CN113429222A - Ag/TiO2Photocatalytic ceramic tile and preparation method thereof - Google Patents
Ag/TiO2Photocatalytic ceramic tile and preparation method thereof Download PDFInfo
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- 239000000919 ceramic Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 230000001699 photocatalysis Effects 0.000 claims abstract description 56
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 25
- 229910021649 silver-doped titanium dioxide Inorganic materials 0.000 claims abstract description 22
- 238000005507 spraying Methods 0.000 claims abstract description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 20
- 238000001354 calcination Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 8
- 229940043237 diethanolamine Drugs 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 238000000034 method Methods 0.000 claims description 3
- 239000011941 photocatalyst Substances 0.000 claims description 3
- 230000003746 surface roughness Effects 0.000 claims description 3
- 101710134784 Agnoprotein Proteins 0.000 claims description 2
- 239000007921 spray Substances 0.000 claims description 2
- 239000000956 alloy Substances 0.000 claims 1
- 229910045601 alloy Inorganic materials 0.000 claims 1
- 238000007146 photocatalysis Methods 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 20
- 230000001954 sterilising effect Effects 0.000 abstract description 16
- 238000004659 sterilization and disinfection Methods 0.000 abstract description 16
- 230000000694 effects Effects 0.000 abstract description 10
- 241000588724 Escherichia coli Species 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract description 3
- 238000003980 solgel method Methods 0.000 abstract description 3
- 230000005284 excitation Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract 2
- 238000012360 testing method Methods 0.000 description 19
- 238000002474 experimental method Methods 0.000 description 8
- 239000011521 glass Substances 0.000 description 4
- 238000004506 ultrasonic cleaning Methods 0.000 description 4
- 239000002390 adhesive tape Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 241000607142 Salmonella Species 0.000 description 2
- 241000607768 Shigella Species 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 241000191940 Staphylococcus Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 244000005700 microbiome Species 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
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007655 standard test method Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
- C04B41/5116—Ag or Au
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- 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
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B01J35/39—
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- B01J35/40—
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/80—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only ceramics
- C04B41/81—Coating or impregnation
- C04B41/85—Coating or impregnation with inorganic materials
- C04B41/88—Metals
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Abstract
The invention belongs to the technical field of photocatalytic sterilization materials, and particularly relates to Ag/TiO2A photocatalytic ceramic tile and a preparation method thereof. The photocatalytic material in the invention is Ag/TiO2Ag modified TiO2Can realize the excitation under the light to achieve the sterilization effect. The preparation method firstly prepares Ag/TiO in one step by utilizing a sol-gel method2The precursor liquid of the photocatalytic material is sprayed on glazed ceramic tiles by a spraying method, and after the precursor liquid is calcined at 1000 ℃, Ag/TiO is added2The photocatalytic material is firmly attached to the surface of the ceramic tile, is not easy to fall off, has good photocatalytic activity, and can effectively kill escherichia coli in water.
Description
Technical Field
The invention belongs to the technical field of photocatalytic sterilization materials, and particularly relates to Ag/TiO2A photocatalytic ceramic tile and a preparation method thereof.
Background
TiO2The photocatalytic material is a non-toxic and environment-friendly novel semiconductor material, can generate active species with strong oxidation reduction property by utilizing light energy, has no obvious selectivity when treating microbial pollution, can efficiently kill microorganisms, has good stability, and shows good application prospect as a sterilization material. But pure TiO2Because the band gap is wider (more than or equal to 3.2 eV), the excitation can not be carried out under visible light, and the practical application is greatly reduced.
Secondly, the powdered titanium dioxide is difficult to separate, recover and reuse, resulting in a great increase in cost in practical use, and thus, TiO can be used2The photocatalytic material is loaded on the glazed ceramic tile to solve the above problems. However, TiO with high catalytic performance is loaded on the ceramic tile under the condition of higher temperature2The anatase phase will transform into the rutile phase, which has relatively low catalytic properties, even deactivating the catalyst, while at lower temperatures the adhesion of the material to the tile surface is poor, so that the effect of temperature on the material properties must be taken into account when selecting the temperature.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a novel TiO2Photocatalytic ceramic tiles.
The technical scheme of the invention is that Ag/TiO2Photocatalytic ceramic tile, prepared by mixing Ag/TiO photocatalytic material2Loaded on the surface of the ceramic tile; photocatalytic material Ag/TiO2The prepared photocatalytic ceramic tile is an irregular polyhedron with the grain diameter of 1-2 mu m, the surface roughness of the prepared photocatalytic ceramic tile is 65.7-211 nm, and the photocatalyst load on the photocatalytic ceramic tile is 14.1 +/-0.3N.
The invention also provides the Ag/TiO2The preparation method of the photocatalytic ceramic tile comprises the following steps:
(1) adding anhydrous ethanol CH3Mixing and stirring COOH and diethanol amine to obtain solution A;
(2) adding titanium Tetraisopropoxide (TIIP) into the solution A, and stirringAfter being mixed evenly, AgNO is added3Slowly dripping the solution into the solution, and stirring to obtain white sol gel B;
(3) and (3) after aging the sol-gel B at room temperature, atomizing the sol-gel B by using a spray gun at a distance of 10-15 cm, spraying the atomized sol-gel B onto the ceramic tile, drying the ceramic tile in an oven, and finally calcining the ceramic tile in a muffle furnace to obtain the Ag/TiO2 photocatalytic ceramic tile.
Specifically, in the step (1), the volume ratio of the absolute ethyl alcohol to the diethanolamine is 32-35 mL: 1.9-2.1 mL.
Wherein, in the step (1), the stirring time is 30 minutes.
Further, in the step (2), the addition amount of TIIP is 6.5-7.0 mL, and AgNO3The concentration and the addition amount of the solution were 0.2mol/L and 0.75mL, respectively.
Wherein, in the step (1), the stirring time is 2 hours.
Preferably, in step (3), the aging time is 12 hours.
Specifically, in the step (3), the drying temperature is 100 ℃ and the drying time is 30 minutes.
Specifically, in the step (3), the calcining temperature is 800-1000 ℃, the heating rate is 5 ℃/min, and the calcining time is 2 hours.
Considering the sterilization effect and the adhesion experiment effect comprehensively, preferably, in the step (3), the calcination temperature is 950-1000 ℃.
More preferably, in the step (3), the calcination temperature is 1000 ℃.
Wherein, the stirring in the steps (1) and (2) is magnetic stirring.
Preferably, in the step (3), the ceramic tile is cleaned by ultrasonic for 60 min.
Preferably, in the step (3), the dosage of the sol-gel B is 4-5 mL/18cm2。
The invention also provides Ag/TiO prepared by the method2Photocatalytic ceramic tiles.
At present, the preparation temperature of TiO2 photocatalytic ceramic tiles is mainly 600-850 ℃, because the ceramic tiles are prepared at the temperature in the intervalThe TiO2 photocatalytic ceramic tile can keep anatase phase and has better photocatalytic activity. Although a few studies have reported a preparation method capable of maintaining an anatase phase at a high temperature of 900 to 1100 ℃, no photocatalytic activity test or sterilization test has been conducted at a temperature (900 to 1100 ℃) in this interval, and thus the photocatalytic activity of a material at this temperature range is unknown, but with respect to TiO at 900 ℃ or higher2The reports of a photocatalytic ceramic tile preparation method, photocatalytic activity or sterilization performance are not available at present.
The invention has the beneficial effects that:
the preparation method is simple and easy to operate, and can successfully prepare Ag/TiO2Load to the tile surface. The photocatalytic material is prepared at the high temperature of 1000 ℃, can be excited under visible light to generate active free radicals, and achieves an effective sterilization effect on bacteria in water. In addition, after the material load to glazed ceramic tile, can be firm attached to the ceramic tile surface, be difficult for droing, improved the recoverability of material greatly.
Drawings
FIG. 1 Ag/TiO prepared in example 12AFM drawing of the photocatalytic ceramic tile;
FIG. 2 (a) TiO2 at different temperatures2An XRD spectrum; (b) Ag/TiO at different temperatures2An XRD spectrum;
FIG. 3 calcination temperature vs. Ag/TiO in the preparation Process2Influence of the sterilization effect of the photocatalytic ceramic tile; (a) escherichia coli (b) staphylococcus aureus (c) salmonella (d) shigella.
FIG. 4, image of sample after scratch test; (a) TiO22Photocatalytic ceramic tiles; (b) Ag/TiO22Photocatalytic ceramic tiles.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
The raw materials, tiles and equipment adopted by the invention can be obtained from the market or are commonly used in the field if not specified, and the methods in the examples are conventional in the field if not specified.
EXAMPLE 1 Ag/TiO2Preparation of photocatalytic ceramic tiles
Step 1: first 33.5mL CH3Mixing COOH and 2.05mL of diethanolamine, and magnetically stirring for 30min to obtain a solution A;
step 2: adding 6.7mL of TIIP, stirring uniformly, and adding 0.2mol/L AgNO3Slowly dripping 0.75mL of the solution into the solution, and continuously stirring the solution for 2 hours by magnetic force to obtain white sol-gel B;
and step 3: aging the sol-gel B at room temperature for 12h, spraying the aged sol-gel B on the ceramic tile at a distance of about 15cm from the ceramic tile dried after ultrasonic cleaning for 60min, drying at 90 ℃ for 20min, and calcining at a temperature rise rate of 5 ℃/min and a temperature of 1000 ℃ for 2h to obtain Ag/TiO2Photocatalytic tiles (A/T-PC).
The photocatalytic tiles prepared in example 1 were subjected to AFM tests (Analysis of the roughness of the tile surface by means of the NanoScope Analysis 1.7 software) which showed that Ag/TiO2The surface roughness of the photocatalytic ceramic tile is 112nm, and Ag/TiO on the surface2The particle size of the photocatalytic material is 1-2 μm.
EXAMPLE 2 Ag/TiO2Preparation of photocatalytic ceramic tiles
Step 1: first 33.5mL CH3Mixing COOH and 1.9mL of diethanolamine, and magnetically stirring for 30min to obtain a solution A;
step 2: adding 6.5mL of TIIP, stirring uniformly, and adding 0.2mol/L AgNO3Slowly dripping 0.75mL of the solution into the solution, and continuously stirring the solution for 2 hours by magnetic force to obtain white sol-gel B;
and step 3: aging the sol-gel B at room temperature for 12h, spraying the aged sol-gel B on the ceramic tile at a distance of about 15cm from the ceramic tile dried after ultrasonic cleaning for 60min, drying at 90 ℃ for 20min, and calcining at a temperature rise rate of 5 ℃/min and a temperature of 1000 ℃ for 2h to obtain Ag/TiO2Photocatalytic tiles (A/T-PC).
Example 3 Ag/TiO2Preparation of photocatalytic ceramic tiles
Step 1: 32.0mL CH first3Mixing COOH and 2.1mL of diethanolamine, and magnetically stirring for 30min to obtain a solutionA；
Step 2: adding 7.0mL of TIIP, stirring uniformly, and adding 0.2mol/L AgNO3Slowly dripping 0.75mL of the solution into the solution, and continuously stirring the solution for 2 hours by magnetic force to obtain white sol-gel B;
and step 3: aging the sol-gel B at room temperature for 12h, spraying the aged sol-gel B on the ceramic tile at a distance of about 15cm from the ceramic tile dried after ultrasonic cleaning for 60min, drying at 90 ℃ for 20min, and calcining at a temperature rise rate of 5 ℃/min, at a temperature of 800 ℃, 900 ℃, 950 ℃ and 1000 ℃ for 2h to obtain Ag/TiO2Photocatalytic tiles (A/T-PC).
Example 4 TiO2Preparation of photocatalytic ceramic tiles
Preparation of TiO by sol-gel method2. Titanium tetraisopropoxide (titanium (IV) i-promoter, TIIP) is used as a titanium source, firstly, 33.5mL of CH3COOH and 2.01mL of diethanolamine are mixed and magnetically stirred for 30min to obtain a solution A, then 6.7mL of TIIP is added, and magnetic stirring is continued for 2h to obtain sol-gel B. And (3) aging the sol-gel B at room temperature for 12h, drying half of the sol-gel B in a drying oven at 90 ℃ for 24h, and finally calcining the sol-gel B at 800 ℃ for 2h at the heating rate of 5 ℃/min to obtain pure TiO 2.
The tile (6 x 3cm in size) dried after ultrasonic cleaning for 60min was sprayed with the other half of the aged sol-gel B onto the glazed surface of the tile at a distance of about 15cm, followed by drying at 90 ℃ for 20 min. Finally calcining for 2h at the temperature rise rate of 5 ℃/min and the temperature of 800 ℃, 900 ℃, 950 ℃ and 1000 ℃ respectively to obtain TiO2Photocatalytic tiles, labeled T-PCT.
The XRD patterns of the products prepared in examples 3 and 4 were measured. As shown in FIG. 2, TiO was doped with Ag and the temperature was changed2The diffraction peak of (A) is not changed, which shows that the doping of Ag and the change of temperature are applied to TiO2The crystal form of (A) is not greatly influenced, which shows that TiO prepared by adopting a sol-gel method2And Ag/TiO2Has good high temperature resistance and can be applied to deposition on ceramic tiles.
EXAMPLE 5 Sterilization test
Taking porcelain not loaded with photocatalytic materialTile (Dongpo tile, model 630eln 52005-a), TiO prepared in example 42Photocatalytic Tile, Ag/TiO prepared in example 32The photocatalytic ceramic tile was subjected to sterilization experiments. The bacteria used are Escherichia coli, Staphylococcus, Shigella and Salmonella.
In a photoreactor (Instrument model YM-GHX-V, manufacturer: Shanghai Yuming instruments Ltd.). The glass tube in the apparatus is a photoreaction tube, the bacterial suspension is added in the glass tube, and then the ceramic tile is put in the glass tube. The instrument has xenon lamp and optical filter between the xenon lamp and the peripheral light reaction tube to filter ultraviolet light emitted from the light source. Therefore, in the experiment, a filter is added between the light source and the reactor, and the filter can filter out all ultraviolet light below 420nm, so that the experiment can be ensured to be carried out under the visible light condition. All the ceramic tiles are 3 multiplied by 6cm in size, 1cm in height and 141500 lux in illumination intensity; coexisting ions: 0.9% Cl-(ii) a Initial concentration C of bacterial liquid0：106CFU/mL。
As can be seen from FIG. 3, Ag/TiO compounds were prepared at 800 deg.C, 900 deg.C, 950 deg.C and 1000 deg.C2The sterilization efficiency of the photocatalytic ceramic tile is respectively 99.9999 percent, 99.9990 percent, 99.81 percent and 99.716 percent, which shows that the preparation temperature is opposite to Ag/TiO2The sterilization effect of photocatalytic tiles has a significant impact, with sterilization efficiency decreasing with increasing temperature. TiO without Ag2The photocatalytic ceramic tile has poor sterilization effect at a certain temperature, which shows that the sterilization effect of the material can be obviously improved by doping Ag.
Example 6 attachment experiments
Adhesive Tape experiment (Tape Test)
The prepared photocatalytic ceramic tile was subjected to an Adhesion Test using a Standard Test method for Measuring Adhesion by Tape Test (D3359-08), hereinafter referred to as "Tape Test") of the American Tape Test.
The testing steps are as follows: in an area of 125mm2The test area of (A) was cut into a 5X 5 mm-sized grid with a knife, and the tape was centered on the test areaAbove the grid and with the fingers the center of the grid is smoothed into place. Then after a period of 90 ± 30 s, the free end is grasped, the tape is torn off, and the tape is torn off quickly (without shaking) at an angle as close to 180 ° as possible. Finally, the test area is checked by using a magnifying glass, and the falling proportion of the material is determined by comparing with the attachment area of the material before the test. The entire experiment was repeated three times. The adhesion was scored according to the drop ratio of the material, the evaluation criteria being detailed in table 1.
TABLE 1 evaluation criteria for test results of adhesive tapes
As can be seen from table 2, the temperature has a significant effect on the adhesion of the four materials, with the adhesion increasing gradually with increasing temperature. In the use of Ag to TiO2After modification, the adhesion is improved.
TABLE 2 photocatalytic Tile adhesive tape test results at different temperatures
Micro scratch test
The coating adhesion of the photocatalytic tiles was tested with a micrometer scratch tester (model conventional MCT, manufacturer: switzerland csm). The linear increase of the load ranged from 0.1N to 30N, and the scratch speed was 1 mm/min. TiO at 1000 DEG C2Photocatalytic ceramic tile and Ag/TiO2Photocatalytic tiles were subjected to micron scratch experiments with linearly increasing load.
The results show (table 3, fig. 4) that the incorporation of Ag leads to a very small decrease in the first critical load, but favours an increase in the second critical load. Ag/TiO22The first critical load Lc1 (coating failure) of the photocatalytic material on the surface of the photocatalytic tile is 5.2 + -0.2N, and the second critical load Lc1 (coating detachment) is 14.1 + -0.3N.
TABLE 3 sample scratch test results
| Sample numbering | First critical load (Lc 1) | Second critical load (Lc 1) |
| T-PCT | 4.08N | 10.56N |
| A/T-PCT | 3.97N | 14.35N |
Claims (10)
1. Ag/TiO2Photocatalysis ceramic tile, its characterized in that: adding a photocatalytic material Ag/TiO2The photocatalyst is loaded on the surface of the ceramic tile, the surface roughness of the prepared photocatalytic ceramic tile is 65.7-211 nm, and the load of the photocatalyst on the photocatalytic ceramic tile is 14.1 +/-0.3N.
2. The Ag/TiO alloy of claim 12The preparation method of the photocatalytic ceramic tile is characterized by comprising the following steps:
(1) adding anhydrous ethanol CH3Mixing and stirring COOH and diethanol amine to obtain solution A;
(2) adding titanium Tetraisopropoxide (TIIP) into the solution A, stirring uniformly, and adding AgNO3Slowly dripping the solution into the solution, and stirring to obtain white sol gel B;
(3) and (3) after aging the sol-gel B at room temperature, atomizing the sol-gel B by using a spray gun at a distance of about 10-15 cm, spraying the atomized sol-gel B onto the ceramic tile, drying the ceramic tile in an oven, and finally calcining the ceramic tile in a muffle furnace to obtain the Ag/TiO2 photocatalytic ceramic tile.
3. Ag/TiO according to claim 22The preparation method of the photocatalytic ceramic tile is characterized in that in the step (1), the volume ratio of absolute ethyl alcohol to diethanolamine is 32-35 mL: 1.9-2.1 mL.
4. Ag/TiO according to claim 22The preparation method of the photocatalytic ceramic tile is characterized in that in the step (1), the stirring time is 30 minutes.
5. Ag/TiO according to claim 22The preparation method of the photocatalytic ceramic tile is characterized in that in the step (2), the addition amount of TIIP is 6.5-7.0 mL, and AgNO is added3The concentration and the addition amount of the solution were 0.2mol/L and 0.75mL, respectively.
6. Ag/TiO according to claim 22The preparation method of the photocatalytic ceramic tile is characterized in that in the step (1), the stirring time is 2 hours.
7. Ag/TiO according to claim 22The preparation method of the photocatalytic ceramic tile is characterized in that in the step (3), the aging time is 12 hours.
8. Ag/TiO according to claim 22The preparation method of the photocatalytic ceramic tile is characterized in that in the step (3), the drying temperature is 90 ℃ and the drying time is 30 minutes.
9. Ag/TiO according to claim 22The preparation method of the photocatalytic ceramic tile is characterized in that in the step (3), the calcining temperature is 800-1000 ℃, the heating rate is 5 ℃/min, and the calcining time is 2 hours;
preferably, in the step (3), the calcining temperature is 950-1000 ℃;
preferably, in the step (3), the calcining temperature is 1000 ℃;
preferably, the stirring in the steps (1) and (2) is magnetic stirring;
preferably, in the step (3), the ceramic tile is cleaned by ultrasonic for 60 min;
preferably, in the step (3), the dosage of the sol-gel B is 4-5 mL/18cm2。
10. Prepared by the method of any one of claims 2 to 9To Ag/TiO2Photocatalytic ceramic tiles.
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