CN106396394A

CN106396394A - Ecological ceramic tile and preparation method thereof

Info

Publication number: CN106396394A
Application number: CN201610749297.0A
Authority: CN
Inventors: 黎淑娟
Original assignee: Foshan Gaoming Technology Co Ltd
Current assignee: Foshan Gaoming Technology Co Ltd
Priority date: 2016-08-29
Filing date: 2016-08-29
Publication date: 2017-02-15

Abstract

The invention discloses an ecological ceramic tile and a preparation method thereof. The preparation method comprises the steps of: A, glaze slurry preparation; B, glaze slurry impregnation: impregnating cordierite honeycomb ceramic in the glaze slurry, conducting vacuum pumping, and carrying out pressurized circulation treatment at least 1 time, and then performing first firing at 500-600DEG C; C, glaze slurry spraying: spraying the glaze slurry on the fired honeycomb ceramic surface, and then conducting second firing at 700-800DEG C, thus obtaining the ecological ceramic tile. Compared with existing ceramic tiles, the ceramic tile provided by the invention has the advantages of scientific compounding, reasonable preparation, stable performance, and no lead, cadmium or other extremely toxic substances. Also through reasonable collocation of the photochromic compound, negative ion compound and antibacterial composite material, the ceramic tile has excellent antibacterial, air purification and photochromic characteristics, thus further broadening the application scope of ceramics.

Description

A kind of ecological ceramic brick and preparation method thereof

Technical field

The present invention relates to ceramic technology field, a kind of more particularly to ecological ceramic brick and preparation method thereof.

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.

Photochromic refer to due to cause photochromic of the difference of light source and by reflection, refraction and the physical phenomenon such as interfere The color change causing.Photochromic material is divided into organic photochromic material and inorganic photochromic material, wherein to inorganic The research of photochromic material is less, mainly includes transition metal oxide, metal halide and three kinds of rare earth compounding.

For environmental protection aspect, negative aeroion can eliminate foreign flavor indoors and various pernicious gas.Fit up indoors Leftovers leftovers in the irritative gas such as benzene that used in process, art work evaporates, formaldehyde, ketone, ammonia and daily life Acid smell, the harmful peculiar smell such as cigarette, with the material rich in anion, the negative aeroion of its release can be effectively Eliminated, reached the purpose of purify air, and had good suppression to golden staphylococci, Escherichia coli, candida albicans and mould etc. Make and use.

Existing Ceramic Tiles are usually the product of simple function, such as antibacterial, antistatic, noctilucence, photochromic etc., and that is, one Plant product and do not possess multiple function, this strongly limits its range of application and arranged in pairs or groups using two kinds of functional agents although also having, but Effect is still undesirable, 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 ecological ceramic brick and preparation method thereof.

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

A kind of ecological ceramic brick and preparation method thereof, this preparation method comprises the following steps：

Step A, prepare glaze slip：First prepare lead and cadmium free low temperature frit, then through sieving, after ground and mixed, add binding agent and outstanding Floating agent obtains mixed powder, and mixed powder is added water prepared glaze slip；

Step B, dipping glaze slip：Cordierite-quality honeycombed ceramics are impregnated glaze slip → vacuumize → pressurized circulation process, at least circulate 1 Secondary；Then carry out 500 ~ 600 DEG C once sintered；

Step C, spraying glaze slip：By the way of glaze spraying, by glaze slip spraying ceramic honey comb surface after sintering, then carry out 700 ~ 800 DEG C of double sintering, prepared ecological ceramic brick；Wherein,

Described lead and cadmium free low temperature frit is obtained by the following method：By 10 ~ 18% quartz, 5 ~ 12% feldspars, 15 ~ 25% boraxs, 3 ~ 12% carbonate, 20 ~ 35% boric acid, 3 ~ 8% spodumenes, 1 ~ 4% fluoride salt, 0 ~ 5% kaolin mixed grinding uniformly, add 1 ~ 5% Antibiotic complex, 3 ~ 8% anion compounds and 1 ~ 10% photochromic compound, grind and compound are uniformly obtained；Compound cloth Spread in loading fire resistant sagger, carry out 1250 ~ 1320 DEG C of high temperature meltings, obtain the slurry of molten state；By slurry water quenching cooling, and break It is broken into graininess and can get lead and cadmium free low temperature frit.

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 photochromic compound preparation method is as follows：Under nitrogen environment, by concentration be 0.05 ~ The protonic acid solution of the 0.5mol/L and concentration DBSA for 0.05 ~ 0.5mol/L is with volume ratio 3:1 ~ 3 mixing, with When add photochromic powder, add aniline after magnetic agitation 60 ~ 120min, the color-change powder of light and aniline mass ratio are 1:5~10； After continuously stirred 60 ~ 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1；Anti- at 20 DEG C～30 DEG C Answer 12 ~ 36h；Acetone, deionized water washing are vacuum dried for several times afterwards, nano polyaniline/photochromic flour complexes of milling to obtain；Will 1 ~ 10g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in the aqueous solution；Add volume ratio 4 afterwards:1 water And ammoniacal liquor, it is stirring evenly and then adding into tetraethyl orthosilicate（Mass ratio with nano polyaniline/photochromic flour complexes is 5:1~ 3）, 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；By this precipitation drying, 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.Wherein, described photochromic powder is MoO3 nano powder and/or rare earth oxygen Compound, described rare earth oxide be Nd2O3, Er2O3, Pr2O3, CeO2, Sm2O3, La2O3, Y2O3, Yb2O3, Ho2O3 in extremely Few one kind.

In the present invention, described anion compound preparation method is as follows：By 5 ~ 10% astroies, 10 ~ 15% tourmaline, 20 ~ 30% opals, 1 ~ 5% serpentine, 5 ~ 10% medical stones, 1 ~ 5% Strange ice stone, 1 ~ 5% hokutolite, 1 ~ 5% Doctor king stone, 5 ~ 10% shellfishes Shell, 10 ~ 15% diatomite, 1 ~ 3% di-iron trioxide, 2 ~ 5% alundum (Al2O3)s, 3 ~ 8% zirconium oxides and 1 ~ 5% basic zirconium phosphate mix, Add in grinding equipment and carry out ultra-fine grinding, until particle diameter distribution, in 50 ~ 80nm, is sieved, be dried, you can be obtained described negative Ion powder；5 ~ 10g negative ion powder is taken to be scattered in 100 ~ 200ml ultra-pure water, water bath sonicator 1 ~ 2h obtains all even stable dividing Dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, Roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, due to having when CNT is near 8 DEG C There is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, CNT has thin Aqueous and hydrone is driven away leave behind negative ion powder adsorb in multiple net holes of carbon nanotube mesh film；After drying, will inhale Carbon nanotube mesh film with negative ion powder scrapes off this substrate, obtains negative ion powder/CNT, i.e. anion compound.

In the present invention, described antibiotic complex 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 Antibacterial powder；

（5）Under nitrogen environment, by concentration be the protonic acid solution of 0.05 ~ 0.5mol/L and concentration is the ten of 0.05 ~ 0.5mol/L Dialkyl benzene sulfonic acids are with volume ratio 2 ~ 4:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, after magnetic agitation 60 ~ 120min Add aniline, antibacterial powder and aniline mass ratio are 2:12~18；After continuously stirred 60 ~ 90min, dropwise drip ammonium persulfate, aniline It is 1 with ammonium persulfate mol ratio:1；15 ~ 30h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing are vacuum dried for several times afterwards, Mill to obtain nano polyaniline/antibacterial flour complexes；

（6）Prepare TiO 2 sol with sol-gel process, add the nanometer polyphenyl accounting for colloidal sol 0.01 ~ 1.0wt% in colloidal sol Amine/antibacterial flour complexes, mixes；60 DEG C～120 DEG C drying of the rearmounted baking oven of still aging 3～5d；After milling, gained is multiple Calcine 1 ~ 2h at 400～550 DEG C of compound, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；

（7）1 ~ 3g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 100 ~ 200ml ultra-pure water, water bath sonicator 2h obtains All even stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added concave shape Substrate in, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, due to carbon nanometer When pipe is near 8 DEG C, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, CNT has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes absorption to be received in carbon In multiple net holes of mitron reticular membrane；After drying, the carbon nanotube mesh of poriferous titanium dioxide/antibacterial flour complexes will be adsorbed with Film scrapes off this substrate, obtains antibiotic complex.

It is preferred that in step（4）With（5）Between increase by a step：Three-dimensional sponge shape Graphene ultrasonic agitation is taken to be scattered in In the aqueous solution, it is 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；Ultrasonic 60 ~ the 120min of 10 ~ 100W, standing, deionized water is washed for several times, is dried Obtain GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder.

In the present invention, described antibiotic complex 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 antibacterial powder；

（4）Under nitrogen environment, by concentration be the protonic acid solution of 0.05 ~ 0.5mol/L and concentration is the ten of 0.05 ~ 0.5mol/L Dialkyl benzene sulfonic acids are with volume ratio 2 ~ 4:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, after magnetic agitation 60 ~ 120min Add aniline, antibacterial powder and aniline mass ratio are 2:12~18；After continuously stirred 60 ~ 90min, dropwise drip ammonium persulfate, aniline It is 1 with ammonium persulfate mol ratio:1；15 ~ 30h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing are vacuum dried for several times afterwards, Mill to obtain nano polyaniline/antibacterial flour complexes；

（5）Prepare TiO 2 sol with sol-gel process, add the nanometer polyphenyl accounting for colloidal sol 0.01 ~ 1.0wt% in colloidal sol Amine/antibacterial flour complexes, mixes；60 DEG C～120 DEG C drying of the rearmounted baking oven of still aging 3～5d；After milling, gained is multiple Calcine 1 ~ 2h at 400～550 DEG C of compound, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；

（6）1 ~ 3g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 100 ~ 200ml ultra-pure water, water bath sonicator 2h obtains All even stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added concave shape Substrate in, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, due to carbon nanometer When pipe is near 8 DEG C, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, CNT has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes absorption to be received in carbon In multiple net holes of mitron reticular membrane；After drying, the carbon nanotube mesh of poriferous titanium dioxide/antibacterial flour complexes will be adsorbed with Film scrapes off this substrate, obtains antibiotic complex.

It is preferred that in step（3）With（4）Between increase by a step：Three-dimensional sponge shape Graphene ultrasonic agitation is taken to be scattered in In the aqueous solution, it is added dropwise over GQDs/Ag₂In the O/ZnO aqueous solution, three-dimensional sponge shape Graphene and GQDs/Ag₂The weight ratio of O/ZnO For 1:1~5；Ultrasonic 60 ~ the 120min of 10 ~ 100W, standing, deionized water is washed for several times, dry GQDs/Ag₂O/ZnO/ Graphene Antibacterial powder.

The present invention has the advantages that：This method loads and fixing antiseptic on the carbon nanotubes, not only prevents it Reunite, significantly improve the stability of the antiseptics such as metal nanoparticle so as to can more preferably be dispersed in low temperature frit, and have more Long-acting antibacterial activity and silver ion will not overflow oxidation stain；It is compounded with the anti-microbial property of multiple antiseptics simultaneously, compare There is more preferable antibacterial effect in single silver nano antibacterial agent, antibacterial is lasting；Photochromic compound has photochromic Effect, makes product more rich and varied, is cannot to be compared using the Ceramic Tiles that conventional colorants produce using the Ceramic Tiles that it produces Intend, the shades of colour that can change with the strong and weak difference of irradiation light, be a splendid legacy, full of magnificent carriage, so that pottery produces Product seem beautiful magical, pure and fresh elegance, intersperse city night life, increase sentiment and artistic effect to building and interior decoration； Anion compound can efficiently continual anion releasing, under having light or no light condition all can uninterrupted anion releasing, Effectively purify air, the organic gas such as decomposing formaldehyde, improves IAQ, also has the effect of antibacterial, be beneficial to human body Health.

Compare with existing Ceramic Tiles, the Ceramic Tiles dispensing science that the present invention manufactures, preparation is reasonable, stable performance, and not Containing extremely toxic substances such as lead cadmiums, through rational arrange in pairs or groups photochromic compound, anion compound and antimicrobial composite material, make Obtain Ceramic Tiles and there is excellent antibacterial, purify air and photochromic characteristic, widen the range of application of pottery further.

Specific embodiment

To further illustrate technical scheme below by specific preferred embodiment.

Embodiment 1

Step A, prepares glaze slip：By 12% quartz, 12% feldspar, 15% borax, 6% carbonate, 35% boric acid, 5% spodumene, 1% fluorination Salt, 2% kaolin mixed grinding uniformly, add 1% antibiotic complex, 3% anion compound and 8% photochromic compound, Grind and compound is uniformly obtained；The compound being obtained is dispensed in loading fire resistant sagger, carries out 1250 ~ 1320 DEG C of high temperature meltings, Obtain the slurry of molten state；High temperature melting technique is：Room temperature, to 1000 DEG C, is incubated 10min；It is warming up to 1300 DEG C, insulation 30min；It is cooled to 1250 DEG C, be incubated 15min；It is warming up to 1320 DEG C, be incubated 30min；By slurry water quenching cooling, and it is broken into Granular can get lead and cadmium free low temperature frit；By low temperature frit through sieving, after ground and mixed, interim as normal temperature by the use of PVA Binding agent, adds gum arabic suspending agent, mixed powder addition water is made the glaze slip possessing certain suspendability, controls slurry Material 300 ~ 350 mesh.

Step B, impregnates glaze slip：Cordierite-quality honeycombed ceramics are carried out impregnate glaze slip → vacuumize → pressurized circulation and process （It is specially：It is immersed in 10min in the glaze slip that step A is obtained, takes out, the porous ceramics after dipping is carried out vacuumizing → pressurizeing Process, vacuumizing vacuum is -0.02Mpa, pressurize 5min；It is forced into 0.3Mpa, pressurize 10min）, circulate 7 times；Then carry out 500 ~ 600 DEG C once sintered；

Step C, sprays glaze slip：By the way of glaze spraying, by glaze slip spraying cordierite-quality honeycombed ceramics surface after sintering, spray During glaze, at 75 ± 2 DEG C, the adobe of the every 600mm × 600mm of weight of glazing sprays cordierite-quality honeycombed ceramics surface temperature control 160g；Then 700 ~ 800 DEG C of double sintering, prepared ecological ceramic brick are carried out.

Wherein, described feldspar is by potassium feldspar and albite by weight 4:1 is obtained by mixing；Described carbonate by potassium carbonate, Sodium carbonate, brium carbonate, lithium carbonate and calcium carbonate by weight 3:1:3:2:1 is obtained by mixing；Described fluoride salt is by sodium fluoride, fluorination Calcium and lithium fluoride by weight 4:2:1 is obtained by mixing.

Wherein, described photochromic compound preparation method is as follows：Under nitrogen environment, by the proton for 0.3mol/L for the concentration The acid solution and concentration DBSA for 0.3mol/L is with volume ratio 3:2 mixing, are simultaneously introduced photochromic powder （Nd2O3, Er2O3 and Pr2O3 by weight 2:1:1 mixing）, after magnetic agitation 90min, add aniline, the color-change powder of light and benzene Amine mass ratio is 1:8；After continuously stirred 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1；20℃ 20h is reacted at～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/photochromic powder is multiple Compound；8g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in the aqueous solution；Add volume ratio 4 afterwards:1 Water and ammoniacal liquor, be stirring evenly and then adding into tetraethyl orthosilicate（Mass ratio with nano polyaniline/photochromic flour complexes is 5: 2）, adjusting pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out centrifugation and use acetone and deionized water successively Cleaning obtains precipitation；This is deposited at 90 DEG C 3h is dried, to obtain nano polyaniline/photochromic flour complexes/SiO₂；Will Nano polyaniline/photochromic flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove polyaniline, light Mutagens toner/porous SiO₂, obtain final product photochromic compound.

Described anion compound preparation method is as follows：By 8% astroies, 12% tourmaline, 25% opal, 4% snake Stone, 7% medical stone, 4% Strange ice stone, 4% hokutolite, 3% Doctor king stone, 8% shell, 12% diatomite, 2% di-iron trioxide, 3% 3 oxidation Two aluminium, 5% zirconium oxide and 3% basic zirconium phosphate mix, and add in grinding equipment and carry out ultra-fine grinding, until particle diameter distribution exists 50 ~ 80nm, sieves, and is dried, you can described negative ion powder is obtained；8g negative ion powder is taken to be scattered in 150ml ultra-pure water, water-bath surpasses Sound 2h obtains all even stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added In the substrate of concave shape, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, by When CNT is near 8 DEG C, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；Heat up To about 25 DEG C, CNT has hydrophobicity drive hydrone away and leaves behind negative ion powder and adsorbs in carbon nanotube mesh film In multiple net holes；After drying, the carbon nanotube mesh film being adsorbed with negative ion powder is scraped off this substrate, obtain final product anion and be combined Thing.

Described antibiotic complex 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 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 antibacterial powder；

（5）Under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/L for the protonic acid solution and concentration for 0.2mol/L for the concentration Acid is with volume ratio 3:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min It is 2 with aniline mass ratio:After 18 continuously stirred 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple Compound；

（6）Prepare TiO 2 sol with sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 1.0wt%/anti- Bacterium powder compound, mixes；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained compound after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；

（7）1g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains all even Stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added the substrate of concave shape In, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, because CNT is at 8 DEG C When nearby, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer Pipe has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes and adsorbs in carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial flour complexes is scraped off this base Plate, obtains antibiotic complex.

Embodiment 2

Step A, prepares glaze slip：By 15% quartz, 5% feldspar, 20% borax, 8% carbonate, 25% boric acid, 8% spodumene, 3% fluorination Salt, 3% kaolin mixed grinding uniformly, add 3% antibiotic complex, 5% anion compound and 5% photochromic compound, Grind and compound is uniformly obtained；The compound being obtained is dispensed in loading fire resistant sagger, carries out 1250 ~ 1320 DEG C of high temperature meltings, Obtain the slurry of molten state；High temperature melting technique is：Room temperature, to 1000 DEG C, is incubated 10min；It is warming up to 1300 DEG C, insulation 30min；It is cooled to 1250 DEG C, be incubated 15min；It is warming up to 1320 DEG C, be incubated 30min；By slurry water quenching cooling, and it is broken into Granular can get lead and cadmium free low temperature frit；By low temperature frit through sieving, after ground and mixed, interim as normal temperature by the use of PVA Binding agent, adds gum arabic suspending agent, mixed powder addition water is made the glaze slip possessing certain suspendability, controls slurry Material 300 ~ 350 mesh.

Wherein, the preparation method of described photochromic compound is as follows：Under nitrogen environment, by the matter for 0.3mol/L for the concentration The sub- acid solution and concentration DBSA for 0.3mol/L is with volume ratio 3:2 mixing, are simultaneously introduced photochromic powder （MoO3 nano powder）, add aniline after magnetic agitation 90min, the color-change powder of light and aniline mass ratio are 1:8；Continuously stirred After 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1；20h is reacted at 20 DEG C～30 DEG C；Acetone, Deionized water washing is vacuum dried for several times afterwards, nano polyaniline/photochromic flour complexes of milling to obtain；By 8g nano polyaniline/ Photochromic flour complexes ultrasonic agitation is scattered in the aqueous solution；Add volume ratio 4 afterwards:1 water and ammoniacal liquor, after stirring Add tetraethyl orthosilicate（Mass ratio with nano polyaniline/photochromic flour complexes is 5:2）, adjusting pH value is 9 ~ 10, instead Answer temperature to be 20 ~ 25 DEG C, react 60min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is precipitated 3h is dried at 90 DEG C, to obtain nano polyaniline/photochromic flour complexes/SiO₂；By nano polyaniline/photochromic powder Compound/SiO₂It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove polyaniline, photochromic powder/porous SiO₂, obtain final product Photochromic compound.

Described antibiotic complex is obtained by the following method：

（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 antibacterial powder；

（5）Under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/L for the protonic acid solution and concentration for 0.2mol/L for the concentration Acid is with volume ratio 3:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min It is 2 with aniline mass ratio:After 15 continuously stirred 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple Compound；

（6）Prepare TiO 2 sol with sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 0.5wt%/anti- Bacterium powder compound, mixes；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained compound after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；

（7）2g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains all even Stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added the substrate of concave shape In, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, because CNT is at 8 DEG C When nearby, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer Pipe has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes and adsorbs in carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial flour complexes is scraped off this base Plate, obtains antibiotic complex.

Embodiment 3

Step A, prepares glaze slip：By 18% quartz, 5% feldspar, 24% borax, 8% carbonate, 20% boric acid, 6% spodumene, 1% fluorination Salt, 4% kaolin mixed grinding uniformly, add 5% antibiotic complex, 8% anion compound and 1% photochromic compound, Grind and compound is uniformly obtained；The compound being obtained is dispensed in loading fire resistant sagger, carries out 1250 ~ 1320 DEG C of high temperature meltings, Obtain the slurry of molten state；High temperature melting technique is：Room temperature, to 1000 DEG C, is incubated 10min；It is warming up to 1300 DEG C, insulation 30min；It is cooled to 1250 DEG C, be incubated 15min；It is warming up to 1320 DEG C, be incubated 30min；By slurry water quenching cooling, and it is broken into Granular can get lead and cadmium free low temperature frit；By low temperature frit through sieving, after ground and mixed, interim as normal temperature by the use of PVA Binding agent, adds gum arabic suspending agent, mixed powder addition water is made the glaze slip possessing certain suspendability, controls slurry Material 300 ~ 350 mesh.

Wherein, the preparation method of described photochromic compound is as follows：Under nitrogen environment, by the matter for 0.3mol/L for the concentration The sub- acid solution and concentration DBSA for 0.3mol/L is with volume ratio 3:2 mixing, are simultaneously introduced photochromic powder （Ho2O3）, add aniline after magnetic agitation 90min, the color-change powder of light and aniline mass ratio are 1:8；After continuously stirred 90min, Dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1；20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water Washing is vacuum dried for several times afterwards, nano polyaniline/photochromic flour complexes of milling to obtain；By 8g nano polyaniline/photochromic Flour complexes 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 silicon Acetoacetic ester（Mass ratio with nano polyaniline/photochromic flour complexes is 5:2）, adjusting pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, react 60min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；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 DEG C of heat treatment 1h, remove polyaniline, photochromic powder/porous SiO₂, obtain final product light-induced variable Color compound.

Antibiotic complex is obtained by the following method：

（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 antibacterial powder；

（5）Under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/L for the protonic acid solution and concentration for 0.2mol/L for the concentration Acid is with volume ratio 3:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min It is 2 with aniline mass ratio:After 12 continuously stirred 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple Compound；

（6）Prepare TiO 2 sol with sol-gel process, add in colloidal sol account for the nano polyaniline of colloidal sol 0.01wt%/ Antibacterial flour complexes, mix；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；Forge at 500 DEG C of gained compound after milling Burn 1h, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；

（7）3g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains all even Stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added the substrate of concave shape In, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, because CNT is at 8 DEG C When nearby, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer Pipe has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes and adsorbs in carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial flour complexes is scraped off this base Plate, obtains antibiotic complex.

Embodiment 4

Based on the preparation method of embodiment 2, difference is：Step（4）With（5）Between increase following steps：Take three-dimensional sea Continuous shape Graphene ultrasonic agitation is scattered in the aqueous solution, is added dropwise over GQDs/Ag₂O/Ag-Zn-Ce/SiO₂In the aqueous solution, three-dimensional Spongy graphene and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂Weight than for 1:3；The ultrasonic 90min of 50W, standing, deionized water Washing for several times, dry GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder.

Three-dimensional sponge shape graphene preparation method is as follows：By 3g graphite powder, 1g NaNO3 in ice-water bath with 250ml 98% concentrated sulfuric acid mixes, and is slowly added to 6g KMnO4.Then heat at 35 DEG C, after stirring 40min, add 95ml to go Ionized water, is warming up to 98 DEG C of reaction 20min；Add 270ml water dilution, and with 5ml 30% H2O2 with unnecessary KMnO4, The color of mixed solution is brown color, filters while hot, and deionized water cyclic washing obtains GO to neutrality, ultrasonic disperse；Take 200ml mass fraction is that 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, in reaction utensil Graphene oxide Spontaneous Contraction be cross-linked into three-dimensional sponge structure, freeze-drying, obtain flexibility three-dimensional sponge shape Graphene.

Embodiment 5

Based on the preparation method of embodiment 1, difference is：Described antibiotic complex 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 antibacterial powder；

（4）Under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/L for the protonic acid solution and concentration for 0.2mol/L for the concentration Acid is with volume ratio 3:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min It is 2 with aniline mass ratio:After 18 continuously stirred 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple Compound；

（5）Prepare TiO 2 sol with sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 1.0wt%/anti- Bacterium powder compound, mixes；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained compound after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；

（6）1g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains all even Stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added the substrate of concave shape In, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, because CNT is at 8 DEG C When nearby, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer Pipe has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes and adsorbs in carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial flour complexes is scraped off this base Plate, obtains antibiotic complex.

Embodiment 6

Based on the preparation method of embodiment 2, difference is：Described antibiotic complex 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 antibacterial powder；

（4）Under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/L for the protonic acid solution and concentration for 0.2mol/L for the concentration Acid is with volume ratio 3:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min It is 2 with aniline mass ratio:After 15 continuously stirred 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple Compound；

（5）Prepare TiO 2 sol with sol-gel process, add in colloidal sol and account for the nano polyaniline of colloidal sol 0.5wt%/anti- Bacterium powder compound, mixes；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；To calcine at 500 DEG C of gained compound after milling 1h, removes polyaniline, obtains poriferous titanium dioxide/antibacterial flour complexes；

（6）2g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains all even Stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added the substrate of concave shape In, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, because CNT is at 8 DEG C When nearby, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer Pipe has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes and adsorbs in carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial flour complexes is scraped off this base Plate, obtains antibiotic complex.

Embodiment 7

Based on the preparation method of embodiment 3, difference is：Described antibiotic complex 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 antibacterial powder；

（4）Under nitrogen environment, by the detergent alkylate sulphur for 0.1mol/L for the protonic acid solution and concentration for 0.2mol/L for the concentration Acid is with volume ratio 3:2 mixing, are simultaneously introduced step（4）Prepared antibacterial powder, adds aniline, antibacterial powder after magnetic agitation 100min It is 2 with aniline mass ratio:After 12 continuously stirred 90min, dropwise drip ammonium persulfate, aniline and ammonium persulfate mol ratio are 1:1； 20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing be vacuum dried afterwards for several times, mill nano polyaniline/antibacterial powder is multiple Compound；

（5）Prepare TiO 2 sol with sol-gel process, add in colloidal sol account for the nano polyaniline of colloidal sol 0.01wt%/ Antibacterial flour complexes, mix；The 90 DEG C of drying of the rearmounted baking oven of still aging 4d；Forge at 500 DEG C of gained compound after milling Burn 1h, remove polyaniline, obtain poriferous titanium dioxide/antibacterial flour complexes；

（6）3g poriferous titanium dioxide/antibacterial flour complexes are taken to be scattered in 150ml ultra-pure water, water bath sonicator 2h obtains all even Stable dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added the substrate of concave shape In, meanwhile, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, because CNT is at 8 DEG C When nearby, there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, carbon nanometer Pipe has hydrophobicity drive hydrone away and leaves behind poriferous titanium dioxide/antibacterial flour complexes and adsorbs in carbon nanotube mesh film Multiple net holes in；After drying, the carbon nanotube mesh film being adsorbed with poriferous titanium dioxide/antibacterial flour complexes is scraped off this base Plate, obtains antibiotic complex.

Embodiment 8

Based on the preparation method of embodiment 6, difference is：Step（3）With（4）Between increase as next step：Take three-dimensional Spongy graphene ultrasonic agitation is scattered in the aqueous solution, is added dropwise over GQDs/Ag₂In the O/ZnO aqueous solution, three-dimensional sponge shape stone Black alkene and GQDs/Ag₂The weight of O/ZnO is than for 1:3；The ultrasonic 90min of 50W, standing, deionized water is washed for several times, dry GQDs/Ag₂O/ZnO/ Graphene antibiosis powder.

Comparative example 1

Based on the preparation method of embodiment 1, difference is：Described antibiotic complex is the titanium dioxide carrying metal antibacterial agent Titanium；Without photochromic compound and anion compound.

Comparative example 2

Based on the preparation method of embodiment 5, difference is：Described antibiotic complex is the mixing of zinc oxide and titanium dioxide Thing；Described photochromic compound is MoO3 nano powder；Described anion compound be negative ion powder, by 8% astroies, 12% Tourmaline, 25% opal, 4% serpentine, 7% medical stone, 4% Strange ice stone, 4% hokutolite, 3% Doctor king stone, 8% shell, 12% diatom Soil, 2% di-iron trioxide, 3% alundum (Al2O3), 5% zirconium oxide and 3% basic zirconium phosphate mix, and add in grinding equipment and are surpassed Finely divided, until particle diameter distribution, in 50 ~ 80nm, is sieved, it is dried, you can described negative ion powder is obtained.

Each embodiment and the low temperature frit of comparative example offer, wherein not leaded, cadmium toxic element, the experiment proved that and be less than It is melting at 800 DEG C, can be used for preparing the flux material of various low-temperature environment-friendly potteries.

The Ceramic Tiles that embodiment 1 ~ 8, comparative example 1 ~ 2 are obtained carry out antibacterial antifouling property test and photochromic properties Test, test result is as follows：

Sterilization rate：Take 10⁵The Escherichia coli 0.1ml of individual/ml, is spread evenly across in Ceramic Tiles, places 2h indoors, then will Bacterium solution sterilized water is eluted in culture medium, cultivates 24h, then detects bacterium number, calculate sterilization rate at 37 DEG C.

Wear testing：The abrasive material being 3～4 from Mohs' hardness, friction in Ceramic Tiles uses 2 imitating paving 1000 times Effect after year, tests 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.

Antifouling test：It is pollutant from chrome green.

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.

Anion burst size：COM-3010PRO type ion detector test anion burst size is produced using Japan, by this sample Product are positioned over 1m³Test box (length is 1m) in, record in the air air-anion concentration（Initial and 24h）；Adopt With the test of Han Wang M1 type haze table, PM2.5 concentration in test box（Initial and 24h）；0.1mg formaldehyde (formaldehyde is dripped in test box Concentration 0.1mg/m³), record concentration of formaldehyde after 24h.

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 ecological ceramic brick, it comprises the following steps：

2. the preparation method of ecological ceramic brick according to claim 1 is it is characterised in that described photochromic compound system Preparation Method is as follows：Under nitrogen environment, by concentration be the protonic acid solution of 0.05 ~ 0.5mol/L and concentration is 0.05 ~ 0.5mol/L DBSA with volume ratio 3:1 ~ 3 mixing, is simultaneously introduced photochromic powder, adds after magnetic agitation 60 ~ 120min Aniline, the color-change powder of light and aniline mass ratio are 1:5~10；After continuously stirred 60 ~ 90min, dropwise drip ammonium persulfate, aniline It is 1 with ammonium persulfate mol ratio:1；12 ~ 36h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing are vacuum dried for several times afterwards, Mill to obtain nano polyaniline/photochromic flour complexes；By 1 ~ 10g nano polyaniline/photochromic flour complexes ultrasonic agitation It is scattered in the aqueous solution；Add volume ratio 4 afterwards:1 water and ammoniacal liquor, are stirring evenly and then adding into tetraethyl orthosilicate, 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；By this precipitation drying, to obtain nano polyaniline/photochromic flour complexes/SiO₂；By nano polyaniline/light-induced variable Toner compound/SiO₂It is placed under argon gas atmosphere and carry out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h, removal polyaniline, photochromic powder/ Porous SiO₂, i.e. photochromic compound.

3. the preparation method of ecological ceramic brick according to claim 2 is it is characterised in that described tetraethyl orthosilicate and nanometer The mass ratio of polyaniline/photochromic flour complexes is 5:1~3.

4. the preparation method of ecological ceramic brick according to claim 1 is it is characterised in that prepared by described anion compound Method is as follows：5 ~ 10g negative ion powder is taken to be scattered in 100 ~ 200ml ultra-pure water, water bath sonicator 1 ~ 2h obtains all even stable Dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, with When, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, because CNT is near 8 DEG C When there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, CNT has There is hydrophobicity drive hydrone away to leave behind negative ion powder to adsorb in multiple net holes of carbon nanotube mesh film；After drying, The carbon nanotube mesh film being adsorbed with negative ion powder is scraped off this substrate, obtains anion compound.

5. the preparation method of the ecological ceramic brick according to claim 1,2 or 4 is it is characterised in that described antibiotic complex 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；

（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, adjust pH value be 9 ~ 10, reaction temperature be 20 ~ 25 DEG C, react 30 ~ 60min；Carry out Centrifugation simultaneously cleans 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/SiO₂It is placed under argon gas atmosphere and carry out 500 ~ 800 DEG C of heat Process 1 ~ 2h, after being cooled to room temperature, be immersed in hydrofluoric acid and ultrasonic 10 ~ 15min is carried out with ultrasonic power 100 ~ 150W, remove table Face local silica, is centrifuged and is dried, obtain antibacterial powder；

6. a kind of preparation method of ecological ceramic brick, it comprises the following steps：

Described lead and cadmium free low temperature frit is obtained by the following method：By 10 ~ 18% quartz, 5 ~ 12% feldspars, 15 ~ 25% boraxs, 3 ~ 12% carbonate, 20 ~ 35% boric acid, 3 ~ 8% spodumenes, 1 ~ 4% fluoride salt, 0 ~ 5% kaolin mixed grinding uniformly, add 1 ~ 5% Antibiotic complex, 3 ~ 8% anion compounds and 1 ~ 10% photochromic compound, grind and compound are uniformly obtained；Compound cloth Spread in loading fire resistant sagger, carry out 1250 ~ 1320 DEG C of high temperature meltings, obtain the slurry of molten state；By slurry water quenching cooling, and break It is broken into graininess and can get lead and cadmium free low temperature frit；

Wherein, the preparation method of described antibiotic complex is as follows：

7. the preparation method of ecological ceramic brick according to claim 6 is it is characterised in that described photochromic compound system Preparation Method is as follows：Under nitrogen environment, by concentration be the protonic acid solution of 0.05 ~ 0.5mol/L and concentration is 0.05 ~ 0.5mol/L DBSA with volume ratio 3:1 ~ 3 mixing, is simultaneously introduced photochromic powder, adds after magnetic agitation 60 ~ 120min Aniline, the color-change powder of light and aniline mass ratio are 1:5~10；After continuously stirred 60 ~ 90min, dropwise drip ammonium persulfate, aniline It is 1 with ammonium persulfate mol ratio:1；12 ~ 36h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water washing are vacuum dried for several times afterwards, Mill to obtain nano polyaniline/photochromic flour complexes；By 1 ~ 10g nano polyaniline/photochromic flour complexes ultrasonic agitation It is scattered in the aqueous solution；Add volume ratio 4 afterwards:1 water and ammoniacal liquor, are stirring evenly and then adding into tetraethyl orthosilicate, 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；By this precipitation drying, to obtain nano polyaniline/photochromic flour complexes/SiO₂；By nano polyaniline/light-induced variable Toner compound/SiO₂It is placed under argon gas atmosphere and carry out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h, removal polyaniline, photochromic powder/ Porous SiO₂, i.e. photochromic compound.

8. the preparation method of ecological ceramic brick according to claim 7 is it is characterised in that described tetraethyl orthosilicate and nanometer The mass ratio of polyaniline/photochromic flour complexes is 5:1~3.

9. the preparation method of ecological ceramic brick according to claim 5 is it is characterised in that prepared by described anion compound Method is as follows：5 ~ 10g negative ion powder is taken to be scattered in 100 ~ 200ml ultra-pure water, water bath sonicator 1 ~ 2h obtains all even stable Dispersion liquid；When the substrate with carbon nanotube mesh film is placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, with When, roll around roller, so that this homogeneous dispersion is scattered in this carbon nanotube mesh film, because CNT is near 8 DEG C When there is hydrophily, this dispersion liquid is attracted to multiple net holes of carbon nanotube mesh film；It is warming up to about 25 DEG C, CNT has There is hydrophobicity drive hydrone away to leave behind negative ion powder to adsorb in multiple net holes of carbon nanotube mesh film；After drying, The carbon nanotube mesh film being adsorbed with negative ion powder is scraped off this substrate, obtains anion compound.

10. a kind of ecological ceramic brick is it is characterised in that be obtained by the preparation method as described in claim 2 or 6.