CN106396405A

CN106396405A - Photochromic ceramic tile and preparation method thereof

Info

Publication number: CN106396405A
Application number: CN201610748676.8A
Authority: CN
Inventors: 麦浩
Original assignee: Bright Cities And Towns Gaoming District Foshan City New Forms Of Energy New Material Industry Innovation Centers
Current assignee: Bright Cities And Towns Gaoming District Foshan City New Forms Of Energy New Material Industry Innovation Centers
Priority date: 2016-08-29
Filing date: 2016-08-29
Publication date: 2017-02-15

Abstract

The invention discloses a photochromic ceramic tile and a preparation method thereof. The preparation method comprises the steps of: A, preparation of ground glaze: by mass percentage, mixing 30-35% of frit, 3-7% of a functional agent, 20-28% of lithium porcelain stone, 5-10% of zirconium silicate, 20-25% of kaolin and 10-12% of quartz evenly, conducting wet ball-milling, and performing sieving to obtain slurry ground glaze; B, preparation of surface glaze: by mass percentage, mixing 70-80% of frit, 1-4% of conductive powder, 10-20% of kaolin, 5-8% of alumina, 1-2% of zinc oxide and 1-5% of zirconium silicate evenly, performing wet ball-milling, and conducting sieving so as to obtain slurry surface glaze; and C, applying the ground glaze and surface glaze prepared by step A and step B respectively to a tile blank in order, and performing firing so as to obtain the ceramic tile. Compared with the existing ceramic tiles, the ceramic tile prepared by the method provided by the invention has the characteristics of scientific compounding, reasonable preparation and stable performance. Also through reasonable collocation with conductive powder, photochromic compounds and antibacterial powder, the ceramic tile has excellent antibacterial, antistatic and photochromic properties, thus further broadening the application scope of ceramic tiles.

Description

A kind of photochromic Ceramic Tiles and preparation method thereof

Technical field

The present invention relates to quartz technical field, more particularly to a kind of photochromic 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 photochromic Ceramic Tiles and its preparation side Method.

The technical problem to be solved is achieved by the following technical programs：

A kind of photochromic 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, 3 ~ 7% functional agents, 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 ~ 4% conducting powder, 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 conduction powder, preparation method thereof is as follows：By 30 ~ 40% epoxy resin, 35 ~ 50% phenolic resin, 1 ~ 5% nano-graphene, 2 ~ 6% aluminium powders, 5 ~ 10% carbon blacks and 3 ~ 8% graphite are sufficiently mixed, wherein, described nano-graphene, aluminium powder, carbon Black and graphite weight sum accounts for the 15 ~ 25% of conducting powder gross weight, adds appropriate butyl acetate to put into dispersion solution in ball mill Glue, after discharge, detection, adjustment are configured to the slurry that can apply；By this slurry coating on substrate, drying and forming-film；Then put In nitrogen filled protection atmosphere furnace, it is warmed up to 900 ~ 1000 DEG C, be incubated 1 ~ 2h；Film is scraped off this substrate, obtains conductive porous reticulated carbon Film, i.e. conducting powder.

In the present invention, described functional agent 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；

（6）Antibacterial powder and photochromic compound is taken to be scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains all even Stable dispersion liquid, the wherein weight of antibacterial powder and photochromic compound are than for 5 ~ 10:1~6；To have carbon nanotube mesh When the substrate of film is placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, make this dispersion liquid It is dispersed in this carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophily, this dispersion liquid is adsorbed Multiple net holes in carbon nanotube mesh film；It is warming up to about 25 DEG C, CNT has hydrophobicity and catches up with most of moisture Walk to stay absorption antibacterial powder and photochromic compound in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in close Close in space, carry out vacuumizing → heat pressurized circulation 3 ~ 5 times（Pumpdown time is 20 ~ 30min；It is pressurised into and be passed through height Warm gases at high pressure, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.3 ~ 0.6Mpa, pressurize 20 ~ 30min）, then will be adsorbed with The carbon nanotube mesh film of antibacterial powder and photochromic compound scrapes off this substrate, obtains antibacterial-photochromic function agent.

In the present invention, described functional agent can also be obtained by the following method：

（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；

（5）Antibacterial powder and photochromic compound is taken to be scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains all even Stable dispersion liquid, the wherein weight of antibacterial powder and photochromic compound are than for 5 ~ 10:1~6；To have carbon nanotube mesh When the substrate of film is placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, make this dispersion liquid It is dispersed in this carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophily, this dispersion liquid is adsorbed Multiple net holes in carbon nanotube mesh film；It is warming up to about 25 DEG C, CNT has hydrophobicity and catches up with most of moisture Walk to stay absorption antibacterial powder and photochromic compound in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in close Close in space, carry out vacuumizing → heat pressurized circulation 3 ~ 5 times（Pumpdown time is 20 ~ 30min；It is pressurised into and be passed through height Warm gases at high pressure, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.3 ~ 0.6Mpa, pressurize 20 ~ 30min）, then will be adsorbed with The carbon nanotube mesh film of antibacterial powder and photochromic compound scrapes off this substrate, obtains antibacterial-photochromic function agent.

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.

Wherein, described photochromic compound preparation method is as follows：Under nitrogen environment, concentration is 0.05 ~ 0.5mol/L Protonic acid solution and concentration be 0.05 ~ 0.5mol/L DBSA with volume ratio 3:1 ~ 3 mixing, is simultaneously introduced light Mutagens toner, adds aniline after magnetic agitation 60 ~ 120min, photochromic powder and aniline mass ratio are 1:5~10；Continuously stirred After 60 ~ 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1；12 ~ 36h is reacted at 20 DEG C～30 DEG C； Acetone, deionized water washing are vacuum dried for several times afterwards, nano polyaniline/photochromic flour complexes of milling to obtain；By 1 ~ 10g nanometer Polyaniline/photochromic flour complexes ultrasonic agitation is scattered in the aqueous solution；Add volume ratio 4 afterwards:1 water and ammoniacal liquor, stir Mix and uniformly add tetraethyl orthosilicate afterwards（Mass ratio with nano polyaniline/photochromic flour complexes is 5:1~3）, adjust pH value For 9 ~ 10, reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；Carry out being centrifuged and cleaning acquisition with acetone and deionized water successively Precipitation；This is deposited at 90 DEG C 3h is dried, to obtain nano polyaniline/photochromic flour complexes/SiO₂；By nanometer polyphenyl Amine/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h, remove polyaniline, light Mutagens toner/porous SiO₂, i.e. photochromic compound.

Described photochromic powder is rare earth oxide, and described rare earth oxide is Nd₂O₃、Er₂O₃、Pr₂O₃、CeO₂、Sm₂O₃、 La₂O₃、Y₂O₃、Yb₂O₃At least one of.

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 conducting powder, photochromic compound and antibacterial powder, both are collaborative to make With so that Ceramic Tiles have excellent antibacterial and antistatic and photochromic properties, having widened the application model of Ceramic Tiles further Enclose；

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；Photochromic compound has photochromic effect, makes product more rich and varied, profit It is that the Ceramic Tiles being produced using conventional colorants are incomparable with the Ceramic Tiles that it produces, can be strong and weak not with irradiation light The shades of colour changing, is a splendid legacy together, and full of magnificent carriage, beautiful magical, the pure and fresh elegance so that ceramic product seems is interspersed City night life, increases sentiment and artistic effect to building and interior decoration.

Specific embodiment

To further illustrate technical scheme below by specific preferred embodiment.

Embodiment 1

Step A, prepares ground-coat enamel：By mass percentage, by 30% frit, 7% functional agent, 26% 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% conducting powder, 20% kaolin, 5% aluminum oxide, 1% oxygen Change zinc and 1% zirconium silicate mixes, wet ball grinding, after crossing 300 ~ 350 mesh sieves, obtain pulpous state 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, described conduction powder, preparation method thereof is as follows：By 40% epoxy resin, 45% phenolic resin, 1% nano-graphene, 6% Aluminium powder, 5% carbon black and 3% graphite are sufficiently mixed, and wherein, the weight sum of described nano-graphene, aluminium powder, carbon black and graphite accounts for be led The 15% of electric powder gross weight, adds appropriate butyl acetate to put into dispersion dispergation in ball mill, and after discharge, detection, adjustment are configured to The slurry that can apply；By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, be warmed up to 1000 DEG C, it is incubated 1.5h；Film is scraped off this substrate, obtains conductive porous netted carbon film, i.e. conducting powder.

Wherein, the preparation method of described functional agent 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；

（6）Prepare photochromic compound：Under nitrogen environment, the protonic acid solution for 0.4mol/L for the concentration and concentration are The DBSA of 0.3mol/L is with volume ratio 3:2 mixing, are simultaneously introduced photochromic powder（Nd₂O₃、Pr₂O₃、La₂O₃With Yb₂O₃By weight 1:2:2:1 is obtained by mixing）, add aniline after magnetic agitation 90min, photochromic powder with aniline mass ratio is 1:8；After continuously stirred 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1；Anti- at 20 DEG C～30 DEG C Answer 20h；Acetone, deionized water washing are vacuum dried for several times afterwards, nano polyaniline/photochromic flour complexes of milling to obtain；By 6g Nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in the aqueous solution；Add volume ratio 4 afterwards:1 water and ammonia Water, is stirring evenly and then adding into tetraethyl orthosilicate（Mass ratio with nano polyaniline/photochromic flour complexes is 5:2）, adjust PH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out being centrifuged and cleaning acquisition with acetone and deionized water successively Precipitation；This is deposited at 90 DEG C 3h is dried, to obtain nano polyaniline/photochromic flour complexes/SiO₂；By nanometer polyphenyl Amine/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove polyaniline, obtain photochromic Powder/porous SiO₂, i.e. photochromic compound；

（7）Antibacterial powder and photochromic compound is taken to be scattered in 150ml ultra-pure water, ultrasonic agitation 2h obtains all even stable Dispersion liquid, the wherein weight of antibacterial powder and photochromic compound are than for 5:6；The substrate with carbon nanotube mesh film is placed in When about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, make this homogeneous dispersion be scattered in this In carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophily, this dispersion liquid is attracted to carbon nano-tube network Multiple net holes of shape film；It is warming up to about 25 DEG C, CNT has hydrophobicity drive most of moisture away and stays absorption to exist Antibacterial powder and photochromic compound in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in confined space, carry out Vacuumize → heat pressurized circulation 4 times（Pumpdown time is 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heats Temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, then will be adsorbed with the carbon of antibacterial powder and photochromic compound Nanotube reticular membrane scrapes off this substrate, obtains antibacterial-photochromic function agent.

Embodiment 2

Step A, prepares ground-coat enamel：By mass percentage, by 32% frit, 5% functional agent, 24% 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, 3% conducting powder, 15% kaolin, 7% aluminum oxide, 1% oxygen Change zinc and 3% zirconium silicate mixes, wet ball grinding, after crossing 300 ~ 350 mesh sieves, obtain pulpous state cover-coat enamel；

Wherein, described conduction powder, preparation method thereof is as follows：By 35% epoxy resin, 43% phenolic resin, 3% nano-graphene, 5% Aluminium powder, 8% carbon black and 6% graphite are sufficiently mixed, and wherein, the weight sum of described nano-graphene, aluminium powder, carbon black and graphite accounts for be led The 22% of electric powder gross weight, adds appropriate butyl acetate to put into dispersion dispergation in ball mill, and after discharge, detection, adjustment are configured to The slurry that can apply；By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, be warmed up to 1000 DEG C, it is incubated 1.5h；Film is scraped off this substrate, obtains conductive porous netted carbon film, i.e. conducting powder.

Wherein, the preparation method of described functional agent is as follows：

（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；

（7）Antibacterial powder and photochromic compound is taken to be scattered in 150ml ultra-pure water, ultrasonic agitation 2h obtains all even stable Dispersion liquid, the wherein weight of antibacterial powder and photochromic compound are than for 10:3；The substrate with carbon nanotube mesh film is put When about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, so that this homogeneous dispersion is scattered in In this carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophily, this dispersion liquid is attracted to CNT Multiple net holes of reticular membrane；It is warming up to about 25 DEG C, CNT has hydrophobicity and drives most of moisture away and leave absorption Antibacterial powder and photochromic compound in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in confined space, enter Row vacuumizes → heats pressurized circulation 4 times（Pumpdown time is 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas adds Hot temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, then will be adsorbed with antibacterial powder and photochromic compound Carbon nanotube mesh film scrapes off this substrate, obtains antibacterial-photochromic function agent.

Embodiment 3

Step A, prepares ground-coat enamel：By mass percentage, by 34% frit, 3% functional agent, 18% 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% conducting powder, 20% kaolin, 8% aluminum oxide, 1% oxygen Change zinc and 3% zirconium silicate mixes, wet ball grinding, after crossing 300 ~ 350 mesh sieves, obtain pulpous state cover-coat enamel；

Wherein, described conduction powder, preparation method thereof is as follows：By 30% epoxy resin, 45% phenolic resin, 5% nano-graphene, 2% Aluminium powder, 10% carbon black and 8% graphite are sufficiently mixed, and wherein, the weight sum of described nano-graphene, aluminium powder, carbon black and graphite accounts for The 25% of conducting powder gross weight, adds appropriate butyl acetate to put into dispersion dispergation in ball mill, and after discharge, detection, adjustment are prepared The slurry that one-tenth can apply；By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, heat up To 1000 DEG C, it is incubated 1.5h；Film is scraped off this substrate, obtains conductive porous netted carbon film, i.e. conducting powder.

Wherein, the preparation method of described functional agent is as follows：

（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；

（7）Antibacterial powder and photochromic compound is taken to be scattered in 150ml ultra-pure water, ultrasonic agitation 2h obtains all even stable Dispersion liquid, the wherein weight of antibacterial powder and photochromic compound are than for 8:1；The substrate with carbon nanotube mesh film is placed in When about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, make this homogeneous dispersion be scattered in this In carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophily, this dispersion liquid is attracted to carbon nano-tube network Multiple net holes of shape film；It is warming up to about 25 DEG C, CNT has hydrophobicity drive most of moisture away and stays absorption to exist Antibacterial powder and photochromic compound in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in confined space, carry out Vacuumize → heat pressurized circulation 4 times（Pumpdown time is 30min；It is pressurised into and is passed through high temperature and high pressure gas, gas heats Temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, then will be adsorbed with the carbon of antibacterial powder and photochromic compound Nanotube reticular membrane scrapes off this substrate, obtains antibacterial-photochromic function agent.

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：

（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：

（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：

（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；Described photochromic multiple Compound is by Nd₂O₃、Pr₂O₃、La₂O₃And Yb₂O₃By weight 1:2:2:1 is obtained by mixing；Without conducting powder.

Comparative example 2

Based on the preparation method of embodiment 4, difference is：Described antibacterial powder is zinc oxide antiseptic；Without light-induced variable Color compound；Described conducting powder is mixed by nano-graphene, aluminium powder, carbon black and graphite.

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.

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

1. a kind of preparation method of photochromic Ceramic Tiles, it comprises the following steps：

Step A, prepares ground-coat enamel：By mass percentage, by 30 ~ 35% frits, 3 ~ 7% functional agents, 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 functional agent is photochromic compound and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder；

Step B, prepares cover-coat enamel：By mass percentage, by 70 ~ 80% frits, 1 ~ 4% conducting powder, 10 ~ 20% kaolin, 5 ~ 8% oxygen Change aluminium, 1 ~ 2% zinc oxide and 1 ~ 5% zirconium silicate to mix, wet ball grinding, after crossing 300 ~ 350 mesh sieves, obtain pulpous state cover-coat enamel；

2. the preparation method of photochromic Ceramic Tiles according to claim 1 is it is characterised in that described conducting powder preparation side Method is as follows：By 30 ~ 40% epoxy resin, 35 ~ 50% phenolic resin, 1 ~ 5% nano-graphene, 2 ~ 6% aluminium powders, 5 ~ 10% carbon blacks and 3 ~ 8% graphite is sufficiently mixed, and wherein, the weight sum of described nano-graphene, aluminium powder, carbon black and graphite accounts for conducting powder gross weight 15 ~ 25%, add appropriate butyl acetate to put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to apply Slurry；By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, be warmed up to 900 ~ 1000 DEG C, it is incubated 1 ~ 2h；Film is scraped off this substrate, obtains conductive porous netted carbon film, i.e. conducting powder.

3. the preparation method of photochromic Ceramic Tiles according to claim 1 and 2 is it is characterised in that described functional agent Preparation method is 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；

（6）Antibacterial powder and photochromic compound is taken to be scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains all even Stable dispersion liquid, the wherein weight of antibacterial powder and photochromic compound are than for 5 ~ 10:1~6；To have carbon nanotube mesh When the substrate of film is placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, make this dispersion liquid It is dispersed in this carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophily, this dispersion liquid is adsorbed Multiple net holes in carbon nanotube mesh film；It is warming up to about 25 DEG C, CNT has hydrophobicity and catches up with most of moisture Walk to stay absorption antibacterial powder and photochromic compound in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in close Close in space, carry out vacuumizing → heat pressurized circulation 3 ~ 5 times, then will be adsorbed with the carbon of antibacterial powder and photochromic compound Nanotube reticular membrane scrapes off this substrate, obtains antibacterial-photochromic function agent.

4. a kind of preparation method of photochromic Ceramic Tiles, it comprises the following steps：

Step A, prepares ground-coat enamel：By mass percentage, by 30 ~ 35% frits, 3 ~ 7% functional agents, 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 functional agent is photochromic compound and GQDs/Ag₂O/ZnO/ Graphene antibiosis powder；

5. the preparation method of photochromic Ceramic Tiles according to claim 4 is it is characterised in that described conducting powder preparation side Method is as follows：By 30 ~ 40% epoxy resin, 35 ~ 50% phenolic resin, 1 ~ 5% nano-graphene, 2 ~ 6% aluminium powders, 5 ~ 10% carbon blacks and 3 ~ 8% graphite is sufficiently mixed, and wherein, the weight sum of described nano-graphene, aluminium powder, carbon black and graphite accounts for conducting powder gross weight 15 ~ 25%, add appropriate butyl acetate to put into dispersion dispergation in ball mill, after discharge, detection, adjustment are configured to apply Slurry；By this slurry coating on substrate, drying and forming-film；Then it is placed in nitrogen filled protection atmosphere furnace, be warmed up to 900 ~ 1000 DEG C, it is incubated 1 ~ 2h；Film is scraped off this substrate, obtains conductive porous netted carbon film, i.e. conducting powder.

6. the preparation method of photochromic Ceramic Tiles according to claim 4 or 5 is it is characterised in that described functional agent Preparation method is as follows：

（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；

（5）Antibacterial powder and photochromic compound is taken to be scattered in 100 ~ 200ml ultra-pure water, ultrasonic agitation 2 ~ 3h obtains all even Stable dispersion liquid, the wherein weight of antibacterial powder and photochromic compound are than for 5 ~ 10:1~6；To have carbon nanotube mesh When the substrate of film is placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, make this dispersion liquid It is dispersed in this carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophily, this dispersion liquid is adsorbed Multiple net holes in carbon nanotube mesh film；It is warming up to about 25 DEG C, CNT has hydrophobicity and catches up with most of moisture Walk to stay absorption antibacterial powder and photochromic compound in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in close Close in space, carry out vacuumizing → heat pressurized circulation 3 ~ 5 times, then will be adsorbed with the carbon of antibacterial powder and photochromic compound Nanotube reticular membrane scrapes off this substrate, obtains antibacterial-photochromic function agent.

7. the preparation method of the photochromic Ceramic Tiles according to claim 3 or 6 is it is characterised in that described three-dimensional sponge Shape graphene preparation method is as follows：By 3g graphite powder, 1g NaNO3 is mixed with 250ml 98% concentrated sulfuric acid in ice-water bath, 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 instead Answer 20min；Add the dilution of 270ml water, and with 5ml 30% H2O2 and unnecessary KMnO4, the color of mixed solution is brown Yellow, filters while hot, and deionized water cyclic washing obtains GO to neutrality, ultrasonic disperse；200ml mass fraction is taken to be 5mg/ The graphene oxide solution of ml pours diameter 25cm into, in the discoid reaction utensil of high 2cm, adds 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, the graphene oxide Spontaneous Contraction in reaction utensil It is cross-linked into three-dimensional sponge structure, freeze-drying, obtain the three-dimensional sponge shape Graphene of flexibility.

8. the preparation method of the photochromic Ceramic Tiles according to claim 3 or 6 is it is characterised in that described photochromic Compound preparation method is as follows：Under nitrogen environment, concentration is the protonic acid solution of 0.05 ~ 0.5mol/L and concentration be 0.05 ~ The DBSA of 0.5mol/L is with volume ratio 3:1 ~ 3 mixing, is simultaneously introduced photochromic powder, and magnetic agitation 60 ~ Aniline is added, photochromic powder and aniline mass ratio are 1 after 120min:5~10；After continuously stirred 60 ~ 90min, dropwise dripped Ammonium sulfate, aniline and ammonium persulfate mol ratio are 1:1；12 ~ 36h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water are washed for several times After be vacuum dried, nano polyaniline/photochromic flour complexes of milling to obtain；1 ~ 10g nano polyaniline/photochromic powder is combined Thing ultrasonic agitation is scattered in the aqueous solution；Add volume ratio 4 afterwards:1 water and ammoniacal liquor, are stirring evenly and then adding into positive silicic acid second Ester, adjusting pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；Carry out centrifugation and use acetone and deionization successively Water cleaning obtains precipitation；This is deposited at 90 DEG C 3h is dried, to obtain nano polyaniline/photochromic flour complexes/SiO₂； By nano polyaniline/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h, remove Polyaniline, photochromic powder/porous SiO₂, i.e. photochromic compound.

9. a kind of photochromic Ceramic Tiles are it is characterised in that be obtained by the preparation method as described in claim 1 or 4.