of drawing high；
3. by carrier 2 immerse overlay film liquid in, fall off rate be 5-10 centimeters/it is per minute；
4. start to draw high overlay film, climbing speed is 5-10 centimeters/it is per minute；
5. after overlay film, being placed under ultraviolet lamp and irradiating 30 minutes；
6. the carrier 2 after treatment with ultraviolet light is placed in baking oven, it is dry at 60-160 DEG C, that is, complete photocatalysis layer 1
Overlay film job；And
7. make multilayer coating film, above-mentioned every step must be repeated.
Experimental example 1
In 0 DEG C of ice bath, titanium tetrachloride is slowly dropped into the aqueous hydrochloric acid solution of 5 molar concentrations (5M), then by 30%
Ammonium hydroxide be slowly added to titanium tetrachloride dispersion liquid, be stirred continuously until dispersion liquid pH value be 7, by centrifuging, washing for several times, directly
Concentration to chlorine is less than 5000ppm, obtained colloid is placed in distilled water again at this time, and hydrogen peroxide is added.It is formed by glue
Liquid solution is placed in three neck Conical flasks, is connected condenser pipe and is heated 1 hour at 90 DEG C, and ceria and silver nitrate solution is added,
The weight ratio for adjusting titanium dioxide, hydrogen peroxide, water, ceria solution and silver nitrate solution is 0.02%：0.0255%：
99.902%：0.05%：0.025%, it reheats 2 hours, obtains ceria-silver/titanium dioxide complex sol solution.Finally
In the catalysis material of formation, titanium dioxide, ceria, the silver-colored weight ratio with water are about 0.01%-2%：0.01%-1%：
0.001%-1%：96%-96.979%.
Comparative example 1
Commercially available titanium dioxide (Evonik-Degussa Products, nano-titanium dioxide P-25) is mixed with water, weight
Amount is than being 1/100.
Comparative example 2
In 0 DEG C of ice bath, titanium tetrachloride is slowly dropped into the aqueous hydrochloric acid solution of 5 molar concentrations (5M), then by 30%
Ammonium hydroxide be slowly added to titanium tetrachloride dispersion liquid, be stirred continuously until solution pH value be 7, by centrifuging, washing for several times, until
The concentration of chlorine is less than 5000ppm, obtained colloid is placed in distilled water again at this time, and hydrogen peroxide and silver nitrate is added, and adjusts
Titanium dioxide, hydrogen peroxide, water and silver nitrate solution weight ratio be 0.02%：0.0255%：99.952%：0.0025%, this
Solution connects condenser pipe and is heated 2 hours at 90 DEG C, obtain silver/titanium dioxide complex sol solution in three neck Conical flasks.
Test decontamination and self-cleaning ability
The photocatalysis layer containing experimental example 1 Yu the catalysis material of Comparative Examples 1 and 2 is formed on glass carrier, and utilizes Asia
Methylene blue light-catalyzed reaction tests decontamination and self-cleaning effect as standard.Glass carrier with photocatalysis layer is immersed into methylene
Alkene indigo plant solution (methylene blue containing the Asias 10,000ppm), the ultraviolet light (fluorescent tube of 2 10W) or fluorescent lamp for being around 254nm with wavelength
Pipe irradiates (fluorescent tube of 2 10W), is sampled every 10 minutes, and measuring wavelength with UV-visible spectroscopy again after centrifugation is
Absorption value when 662nm changes situation to judge the disappearance rate of sub- methylene blue by trap.Sub- methylene blue after testing 4 hours
Disappearance rate is as follows.
Table one
| With ultraviolet light | With daylight light irradiation | |
| Comparative example 1 | 2.1 | 0.2 |
| Comparative example 2 | 9.8 | 0.4 |
| Experimental example 1 | 11.3 | 5.1 |
Test antibacterial bacteriostatic ability
The photocatalysis layer containing experimental example 1 Yu the catalysis material of Comparative Examples 1 and 2, and profit ISO are formed on glass carrier
27447:2009 standards worked out test antibacterial under conditions of unglazed irradiation, ultraviolet light and daylight light irradiation respectively
Bacteriostasis.Test strain include be easier to processing Escherichia coli (original 2.68 × 106CFU/ml of bacterial concentration) with it is more difficult
The mycobacteria (original 2.32 × 106CFU/ml of bacterial concentration) of processing.
Table two
Test result shows, optically catalytic TiO 2 (comparative example 1) is only under conditions of ultraviolet light, to Escherichia coli
There is preferable antibacterial effect with mycobacteria, 99% and 80-90% can be reached respectively to the antibiotic rate of two kinds of bacterium.Silver/bis-
Titanium oxide photochemical catalyst (comparative example 2) has with mycobacteria Escherichia coli very excellent although under conditions of ultraviolet light
Different antibacterial effect may be up to 99% to the antibiotic rate of two kinds of bacterium；But it is under conditions of daylight light irradiation, to more intractable
Mycobacteria antibacterial effect it is limited, antibiotic rate only has 50-60%.It is different from optically catalytic TiO 2 and silver/titanium dioxide
Photocatalysis, ceria-silver/titanium dioxide photocatalysis (experimental example 1) is not only in the condition of ultraviolet light and daylight light irradiation
Under, there is very excellent antibacterial effect to Escherichia coli and mycobacteria, 99% may be up to the antibiotic rate of two kinds of bacterium, and
Under the conditions of irradiation and not irradiation, also there is certain antibacterial bacteriostatic ability to Escherichia coli and mycobacteria.
The technique effect of embodiment
The beneficial effects of the present invention are, the catalysis material with antibacterial effect that the embodiment of the present invention is provided,
By the way that " each photocatalytic particle includes a core body and one is formed in outer covering layer on the surface of core body, wherein core
Body is made of titanium dioxide, and outer covering layer is made of ceria and silver, and core body and the weight ratio of outer covering layer are between 1:1
To 1:Between 2, and the weight in outer covering layer shared by ceria be more than silver shared by weight " technical characteristic, can be shone
Light and good antibacterial bacteriostatic ability under the conditions of not irradiation, and when photocatalysis layer is by ultraviolet light or daylight light irradiation, can produce
Raw quite high catalytic activity, and have the function of decontamination, self-cleaning and antibacterial.
From the above, the core body of photocatalytic particle has a draw ratio between 1 to 40, so it has quite
High adhesion and storehouse, so as to form the photocatalysis layer with high attachment degree and consistency.
Content disclosed above is only the preferred possible embodiments of the present invention, and the right for not thereby limiting to the present invention is wanted
The protection domain of book is sought, therefore all equivalence techniques variations done with description of the invention and accompanying drawing content, it is both contained in this hair
In the protection domain of bright claims.
Claims (11)
1. a kind of catalysis material with antibacterial effect, which is characterized in that the catalysis material packet with antibacterial effect
Multiple photocatalytic particles are included, wherein each described photocatalytic particle includes：
One core body, the core body are made of titanium dioxide；And
One outer covering layer, the outer covering layer are formed on the surface of the core body, and the outer covering layer is ceria and silver-colored institute structure
At；
Wherein, the core body and the weight ratio of the outer covering layer are between 1:1 to 1:Between 2, and the dioxy in the outer covering layer
Change the weight shared by cerium more than the weight shared by silver.
2. the catalysis material according to claim 1 with antibacterial effect, which is characterized in that each described photocatalysis
The core body of particle is in needle-shaped, and has a draw ratio between 1 to 40.
3. the catalysis material according to claim 1 with antibacterial effect, which is characterized in that the outer covering layer includes more
The average grain diameter of a nano ceric oxide particle and multiple nano-Ag particles, the plurality of nano ceric oxide particle is situated between
Between 5 to 20 nanometers, the average grain diameter of multiple nano-Ag particles is between 1 to 10 nanometer.
4. the catalysis material according to claim 3 with antibacterial effect, which is characterized in that multiple nano-silicas
Change cerium particle and account for the 50% to 75% of the outer covering layer total weight, multiple nano-Ag particles account for the outer covering layer total weight
25% to 50%.
5. the catalysis material according to claim 1 with antibacterial effect, which is characterized in that the outer covering layer is with continuous
Form be formed on the surface of the core body.
6. the catalysis material according to claim 1 with antibacterial effect, which is characterized in that the outer covering layer is to disperse
Form be formed on the surface of the core body.
7. a kind of preparation method of the catalysis material as described in claim 1 with antibacterial effect, which is characterized in that described
The preparation method of catalysis material with antibacterial effect includes the following steps：
Titanium hydroxide colloid is prepared, hydrogen peroxide is then added, to form titanium dioxide colloid solution；And at 60 DEG C to 100 DEG C
At a temperature of, ceria and silver nitrate is added to the titanium dioxide colloid solution, then heated at constant temperature is until colloid hydrolysis
It disappears, to form the catalysis material with antibacterial effect, the wherein weight ratio of titanium dioxide, ceria, silver and water
For 0.01%-2%：0.01%-1%：0.001%-1%：96%-96.979%.
8. the preparation method of the catalysis material according to claim 7 with antibacterial effect, which is characterized in that the hydrogen
Titanium oxide colloid, by titanium tetrachloride and combined, is mixed then at being formed by first at a temperature of 0 DEG C to 15 DEG C
Ammonium hydroxide is added in object and is made.
9. the preparation method of the catalysis material according to claim 8 with antibacterial effect, which is characterized in that described two
The molar ratio of hydrogen peroxide and titanium dioxide is between 2 in titanium oxide colloid solution:1 to 5:Between 1, and the solid content of titanium dioxide is situated between
Between 0.01% to 2%.
10. the preparation method of the catalysis material according to claim 8 with antibacterial effect, which is characterized in that described
Catalysis material with antibacterial effect is with a pH value between 6.5 to 10.
11. a kind of photocatalytic elements, which is characterized in that the photocatalytic elements include a carrier and one using such as claim
The catalysis material with antibacterial effect described in 1 is coated on the carrier and the photocatalysis layer of formation.
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| CN111567560A (en) * | 2020-05-18 | 2020-08-25 | 同曦集团有限公司 | Antibacterial, mildewproof and antiviral composition for mobile phone shell, mobile phone shell and preparation method and application of antibacterial, mildewproof and antiviral composition |
| CN113231053A (en) * | 2020-09-21 | 2021-08-10 | 阿列德拉公司 | Self-disinfecting photocatalyst sheet |
| CN114190401A (en) * | 2021-11-30 | 2022-03-18 | 华中科技大学 | Method for preparing cerium oxide nanoenzyme based on laser liquid phase irradiation and application |
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| CN101049563A (en) * | 2007-05-22 | 2007-10-10 | 成都理工大学 | Preparing Nano Ag/CeO2 catalyst possessing catalytic activity of visible light |
| CN101138342A (en) * | 2007-09-28 | 2008-03-12 | 上海师范大学 | Nanometer mesoporous cerium oxide carrying silver antimicrobials and method for preparing the same |
| CN101485981A (en) * | 2009-02-13 | 2009-07-22 | 中南大学 | Method for preparing inorganic antimicrobial composite material |
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| WO2007066934A1 (en) * | 2005-12-06 | 2007-06-14 | Lg Chem, Ltd. | Core-shell type nanoparticles and method for preparing the same |
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| CN101049563A (en) * | 2007-05-22 | 2007-10-10 | 成都理工大学 | Preparing Nano Ag/CeO2 catalyst possessing catalytic activity of visible light |
| CN101138342A (en) * | 2007-09-28 | 2008-03-12 | 上海师范大学 | Nanometer mesoporous cerium oxide carrying silver antimicrobials and method for preparing the same |
| CN101485981A (en) * | 2009-02-13 | 2009-07-22 | 中南大学 | Method for preparing inorganic antimicrobial composite material |
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| CN111567560A (en) * | 2020-05-18 | 2020-08-25 | 同曦集团有限公司 | Antibacterial, mildewproof and antiviral composition for mobile phone shell, mobile phone shell and preparation method and application of antibacterial, mildewproof and antiviral composition |
| CN111567560B (en) * | 2020-05-18 | 2021-07-20 | 同曦集团有限公司 | Antibacterial, mildewproof and antiviral composition for mobile phone shell, mobile phone shell and preparation method and application of antibacterial, mildewproof and antiviral composition |
| CN113231053A (en) * | 2020-09-21 | 2021-08-10 | 阿列德拉公司 | Self-disinfecting photocatalyst sheet |
| CN114190401A (en) * | 2021-11-30 | 2022-03-18 | 华中科技大学 | Method for preparing cerium oxide nanoenzyme based on laser liquid phase irradiation and application |
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