CN106396387A - Antibacterial radiation-proof ceramic tile and preparation method thereof - Google Patents

Antibacterial radiation-proof ceramic tile and preparation method thereof Download PDF

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Publication number
CN106396387A
CN106396387A CN201610748652.2A CN201610748652A CN106396387A CN 106396387 A CN106396387 A CN 106396387A CN 201610748652 A CN201610748652 A CN 201610748652A CN 106396387 A CN106396387 A CN 106396387A
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gqds
powder
preparation
aqueous solution
ultrasonic
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麦浩
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Bright Cities And Towns Gaoming District Foshan City New Forms Of Energy New Material Industry Innovation Centers
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Bright Cities And Towns Gaoming District Foshan City New Forms Of Energy New Material Industry Innovation Centers
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/06—Frit compositions, i.e. in a powdered or comminuted form containing halogen
    • 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
    • C04B41/52—Multiple coating or impregnating multiple coating or impregnating with the same composition or with compositions only differing in the concentration of the constituents, is classified as single coating or impregnation
    • 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
    • C04B41/89—Coating or impregnation for obtaining at least two superposed coatings having different compositions

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Structural Engineering (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses an antibacterial radiation-proof ceramic tile and a preparation method thereof. The preparation method comprises the steps of: A, preparing ground glaze: by mass percentage: mixing 30-35% of frit, 1-6% of antibacterial powder, 20-28% of lithium chinastone, 5-10% of zirconium silicate, 20-25% of kaolin and 10-12% of quartz evenly, conducting wet ball milling, and performing sieving to obtain pulp ground glaze; B, preparing surface glaze: by mass percentage, mixing 70-80% of frit, 1-5% of nano bamboo charcoal, 10-20% of kaolin, 5-8% of alumina, 1-2% of zinc oxide and 1-5% of zirconium silicate evenly, conducting wet ball milling, and then performing sieving to obtain pulp surface glaze; and C, applying the ground glaze and the surface glaze obtained in step A and step B to a tile blank in order, and performing firing to obtain the ceramic tile. Compared with the existing ceramic tiles, the ceramic tile prepared by the method provided by the invention has the advantages of scientific compounding, reasonable preparation, and stable performance. Also through reasonable collocation of nano bamboo charcoal and the antibacterial powder, the two play a synergistic role and endow the ceramic tile with excellent antibacterial, radiation-proof and air purification performance, thus further broadening the application scope of the ceramic tile.

Description

A kind of antibiotic radiation proof Ceramic Tiles and preparation method thereof
Technical field
The present invention relates to quartz technical field, more particularly to a kind of antibiotic radiation proof Ceramic Tiles and its preparation side Method.
Background technology
Bacterium, mould has very big harm as pathogen to the mankind and animals and plants, and the health of impact people even jeopardizes life Life, brings great economic loss.The research of therefore anti-biotic material and its product increasingly causes the concern of people, antibacterial product Demand will constitute huge market.
Ceramic Tiles are by clay and other inorganic non-metallic raw materials, the tabular through technique productions such as shaping, sintering or bulk Ceramic, for decorating and protecting building, the metope of structures and ground.
But, also it is rarely reported the Ceramic Tiles of the antibacterial functions preferably stable with regard to uniformity at present.And existing pottery Ceramic tile is usually the product of simple function, function such as antibacterial, antistatic etc., and that is, a kind of product does not possess multiple function, this pole Limit greatly its range of application, need to improve further.
Content of the invention
In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of antibiotic radiation proof Ceramic Tiles and its preparation side Method.
The technical problem to be solved is achieved by the following technical programs：
A kind of antibiotic radiation proof Ceramic Tiles and preparation method thereof, this preparation method comprises the following steps：
Step A, prepares ground-coat enamel：By mass percentage, by 30 ~ 35% frits, 1 ~ 6% antibacterial powder, 20 ~ 28% lithium porcelain stones, 5 ~ 10% Zirconium silicate, 20 ~ 25% kaolin and 10 ~ 12% quartz mix, wet ball grinding, obtain pulpous state ground-coat enamel after crossing 300 ~ 350 mesh sieves；
Step B, prepares cover-coat enamel：By mass percentage, by 70 ~ 80% frits, 1 ~ 5% bamboo charcoal nano, 10 ~ 20% kaolin, 5 ~ 8% aluminum oxide, 1 ~ 2% zinc oxide and 1 ~ 5% zirconium silicate mix, wet ball grinding, obtain pulpous state cover-coat enamel after crossing 300 ~ 350 mesh sieves；
Step C, will be native in ceramic tile base using drenching glaze mode priority glazing to the ground-coat enamel of step A, B preparation and cover-coat enamel；Then in kiln Burn till, firing temperature is 800 ~ 900 DEG C, firing period is 40 ~ 50min, obtains Ceramic Tiles；
Wherein, described frit is obtained by the following method：By weight percentage, by 10 ~ 18% quartz, 5 ~ 12% feldspars, 15 ~ 25% borax, 3 ~ 12% carbonate, 20 ~ 35% boric acid, 3 ~ 8% spodumenes, 1 ~ 4% fluoride salt, 1 ~ 5% kaolin mixed grinding are uniform, Then after high-temperature fusion, quick quenching is obtained.
In the present invention, described feldspar is by potassium feldspar and albite by weight 3 ~ 5:1 ~ 2 is obtained by mixing.Described carbonate It is made up of at least one in potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate it is preferable that described carbonate is by carbonic acid Potassium, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate by weight 3:1:3:2:1 is obtained by mixing.Described fluoride salt by sodium fluoride, Calcirm-fluoride and lithium fluoride by weight 4:2:1 is obtained by mixing.
In the present invention, described bamboo charcoal nano is the bamboo charcoal nano of average grain diameter 100 ~ 500nm.
In the present invention, described antibacterial powder can be obtained by the following method：
（1）Weigh 0.3 ~ 1gC60 powder, measure the concentrated sulfuric acid that 80 ~ 100ml mass fraction is 98%, by C60 powder and the concentrated sulfuric acid Beaker mixes, beaker is placed in ice-water bath, stirred with the speed of 500 ~ 600rpm simultaneously, obtain mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, slowly adds in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, instead Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtain Graphene quantum dot（GQDs）Suspension；100 ~ 150rpm speed stirs GQDs suspension, laser irradiation 30 ~ 60min simultaneously, swashs Light irradiation power is 0.5 ~ 2W；Standby；
（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropping concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solution；Dropwise plus Entering concentration is 0.1 ~ 0.5mol/L ammonium dihydrogen phosphate（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2 ~ 3: 1）, ultrasonic agitation 10 ~ 20min；Be added dropwise over 0.5 ~ 1mol/L sodium hydroxide solution, adjust pH value to 11, then standing, from The heart, deionized water and ethanol replace washing three times, vacuum drying, obtain GQDs/Ag2O；
（3）Take 1 ~ 3gGQDs/Ag2O ultrasonic agitation is scattered in 80 ~ 120ml aqueous solution；Be added dropwise over concentration be 0.005 ~ The 0.05mol/L cerous nitrate aqueous solution, being added dropwise over concentration after 30 ~ 60min is 0.005 ~ 0.05mol/L zinc nitrate aqueous solution, GQDs/Ag2The O aqueous solution, the cerous nitrate aqueous solution and zinc nitrate aqueous solution volume ratio are 1:0.1~0.2:0.2~0.4；Continue ultrasonic Stirring, regulation mixed solution pH value to 7.0；Side ultrasonic agitation, side adds the hydrazine hydrate that 4 ~ 8mL mass fraction is 50%, 30 ~ Reduction reaction 0.5 ~ 1h at 40 DEG C；Afterwards, the hydrazine hydrate that 40 ~ 50mL mass fraction is 50%, reduction reaction at 85 DEG C are added After 30 ~ 48h；Filter, be washed with deionized for several times, vacuum drying, obtain GQDs/Ag2O/Ag-Zn-Ce；
（4）By 0.1 ~ 0.5gGQDs/Ag2O/Ag-Zn-Ce ultrasonic agitation is scattered in the aqueous solution；Add volume ratio 3 ~ 5 afterwards:1 Water and ammoniacal liquor, be stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag2The mass ratio of O/Ag-Zn-Ce is 3:1~3）, adjust PH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 30 ~ 60min；Carry out being centrifuged and being cleaned with acetone and deionized water successively Obtain precipitation；This is deposited at 80 ~ 90 DEG C 2 ~ 4h is dried, to obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2；By GQDs/ Ag2O/Ag-Zn-Ce/SiO2It is placed under argon gas atmosphere and carries out 500 ~ 800 DEG C of heat treatment 1 ~ 2h, after being cooled to room temperature, be immersed in hydrogen In fluoric acid, ultrasonic 10 ~ 15min is carried out with ultrasonic power 100 ~ 150W, remove surface local silica, be centrifuged and be dried, obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2；
（5）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2O/Ag-Zn-Ce/ SiO2In the aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag2O/Ag-Zn-Ce/SiO2Weight than for 1:1~5；10~100W Ultrasonic 60 ~ 120min, standing, deionized water is washed for several times, and centrifugation is placed in confined space, carries out vacuumizing → heat pressurization Circulation 3 ~ 8 times（Pumpdown time is 20 ~ 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, it is forced into 0.3 ~ 0.6Mpa, pressurize 20 ~ 30min）, obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2/ Graphene antibiosis powder, that is, resist Bacterium powder.
In the present invention, described antibacterial powder can also be obtained by the following method：
（1）Weigh 0.3 ~ 1gC60 powder, measure the concentrated sulfuric acid that 80 ~ 100ml mass fraction is 98%, by C60 powder and the concentrated sulfuric acid Beaker mixes, beaker is placed in ice-water bath, stirred with the speed of 500 ~ 600rpm simultaneously, obtain mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, slowly adds in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, instead Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtain Graphene quantum dot（GQDs）Suspension；100 ~ 150rpm speed stirs GQDs suspension, laser irradiation 30 ~ 60min simultaneously, swashs Light irradiation power is 0.5 ~ 2W；Standby；
（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropping concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solution；Dropwise plus Entering concentration is 0.1 ~ 0.5mol/L ammonium dihydrogen phosphate（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2 ~ 3: 1）, ultrasonic agitation 10 ~ 20min；Be added dropwise over 0.5 ~ 1mol/L sodium hydroxide solution, adjust pH value to 11, then standing, from The heart, deionized water and ethanol replace washing three times, vacuum drying, obtain GQDs/Ag2O；
（3）Take 1 ~ 3gGQDs/Ag2O ultrasonic agitation is scattered in the aqueous solution；Being added dropwise over concentration is 0.05 ~ 0.5g/100mlZnO The quantum dot aqueous solution, ultrasonic power mixing speed respectively halves；After 60 ~ 90min, standing, filter, be washed with deionized for several times, Vacuum drying, obtains GQDs/Ag2O/ZnO；
（4）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2The O/ZnO aqueous solution In, three-dimensional sponge shape Graphene and GQDs/Ag2The weight of O/ZnO is than for 1:1~5；Ultrasonic 60 ~ the 120min of 10 ~ 100W, standing, Deionized water is washed for several times, and centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 3 ~ 8 times（Pumpdown time For 20 ~ 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.3 ~ 0.6Mpa, Pressurize 20 ~ 30min）, obtain GQDs/Ag2O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.
Wherein, described three-dimensional sponge shape graphene preparation method is as follows：By 3g graphite powder, 1g NaNO3 is in ice-water bath Mix with 250ml 98% concentrated sulfuric acid, be slowly added to 6g KMnO4.Then heat at 35 DEG C, after stirring 40min, add 95ml deionized water, is warming up to 98 DEG C of reaction 20min；Add 270ml water dilution, and with 5ml 30% H2O2 with many Remaining KMnO4, the color of mixed solution is brown color, filters while hot, and deionized water cyclic washing obtains to neutrality, ultrasonic disperse GO；The graphene oxide solution that 200ml mass fraction is 5mg/ml is taken to pour diameter 25cm, the discoid reaction utensil of high 2cm into In, add ascorbic acid (VC) 0.5g stirring so that it is sufficiently mixed；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reactions 15h, Graphene oxide Spontaneous Contraction in reaction utensil is cross-linked into three-dimensional sponge structure, freeze-drying, obtains the three-dimensional sponge shape of flexibility Graphene.
The present invention has the advantages that：
Compare with existing Ceramic Tiles, the Ceramic Tiles dispensing science that the present invention manufactures, preparation is reasonable, stable performance, high mechanical strength, It is unlikely to deform and non-aging；And through rational arrange in pairs or groups bamboo charcoal nano and antibacterial powder, both synergies are so that Ceramic Tiles There is excellent antibacterial and radiation proof and purify air performance, widened the range of application of Ceramic Tiles further；
This method loads and fixing antiseptic on three-dimensional grapheme, not only prevents its reunion, significantly improves metal nanoparticle Deng antiseptic stability so as to can more preferably be dispersed in Ceramic Tiles, and there is more efficient antibacterial activity and silver ion not Oxidation stain can be overflowed；It is compounded with the anti-microbial property of multiple antiseptics simultaneously, have more compared to single silver nano antibacterial agent Good antibacterial effect, antibacterial is lasting；Bamboo charcoal nano contains the multiple beneficial element such as charcoal, hydrogen, oxygen, fine and closely woven porous, can block and Absorb the erosion of the harm ray that various electrical equipment produce, make human body thoroughly exempt the harm of harm ray, bamboo charcoal nano also can produce Raw anion, adsorbs and decomposes various free harmful substances, automatically adjust humidity, also can produce and be best suitable for the far red of human body Outside line.
Specific embodiment
To further illustrate technical scheme below by specific preferred embodiment.
Embodiment 1
A kind of antibiotic radiation proof Ceramic Tiles and preparation method thereof, this preparation method comprises the following steps：
Step A, prepares ground-coat enamel：By mass percentage, by 30% frit, 6% antibacterial powder, 27% lithium porcelain stone, 5% zirconium silicate, 20% height Ridge soil and 12% quartz mix, wet ball grinding, obtain pulpous state ground-coat enamel after crossing 300 ~ 350 mesh sieves；
Step B, prepares cover-coat enamel：By mass percentage, by 72% frit, 1% bamboo charcoal nano（Particle diameter is between 100 ~ 500nm）、 20% kaolin, 5% aluminum oxide, 1% zinc oxide and 1% zirconium silicate mix, wet ball grinding, obtain pulpous state after crossing 300 ~ 350 mesh sieves Cover-coat enamel；
Step C, will be native in ceramic tile base using drenching glaze mode priority glazing to the ground-coat enamel of step A, B preparation and cover-coat enamel；Then in kiln Burn till, firing temperature is 800 ~ 900 DEG C, firing period is 45min, obtains Ceramic Tiles；
Wherein, described frit is obtained by the following method：By weight percentage, by 15% quartz, 9% feldspar, 24% borax, 10% Carbonate, 30% boric acid, 5% spodumene, 3% fluoride salt, 4% kaolin mixed grinding are uniform, then high-temperature fusion（1250~1320 ℃）Quick quenching afterwards, and it is broken into graininess, obtain final product；Wherein, described feldspar is by potassium feldspar and albite by weight 4:1 mixes Close and obtain；Described carbonate is by potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate by weight 3:2:1:2:3 mixing and ?；Described fluoride salt is by sodium fluoride, calcirm-fluoride and lithium fluoride by weight 4:2:3 are obtained by mixing；
Described ceramic tile base soil is obtained by the following method：General glaze for glazed tile base substrate is entered klining, firing period 30min, 1170 DEG C of firing temperature, makes biscuit, standby.
Wherein, the preparation method of described antibacterial powder is as follows：
（1）Weigh 0.6gC60 powder, measure the concentrated sulfuric acid that 100ml mass fraction is 98%, C60 powder and the concentrated sulfuric acid are being burnt Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder, Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot（GQDs）Outstanding Supernatant liquid；100rpm speed stirs GQDs suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1W；Standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.001mol/L silver nitrate aqueous solution；Being added dropwise over concentration is 0.1mol/L ammonium dihydrogen phosphate（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1）, ultrasonic agitation 20min；It is added dropwise over 1mol/L sodium hydroxide solution, regulation pH value to 11, then standing, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag2O；
（3）Take 1gGQDs/Ag2O ultrasonic agitation is scattered in the 100ml aqueous solution；Being added dropwise over concentration is 0.05mol/L cerous nitrate The aqueous solution, being added dropwise over concentration after 30min is 0.005mol/L zinc nitrate aqueous solution, GQDs/Ag2The O aqueous solution, cerous nitrate are water-soluble Liquid and zinc nitrate aqueous solution volume ratio are 1:0.1:0.4；Continue ultrasonic agitation, regulation mixed solution pH value to 7.0；Side is ultrasonic to be stirred Mix, side adds the hydrazine hydrate that 6mL mass fraction is 50%, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45mL mass to divide The hydrazine hydrate for 50% for the number, after reduction reaction 36h at 85 DEG C；Filter, be washed with deionized for several times, vacuum drying, obtain GQDs/Ag2O/Ag-Zn-Ce；
（4）By 0.5gGQDs/Ag2O/Ag-Zn-Ce ultrasonic agitation is scattered in the aqueous solution；Add volume ratio 4 afterwards:1 water and Ammoniacal liquor, is stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag2The mass ratio of O/Ag-Zn-Ce is 3:2）, adjust pH value be 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 30min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；Will This is deposited in and 3h is dried at 90 DEG C, to obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2；By GQDs/Ag2O/Ag-Zn-Ce/SiO2Put Carry out 600 DEG C of heat treatment 1h under argon gas atmosphere, after being cooled to room temperature, be immersed in hydrofluoric acid and surpassed with ultrasonic power 100W Sound 10min, removes surface local silica, is centrifuged and is dried, obtains GQDs/Ag2O/Ag-Zn-Ce/SiO2；
（5）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2O/Ag-Zn-Ce/ SiO2In the aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag2O/Ag-Zn-Ce/SiO2Weight than for 1:5；50W is ultrasonic 100min, standing, deionized water is washed for several times, and centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 3 times （Pumpdown time is 25min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2/ Graphene antibiosis powder, i.e. antibacterial powder.
Embodiment 2
A kind of antibiotic radiation proof Ceramic Tiles and preparation method thereof, this preparation method comprises the following steps：
Step A, prepares ground-coat enamel：By mass percentage, by 32% frit, 4% antibacterial powder, 25% lithium porcelain stone, 6% zirconium silicate, 22% height Ridge soil and 11% quartz mix, wet ball grinding, obtain pulpous state ground-coat enamel after crossing 300 ~ 350 mesh sieves；
Step B, prepares cover-coat enamel：By mass percentage, by 70% frit, 2% bamboo charcoal nano（Particle diameter is between 100 ~ 500nm）、 16% kaolin, 7% aluminum oxide, 1% zinc oxide and 3% zirconium silicate mix, wet ball grinding, obtain pulpous state after crossing 300 ~ 350 mesh sieves Cover-coat enamel；
Step C, will be native in ceramic tile base using drenching glaze mode priority glazing to the ground-coat enamel of step A, B preparation and cover-coat enamel；Then in kiln Burn till, firing temperature is 800 ~ 900 DEG C, firing period is 45min, obtains Ceramic Tiles；
Wherein, described frit is obtained by the following method：By weight percentage, by 15% quartz, 9% feldspar, 24% borax, 10% Carbonate, 30% boric acid, 5% spodumene, 3% fluoride salt, 4% kaolin mixed grinding are uniform, then high-temperature fusion（1250~1320 ℃）Quick quenching afterwards, and it is broken into graininess, obtain final product；Wherein, described feldspar is by potassium feldspar and albite by weight 4:1 mixes Close and obtain；Described carbonate is by potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate by weight 3:2:1:2:3 mixing and ?；Described fluoride salt is by sodium fluoride, calcirm-fluoride and lithium fluoride by weight 4:2:3 are obtained by mixing；
Described ceramic tile base soil is obtained by the following method：General glaze for glazed tile base substrate is entered klining, firing period 30min, 1170 DEG C of firing temperature, makes biscuit, standby.
Wherein, the preparation method of described antibacterial powder is as follows：
（1）Weigh 0.6gC60 powder, measure the concentrated sulfuric acid that 100ml mass fraction is 98%, C60 powder and the concentrated sulfuric acid are being burnt Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder, Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot（GQDs）Outstanding Supernatant liquid；100rpm speed stirs GQDs suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1W；Standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.005mol/L silver nitrate aqueous solution；Being added dropwise over concentration is 0.2mol/L ammonium dihydrogen phosphate（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1）, ultrasonic agitation 20min；It is added dropwise over 1mol/L sodium hydroxide solution, regulation pH value to 11, then standing, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag2O；
（3）Take 2gGQDs/Ag2O ultrasonic agitation is scattered in the 100ml aqueous solution；Being added dropwise over concentration is 0.03mol/L cerous nitrate The aqueous solution, being added dropwise over concentration after 30min is 0.03mol/L zinc nitrate aqueous solution, GQDs/Ag2The O aqueous solution, cerous nitrate are water-soluble Liquid and zinc nitrate aqueous solution volume ratio are 1:0.2:0.3；Continue ultrasonic agitation, regulation mixed solution pH value to 7.0；Side is ultrasonic to be stirred Mix, side adds the hydrazine hydrate that 6mL mass fraction is 50%, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45mL mass to divide The hydrazine hydrate for 50% for the number, after reduction reaction 36h at 85 DEG C；Filter, be washed with deionized for several times, vacuum drying, obtain GQDs/Ag2O/Ag-Zn-Ce；
（4）By 0.3gGQDs/Ag2O/Ag-Zn-Ce ultrasonic agitation is scattered in the aqueous solution；Add volume ratio 4 afterwards:1 water and Ammoniacal liquor, is stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag2The mass ratio of O/Ag-Zn-Ce is 3:2）, adjust pH value be 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 45min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；Will This is deposited in and 3h is dried at 90 DEG C, to obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2；By GQDs/Ag2O/Ag-Zn-Ce/SiO2Put Carry out 600 DEG C of heat treatment 1h under argon gas atmosphere, after being cooled to room temperature, be immersed in hydrofluoric acid and surpassed with ultrasonic power 100W Sound 12min, removes surface local silica, is centrifuged and is dried, obtains GQDs/Ag2O/Ag-Zn-Ce/SiO2；
（5）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2O/Ag-Zn-Ce/ SiO2In the aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag2O/Ag-Zn-Ce/SiO2Weight than for 1:3；50W is ultrasonic 100min, standing, deionized water is washed for several times, and centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 5 times （Pumpdown time is 25min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2/ Graphene antibiosis powder, i.e. antibacterial powder.
Embodiment 3
A kind of antibiotic radiation proof Ceramic Tiles and preparation method thereof, this preparation method comprises the following steps：
Step A, prepares ground-coat enamel：By mass percentage, by 34% frit, 1% antibacterial powder, 20% lithium porcelain stone, 10% zirconium silicate, 25% Kaolin and 10% quartz mix, wet ball grinding, obtain pulpous state ground-coat enamel after crossing 300 ~ 350 mesh sieves；
Step B, prepares cover-coat enamel：By mass percentage, by 63% frit, 5% bamboo charcoal nano（Particle diameter is between 100 ~ 500nm）、20% Kaolin, 8% aluminum oxide, 1% zinc oxide and 3% zirconium silicate mix, wet ball grinding, obtain pulpous state face after crossing 300 ~ 350 mesh sieves Glaze；
Step C, will be native in ceramic tile base using drenching glaze mode priority glazing to the ground-coat enamel of step A, B preparation and cover-coat enamel；Then in kiln Burn till, firing temperature is 800 ~ 900 DEG C, firing period is 45min, obtains Ceramic Tiles；
Wherein, described frit is obtained by the following method：By weight percentage, by 15% quartz, 9% feldspar, 24% borax, 10% Carbonate, 30% boric acid, 5% spodumene, 3% fluoride salt, 4% kaolin mixed grinding are uniform, then high-temperature fusion（1250~1320 ℃）Quick quenching afterwards, and it is broken into graininess, obtain final product；Wherein, described feldspar is by potassium feldspar and albite by weight 4:1 mixes Close and obtain；Described carbonate is by potassium carbonate, sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate by weight 3:2:1:2:3 mixing and ?；Described fluoride salt is by sodium fluoride, calcirm-fluoride and lithium fluoride by weight 4:2:3 are obtained by mixing；
Described ceramic tile base soil is obtained by the following method：General glaze for glazed tile base substrate is entered klining, firing period 30min, 1170 DEG C of firing temperature, makes biscuit, standby.
Wherein, the preparation method of described antibacterial powder is as follows：
（1）Weigh 0.6gC60 powder, measure the concentrated sulfuric acid that 100ml mass fraction is 98%, C60 powder and the concentrated sulfuric acid are being burnt Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder, Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot（GQDs）Outstanding Supernatant liquid；100rpm speed stirs GQDs suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1W；Standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.01mol/L silver nitrate aqueous solution；Being added dropwise over concentration is 0.5mol/L ammonium dihydrogen phosphate（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1）, ultrasonic agitation 20min；It is added dropwise over 1mol/L sodium hydroxide solution, regulation pH value to 11, then standing, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag2O；
（3）Take 3gGQDs/Ag2O ultrasonic agitation is scattered in the 100ml aqueous solution；Being added dropwise over concentration is 0.005mol/L nitric acid The cerium aqueous solution, being added dropwise over concentration after 30min is 0.05mol/L zinc nitrate aqueous solution, GQDs/Ag2The O aqueous solution, cerous nitrate water Solution and zinc nitrate aqueous solution volume ratio are 1:0.2:0.4；Continue ultrasonic agitation, regulation mixed solution pH value to 7.0；Side is ultrasonic Stirring, side adds the hydrazine hydrate that 6mL mass fraction is 50%, reduction reaction 0.5h at 30 DEG C；Afterwards, add 45mL mass Fraction is 50% hydrazine hydrate, after reduction reaction 36h at 85 DEG C；Filter, be washed with deionized for several times, vacuum drying, obtain GQDs/Ag2O/Ag-Zn-Ce；
（4）By 0.1gGQDs/Ag2O/Ag-Zn-Ce ultrasonic agitation is scattered in the aqueous solution；Add volume ratio 4 afterwards:1 water and Ammoniacal liquor, is stirring evenly and then adding into tetraethyl orthosilicate（With GQDs/Ag2The mass ratio of O/Ag-Zn-Ce is 3:2）, adjust pH value be 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；Will This is deposited in and 3h is dried at 90 DEG C, to obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2；By GQDs/Ag2O/Ag-Zn-Ce/SiO2Put Carry out 600 DEG C of heat treatment 1h under argon gas atmosphere, after being cooled to room temperature, be immersed in hydrofluoric acid and surpassed with ultrasonic power 100W Sound 15min, removes surface local silica, is centrifuged and is dried, obtains GQDs/Ag2O/Ag-Zn-Ce/SiO2；
（5）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2O/Ag-Zn-Ce/ SiO2In the aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag2O/Ag-Zn-Ce/SiO2Weight than for 1:1；50W is ultrasonic 100min, standing, deionized water is washed for several times, and centrifugation is placed in confined space, carries out vacuumizing → heat pressurized circulation 8 times （Pumpdown time is 25min；It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2/ Graphene antibiosis powder, i.e. antibacterial powder.
Embodiment 4
Based on the preparation method of embodiment 1, it the difference is that only：Described antibacterial powder is obtained by the following method：
（1）Weigh 0.6gC60 powder, measure the concentrated sulfuric acid that 100ml mass fraction is 98%, C60 powder and the concentrated sulfuric acid are being burnt Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder, Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot（GQDs）Outstanding Supernatant liquid；100rpm speed stirs GQDs suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1W；Standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.001mol/L silver nitrate aqueous solution；Being added dropwise over concentration is 0.1mol/L ammonium dihydrogen phosphate（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1）, ultrasonic agitation 20min；It is added dropwise over 1mol/L sodium hydroxide solution, regulation pH value to 11, then standing, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag2O；
（3）Take 1gGQDs/Ag2O ultrasonic agitation is scattered in the aqueous solution；Being added dropwise over concentration is 0.5g/100mlZnO quantum dot The aqueous solution, ultrasonic power mixing speed respectively halves；After 60min, standing, filter, be washed with deionized for several times, vacuum drying, Obtain GQDs/Ag2O/ZnO；
（4）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2The O/ZnO aqueous solution In, three-dimensional sponge shape Graphene and GQDs/Ag2The weight of O/ZnO is than for 1:5；The ultrasonic 100min of 50W, standing, deionization is washed Wash for several times, centrifugation, it is placed in confined space, carry out vacuumizing → heat pressurized circulation 3 times（Pumpdown time is 25min；Heating It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/ Ag2O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.
Embodiment 5
Based on the preparation method of embodiment 2, it the difference is that only：Described antibacterial powder is obtained by the following method：
（1）Weigh 0.6gC60 powder, measure the concentrated sulfuric acid that 100ml mass fraction is 98%, C60 powder and the concentrated sulfuric acid are being burnt Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder, Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot（GQDs）Outstanding Supernatant liquid；100rpm speed stirs GQDs suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1W；Standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.005mol/L silver nitrate aqueous solution；Being added dropwise over concentration is 0.2mol/L ammonium dihydrogen phosphate（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1）, ultrasonic agitation 20min；It is added dropwise over 1mol/L sodium hydroxide solution, regulation pH value to 11, then standing, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag2O；
（3）Take 2gGQDs/Ag2O ultrasonic agitation is scattered in the aqueous solution；Being added dropwise over concentration is 0.2g/100mlZnO quantum dot The aqueous solution, ultrasonic power mixing speed respectively halves；After 80min, standing, filter, be washed with deionized for several times, vacuum drying, Obtain GQDs/Ag2O/ZnO；
（4）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2The O/ZnO aqueous solution In, three-dimensional sponge shape Graphene and GQDs/Ag2The weight of O/ZnO is than for 1:3；The ultrasonic 100min of 50W, standing, deionization is washed Wash for several times, centrifugation, it is placed in confined space, carry out vacuumizing → heat pressurized circulation 5 times（Pumpdown time is 25min；Heating It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/ Ag2O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.
Embodiment 6
Based on the preparation method of embodiment 3, it the difference is that only：Described antibacterial powder is obtained by the following method：
（1）Weigh 0.6gC60 powder, measure the concentrated sulfuric acid that 100ml mass fraction is 98%, C60 powder and the concentrated sulfuric acid are being burnt Mix in cup, beaker is placed in ice-water bath, stirred with the speed of 600rpm simultaneously, obtain mixed liquor；Weigh 1g potassium permanganate powder, Slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, react 4h；Quickly add Enter 120ml pure water, filter, then dialysed 4 days with the bag filter that molecular cut off is 1000, obtain graphene quantum dot（GQDs）Outstanding Supernatant liquid；100rpm speed stirs GQDs suspension, laser irradiation 40min simultaneously, and laser irradiation power is 1W；Standby；
（2）Ultrasonic agitation 60mlGQDs suspension, dropping concentration is 0.01mol/L silver nitrate aqueous solution；Being added dropwise over concentration is 0.5mol/L ammonium dihydrogen phosphate（Ammonium dihydrogen phosphate and silver nitrate aqueous solution volume ratio are 2:1）, ultrasonic agitation 20min；It is added dropwise over 1mol/L sodium hydroxide solution, regulation pH value to 11, then standing, centrifugation, deionized water and ethanol Alternately washing three times, vacuum drying, obtain GQDs/Ag2O；
（3）Take 3gGQDs/Ag2O ultrasonic agitation is scattered in the aqueous solution；Being added dropwise over concentration is 0.05g/100mlZnO quantum dot The aqueous solution, ultrasonic power mixing speed respectively halves；After 90min, standing, filter, be washed with deionized for several times, vacuum drying, Obtain GQDs/Ag2O/ZnO；
（4）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2The O/ZnO aqueous solution In, three-dimensional sponge shape Graphene and GQDs/Ag2The weight of O/ZnO is than for 1:1；The ultrasonic 100min of 50W, standing, deionization is washed Wash for several times, centrifugation, it is placed in confined space, carry out vacuumizing → heat pressurized circulation 8 times（Pumpdown time is 25min；Heating It is pressurised into and is passed through high temperature and high pressure gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain GQDs/ Ag2O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.
Comparative example 1
Based on the preparation method of embodiment 1, difference is：Described antibacterial powder is metal antibacterial agent.
Comparative example 2
Based on the preparation method of embodiment 4, difference is：Described antibacterial powder is zinc oxide antiseptic；Without nano bamboo Charcoal.
Performance test is carried out to embodiment 1 ~ 6, comparative example 1 ~ 2, test result is as follows：
Wear testing：The abrasive material being 3～4 from Mohs' hardness, in Ceramic Tiles friction 1000 times come to imitate paving use 2 years after Effect, test its sterilization rate.
Heat stability testing：Ceramic Tiles are placed in electric furnace, are raised to 200 DEG C from room temperature, be incubated 20min, put into rapidly 25 In DEG C water, take out after 10min and dry, test its sterilization rate.
Sterilizing Evaluation for Uniformity：100 regions are chosen on same Ceramic Tiles and carries out sterilizing test, the data recording is entered Row Uniformity Analysis, by the uniformity=100* (1- standard deviation/mean value).When the uniformity is more than 97%, then be labeled as ▲；When The uniformity is more than 90% and is less than 97%, then be labeled as ☆；When the uniformity is less than 90%, then it is labeled as.
Air purification effect test is as follows：Contrast uses concentration of formaldehyde indoor in front and back and electromagnetic radiation etc., to characterize it Adsorption capacity.In 10 square metres of vacant room between, place following article：1. make 10, the clamping plate of furniture, surface is no Packaging；2. 5 barrels are painted, bung is opened；3. television set 1, opening；4. electric fan 1, opening.
Radiation performance：Detection indicate that, the quartz of present invention preparation all meets GB6566-2001《Construction material radiates Property radionuclides limitation》Middle A class finishing material requires.
Embodiment described above only have expressed embodiments of the present invention, and its description is more concrete and detailed, but can not Therefore it is interpreted as the restriction to the scope of the claims of the present invention, as long as the skill being obtained in the form of equivalent or equivalent transformation Art scheme, all should fall within the scope and spirit of the invention.

Claims (8)

1. a kind of preparation method of antibiotic radiation proof Ceramic Tiles, it comprises the following steps：
Step A, prepares ground-coat enamel：By mass percentage, by 30 ~ 35% frits, 1 ~ 6% antibacterial powder, 20 ~ 28% lithium porcelain stones, 5 ~ 10% Zirconium silicate, 20 ~ 25% kaolin and 10 ~ 12% quartz mix, wet ball grinding, obtain pulpous state ground-coat enamel after crossing 300 ~ 350 mesh sieves；Institute Stating antibacterial powder is GQDs/Ag2O/Ag-Zn-Ce/SiO2/ Graphene antibiosis powder；
Step B, prepares cover-coat enamel：By mass percentage, by 70 ~ 80% frits, 1 ~ 5% bamboo charcoal nano, 10 ~ 20% kaolin, 5 ~ 8% Aluminum oxide, 1 ~ 2% zinc oxide and 1 ~ 5% zirconium silicate mix, wet ball grinding, obtain pulpous state cover-coat enamel after crossing 300 ~ 350 mesh sieves；
Step C, will be native in ceramic tile base using drenching glaze mode priority glazing to the ground-coat enamel of step A, B preparation and cover-coat enamel；Then in kiln Burn till, firing temperature is 800 ~ 900 DEG C, firing period is 40 ~ 50min, obtains Ceramic Tiles；
Wherein, described frit is obtained by the following method：By weight percentage, by 10 ~ 18% quartz, 5 ~ 12% feldspars, 15 ~ 25% borax, 3 ~ 12% carbonate, 20 ~ 35% boric acid, 3 ~ 8% spodumenes, 1 ~ 4% fluoride salt, 1 ~ 5% kaolin mixed grinding are uniform, Then after high-temperature fusion, quick quenching is obtained.
2. the preparation method of antibiotic radiation proof Ceramic Tiles according to claim 1 is it is characterised in that described bamboo charcoal nano is The bamboo charcoal nano of average grain diameter 100 ~ 500nm.
3. the preparation method of antibiotic radiation proof Ceramic Tiles according to claim 1 and 2 is it is characterised in that described antibacterial powder Preparation method as follows：
（1）Weigh 0.3 ~ 1gC60 powder, measure the concentrated sulfuric acid that 80 ~ 100ml mass fraction is 98%, by C60 powder and the concentrated sulfuric acid Beaker mixes, beaker is placed in ice-water bath, stirred with the speed of 500 ~ 600rpm simultaneously, obtain mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, slowly adds in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, instead Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtain GQDs suspension；100 ~ 150rpm speed stirs GQDs suspension, laser irradiation 30 ~ 60min simultaneously, and laser irradiation power is 0.5~2W；Standby；
（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropping concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solution；Dropwise plus Entering concentration is 0.1 ~ 0.5mol/L ammonium dihydrogen phosphate, ultrasonic agitation 10 ~ 20min；It is added dropwise over 0.5 ~ 1mol/L hydroxide Sodium solution, adjusts pH value to 11, then stands, is centrifuged, deionized water and ethanol replace washing three times, vacuum drying, obtain GQDs/Ag2O；
（3）Take 1 ~ 3gGQDs/Ag2O ultrasonic agitation is scattered in 80 ~ 120ml aqueous solution；Be added dropwise over concentration be 0.005 ~ The 0.05mol/L cerous nitrate aqueous solution, being added dropwise over concentration after 30 ~ 60min is 0.005 ~ 0.05mol/L zinc nitrate aqueous solution；Continue Continuous ultrasonic agitation, regulation mixed solution pH value to 7.0；Side ultrasonic agitation, side adds the hydrazine hydrate that 4 ~ 8mL mass fraction is 50%, Reduction reaction 0.5 ~ 1h at 30 ~ 40 DEG C；Afterwards, add the hydrazine hydrate that 40 ~ 50mL mass fraction is 50%, at 85 DEG C also After former reaction 30 ~ 48h；Filter, be washed with deionized for several times, vacuum drying, obtain GQDs/Ag2O/Ag-Zn-Ce；
（4）By 0.1 ~ 0.5gGQDs/Ag2O/Ag-Zn-Ce ultrasonic agitation is scattered in the aqueous solution；Add volume ratio 3 ~ 5 afterwards:1 Water and ammoniacal liquor, be stirring evenly and then adding into tetraethyl orthosilicate, adjusting pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reaction 30 ~ 60min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited at 80 ~ 90 DEG C 2 ~ 4h is dried, To obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2；By GQDs/Ag2O/Ag-Zn-Ce/SiO2Be placed under argon gas atmosphere carry out 500 ~ 800 DEG C of heat treatment 1 ~ 2h, after being cooled to room temperature, be immersed in hydrofluoric acid carry out ultrasonic 10 with ultrasonic power 100 ~ 150W ~ 15min, removes surface local silica, is centrifuged and is dried, obtains GQDs/Ag2O/Ag-Zn-Ce/SiO2；
（5）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2O/Ag-Zn-Ce/ SiO2In the aqueous solution；Ultrasonic 60 ~ the 120min of 10 ~ 100W, standing, deionized water is washed for several times, and centrifugation is placed in confined space, Carry out vacuumizing → heat pressurized circulation 3 ~ 8 times, obtain GQDs/Ag2O/Ag-Zn-Ce/SiO2/ Graphene antibiosis powder, i.e. antibacterial powder.
4. a kind of preparation method of antibiotic radiation proof Ceramic Tiles, it comprises the following steps：
Step A, prepares ground-coat enamel：By mass percentage, by 30 ~ 35% frits, 1 ~ 6% antibacterial powder, 20 ~ 28% lithium porcelain stones, 5 ~ 10% Zirconium silicate, 20 ~ 25% kaolin and 10 ~ 12% quartz mix, wet ball grinding, obtain pulpous state ground-coat enamel after crossing 300 ~ 350 mesh sieves；Institute Stating antibacterial powder is GQDs/Ag2O/ZnO/ Graphene antibiosis powder；
Step B, prepares cover-coat enamel：By mass percentage, by 70 ~ 80% frits, 1 ~ 5% bamboo charcoal nano, 10 ~ 20% kaolin, 5 ~ 8% Aluminum oxide, 1 ~ 2% zinc oxide and 1 ~ 5% zirconium silicate mix, wet ball grinding, obtain pulpous state cover-coat enamel after crossing 300 ~ 350 mesh sieves；
Step C, will be native in ceramic tile base using drenching glaze mode priority glazing to the ground-coat enamel of step A, B preparation and cover-coat enamel；Then in kiln Burn till, firing temperature is 800 ~ 900 DEG C, firing period is 40 ~ 50min, obtains Ceramic Tiles；
Wherein, described frit is obtained by the following method：By weight percentage, by 10 ~ 18% quartz, 5 ~ 12% feldspars, 15 ~ 25% borax, 3 ~ 12% carbonate, 20 ~ 35% boric acid, 3 ~ 8% spodumenes, 1 ~ 4% fluoride salt, 1 ~ 5% kaolin mixed grinding are uniform, Then after high-temperature fusion, quick quenching is obtained.
5. the preparation method of antibiotic radiation proof Ceramic Tiles according to claim 4 is it is characterised in that described bamboo charcoal nano is The bamboo charcoal nano of average grain diameter 100 ~ 500nm.
6. the preparation method of the antibiotic radiation proof Ceramic Tiles according to claim 4 or 5 is it is characterised in that described antibacterial powder Preparation method as follows：
（1）Weigh 0.3 ~ 1gC60 powder, measure the concentrated sulfuric acid that 80 ~ 100ml mass fraction is 98%, by C60 powder and the concentrated sulfuric acid Beaker mixes, beaker is placed in ice-water bath, stirred with the speed of 500 ~ 600rpm simultaneously, obtain mixed liquor；Weigh 1 ~ 3g high Potassium manganate powder, slowly adds in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep 30 ~ 40 DEG C of bath temperature, instead Answer 3 ~ 5h；Rapidly join 100 ~ 150ml pure water, filter, then dialysed 3 ~ 5 days with the bag filter that molecular cut off is 1000, obtain GQDs suspension；100 ~ 150rpm speed stirs GQDs suspension, laser irradiation 30 ~ 60min simultaneously, and laser irradiation power is 0.5~2W；Standby；
（2）Ultrasonic agitation 50 ~ 60mlGQDs suspension, dropping concentration is 0.001 ~ 0.01mol/L silver nitrate aqueous solution；Dropwise plus Entering concentration is 0.1 ~ 0.5mol/L ammonium dihydrogen phosphate, ultrasonic agitation 10 ~ 20min；It is added dropwise over 0.5 ~ 1mol/L hydroxide Sodium solution, adjusts pH value to 11, then stands, is centrifuged, deionized water and ethanol replace washing three times, vacuum drying, obtain GQDs/Ag2O；
（3）Take 1 ~ 3gGQDs/Ag2O ultrasonic agitation is scattered in the aqueous solution；Being added dropwise over concentration is 0.05 ~ 0.5g/100mlZnO The quantum dot aqueous solution, ultrasonic power mixing speed respectively halves；After 60 ~ 90min, standing, filter, be washed with deionized for several times, Vacuum drying, obtains GQDs/Ag2O/ZnO；
（4）Take three-dimensional sponge shape Graphene ultrasonic agitation to be scattered in the aqueous solution, be added dropwise over GQDs/Ag2In the O/ZnO aqueous solution； Ultrasonic 60 ~ the 120min of 10 ~ 100W, standing, deionized water is washed for several times, and centrifugation is placed in confined space, carries out vacuumizing → adding Hot pressurized circulation 3 ~ 8 times, obtains GQDs/Ag2O/ZnO/ Graphene antibiosis powder, i.e. antibacterial powder.
7. the preparation method of the antibiotic radiation proof Ceramic Tiles according to claim 3 or 6 is it is characterised in that described three-dimensional is extra large Continuous shape graphene preparation method is as follows：By 3g graphite powder, 1g NaNO3 is mixed all with 250ml 98% concentrated sulfuric acid in ice-water bath Even, it is slowly added to 6g KMnO4；Then heat at 35 DEG C, after stirring 40min, add 95ml deionized water, be warming up to 98 DEG C reaction 20min；Add 270ml water dilution, and with 5ml 30% H2O2 with unnecessary KMnO4, the color of mixed solution For brown color, filter while hot, deionized water cyclic washing obtains GO to neutrality, ultrasonic disperse；The 200ml mass fraction is taken to be The graphene oxide solution of 5mg/ml pours diameter 25cm into, in the discoid reaction utensil of high 2cm, adds ascorbic acid (VC) 0.5g Stirring makes it be sufficiently mixed；Then confined reaction ware is placed in 80 DEG C of hydro-thermal reactions 15h, and the graphene oxide in reaction utensil is spontaneous Contraction is cross-linked into three-dimensional sponge structure, freeze-drying, obtains the three-dimensional sponge shape Graphene of flexibility.
8. a kind of antibiotic radiation proof Ceramic Tiles are it is characterised in that be obtained by the preparation method as described in claim 1 or 4.
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