CN106396384A

CN106396384A - Noctilucent deodorant ceramic glaze and preparation method thereof

Info

Publication number: CN106396384A
Application number: CN201610748699.9A
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 noctilucent deodorant ceramic glaze and a preparation method thereof. The preparation method comprises the steps of: firstly preparing a noctilucent deodorant glaze slurry, and then conducting glazing and sintering to obtain ceramic glaze. Specifically, the preparation method of the noctilucent deodorant glaze slurry consists of: by mass percentage, mixing 25-35% of low temperature frit, 30-40% of potassium feldspar, 10-20% of quartz, 3-6% of calcite, 3-6% of talc, 2-5% of calcium phosphate, 1-5% of kaolin, and 5-10% calcined soil to obtain mixed powder, adding a functional agent accounting for 3-10% of the mass of the mixed powder into the mixed powder and mixing the substances evenly, performing fine grinding, and adding water to obtain the glaze slurry, i.e. noctilucent deodorant ceramic glaze slurry. Compared with existing ceramic glazes, the ceramic glaze prepared by the invention has the characteristics of scientific compounding, reasonable preparation, stable performance, and no lead, cadmium or other extremely toxic substances, also has uniform and lasting spectral antibacterial properties, deodorizing properties and noctilucent function, thus further broadening the application scope of ceramic glaze.

Description

A kind of noctilucence deodorization ceramic glaze and preparation method thereof

Technical field

The present invention relates to ceramic technology field, a kind of more particularly to noctilucence deodorization ceramic glaze 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.

Wall brick, no matter household interior decoration, or it is used for industrial production or public place, after meeting outward appearance practicality, How to make it possess more functions of concerning health of people guarantee aspect, be also that industry researcher is kept up with the trend of the times and given birth to Live wind vane and the thinking made.

In the building and ornament materials such as existing wall brick, also it is rarely reported the antibacterial work(preferably stable with regard to uniformity at present The ceramic glaze of energy, if simply add antiseptic, due to high temperature melting technique so that antibacterial stability weakens in some instances it may even be possible to lose Remove antibacterial effect.Existing ceramic material is usually the product of simple function, and that is, a kind of product does not possess multiple function, and this is very big Limit 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 carry further High.

Content of the invention

In order to solve above-mentioned the deficiencies in the prior art, the invention provides a kind of noctilucence deodorization ceramic glaze and its preparation side Method.

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

A kind of noctilucence deodorization ceramic glaze and preparation method thereof, this preparation method comprises the following steps：First prepare the deodorant glaze slip of noctilucence, Noctilucence deodorization ceramic glaze is obtained through glazing, sintering again；Wherein, the preparation method of the deodorant glaze slip of noctilucence is as follows：By mass percentage Meter, by 25 ~ 35% low temperature frits, 30 ~ 40% potassium feldspars, 10 ~ 20% quartz, 3 ~ 6% calcites, 3 ~ 6% talcums, 2 ~ 5% phosphorus Sour calcium, 1 ~ 5% kaolin, 5 ~ 10% calcined earths are mixed to get mixed-powder, add functional agent and mix in mixed-powder, The addition of wherein said functional agent is the 3 ~ 10% of mixed-powder quality, is finely ground to 300 ~ 350 mesh, is subsequently adding water and obtains glaze slip And modulate glaze slip proportion for 1.6 ~ 1.7g/cm³, obtain final product noctilucence deodorization ceramic glaze slip.

Wherein, the mass percent of described low temperature frit consists of：6～10% potassium nitrate, 5～10% quartz, 12～15% potassium Feldspar, 3～8% albites, 10～12% spodumenes, 30～35% boric acid, 3～5% brium carbonates, 5～8% fluorites, 1～3% kaolin, 2～5% sodium fluorides and 5 ~ 10% functional agents.

Wherein,

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, noctilucence compound and deodorant 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, noctilucence compound and deodorant are than for 3 ~ 6:2~4:1~5；To have carbon When the substrate of nanotube reticular membrane is placed in 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 this carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophily, this point 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 and by big portion Divide hydrone to drive away and leave absorption antibacterial powder, noctilucence compound and deodorant in multiple net holes of carbon nanotube mesh film；Go Fall moisture, be placed in confined space, carry out vacuumizing → heat pressurized circulation 3 ~ 5 times（Pumpdown time is 20 ~ 30min；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 0.3 ~ 0.6Mpa, pressurize 20 ~ 30min）, Then the carbon nanotube mesh film being adsorbed with antibacterial powder, noctilucence compound and deodorant is scraped off this substrate, acquisition antibacterial-remove Smelly-noctilucent 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, noctilucence compound and deodorant 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, noctilucence compound and deodorant are than for 3 ~ 6:2~4:1~5；To have carbon When the substrate of nanotube reticular membrane is placed in 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 this carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophily, this point 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 and by big portion Divide hydrone to drive away and leave absorption antibacterial powder, noctilucence compound and deodorant in multiple net holes of carbon nanotube mesh film；Go Fall moisture, be placed in confined space, carry out vacuumizing → heat pressurized circulation 3 ~ 5 times（Pumpdown time is 20 ~ 30min；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 0.3 ~ 0.6Mpa, pressurize 20 ~ 30min）, Then the carbon nanotube mesh film being adsorbed with antibacterial powder, noctilucence compound and deodorant is scraped off this substrate, acquisition antibacterial-remove Smelly-noctilucent 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.

In the present invention, the preparation method of described noctilucence compound 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 luminescent powder, add aniline after magnetic agitation 60 ~ 120min, luminescent 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/noctilucence flour complexes of milling to obtain；By 1 ~ 10g nanometer polyphenyl Amine/noctilucence 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/noctilucence flour complexes is 5:1~3）, adjusting pH value is 9 ~ 10, reaction Temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is sunk Shallow lake drying, to obtain nano polyaniline/noctilucence flour complexes/SiO₂；By nano polyaniline/noctilucence flour complexes/SiO₂It is placed in argon Carry out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h under gas atmosphere, remove polyaniline, obtain luminescent powder/porous SiO₂.Described luminescent powder is flat All particle diameter is less than the long afterglow Sr of 10nm₄Al₁₄O₂₅Nano-phosphor.

In the present invention, described deodoriser preparing process is as follows：Mix the raw material of following percentage by weight：ZrO₂2 ~ 8%, TiO₂5 ~ 15%, SiO₂10 ~ 20%, V₂O₅1 ~ 5%, K₂O 1 ~ 5%, SnO₂1 ~ 5%, Cr₂O₃1 ~ 5%, Al₂O₃10 ~ 15%, Fe₂O₃ 10 ~ 15%, MgO 10 ~ 20%, Na₂O 1 ~ 10%, MnO₂1 ~ 10%, put into the big flow circulation horizontal sand of PUHLER company exploitation It is ground in grinding machine, control particle diameter between 10 ~ 300nm, obtain inorganic oxide；Diatomite is dispersed in 100 ~ 200ml's In the aqueous solution, add inorganic oxide, the weight of wherein said diatomite and inorganic oxide ratio is for 1:1 ~ 6,100 ~ 200W surpass Sound 100 ~ 300rpm stirs 1 ~ 2h, allows nano material well in diatom soil pores, multiple suction filtration cleans；It is placed in confined space Interior, carry out vacuumizing → heat pressurized circulation 3 ~ 8 times（Pumpdown time is 20 ~ 30min；It is pressurised into and be passed through HTHP Gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.3 ~ 0.6Mpa, pressurize 20 ~ 30min）, obtain deodorant.

The present invention has the advantages that：Compare with existing ceramic glaze, the ceramic glaze dispensing science that the present invention manufactures, system Standby reasonable, stable performance, and do not contain the extremely toxic substances such as lead cadmium, the antibacterial also with uniformly lasting spectrum simultaneously is special Property, deodorization functions and noctilucence characteristic, have widened the range of application of ceramic glaze further.

This method loads and fixing antiseptic on three-dimensional grapheme, not only prevents its reunion, significantly improves metal nano The stability of the antiseptics such as particle is so as to can more preferably be dispersed in low temperature frit and glaze slip, and has more efficient antibacterial activity And silver ion will not overflow oxidation stain；It is compounded with the anti-microbial property of multiple antiseptics, compared to single silver nanoparticle simultaneously Antiseptic has more preferable antibacterial effect, and antibacterial is lasting, and uniformly dispersed more preferable；Inorganic oxide main component have magnesium, More than 10 kind of aluminium, iron etc. trace element favourable to human body, because it is a kind of special polarity crystalline solid of structure, itself can grow Phase produces electron ion, and forever discharges negative aeroion, reaches the effect of deodorant purify air.

The present invention is by reasonably combined antibacterial powder, noctilucence compound and deodorant, and adsorbs netted in multilayer respectively On CNT, can further improve dispersing uniformity in ceramic glaze for the functional agent and functional stabilization.

Specific embodiment

To further illustrate technical scheme below by specific preferred embodiment.

Embodiment 1

A kind of noctilucence deodorization ceramic glaze and preparation method thereof, this preparation method comprises the steps：

Step A, prepares low temperature frit：By mass percentage, by 10% potassium nitrate, 7% quartz, 10% potassium feldspar, 5% albite, 10% spodumene, 30% boric acid, 5% brium carbonate, 8% fluorite, 3% kaolin, 2% sodium fluoride and 10% functional agent mix, and pass through Quick quenching after calcining at 1250～1300 DEG C after sieve, ground and mixed, the low temperature having obtained 650～800 DEG C of melt temperature melts Block；

Step B, prepares the deodorant glaze slip of noctilucence：By mass percentage, by 30% low temperature frit, 30% potassium feldspar, 10% quartz, 5% calcite, 8% talcum, 4% calcium phosphate, 5% kaolin, 8% calcined earth are mixed to get mixed-powder, add in mixed-powder Enter functional agent and mix, be finely ground to 300 ~ 350 mesh, be subsequently adding water and obtain glaze slip and modulate glaze slip proportion for 1.6 ~ 1.7g/ cm³, obtain final product noctilucence deodorization ceramic glaze slip；Wherein, the addition of functional agent is the 3% of mixed-powder quality；

Step C, product glazing：By the way of glaze spraying, noctilucence deodorization ceramic glaze is sprayed on adobe surface, adobe temperature during glaze spraying Degree controls at 75 ± 2 DEG C, the adobe spraying 160g of the every 600mm × 600mm of weight of glazing；

Step D, sintering：The adobe that step B is coated with noctilucence deodorization ceramic glaze is put in roller kilns and is burnt till, and firing temperature controls For 900 ± 5 DEG C, firing period is 65 ± 3min.

Wherein, described functional agent 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 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 noctilucence compound：Under nitrogen environment, the protonic acid solution for 0.3mol/L for the concentration and concentration are 0.3mol/L DBSA with volume ratio 3:1 mixing, is simultaneously introduced luminescent powder, adds aniline, luminescent powder after magnetic agitation 90min It is 1 with aniline mass ratio:10；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 are vacuum dried for several times afterwards, nano polyaniline/luminescent powder of milling to obtain Compound；1g nano polyaniline/noctilucence 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 tetraethyl orthosilicate（Mass ratio with nano polyaniline/noctilucence flour complexes is 5:3）, adjust Section pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；It is centrifuged and is cleaned with acetone and deionized water successively and obtained Must precipitate；This is deposited at 90 DEG C 3h is dried, to obtain nano polyaniline/noctilucence flour complexes/SiO₂；By nanometer polyphenyl Amine/noctilucence flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1.5h, remove polyaniline, obtain luminescent powder/many Hole SiO₂, i.e. noctilucence compound.Described luminescent powder is less than the long afterglow Sr of 10nm for average grain diameter₄Al₁₄O₂₅Nano-phosphor；

（7）Prepare deodorant：Mix the raw material of following percentage by weight：ZrO₂2%, TiO₂15%, SiO₂20%, V₂O₅5%, K₂O 1%, SnO₂5%, Cr₂O₃2%, Al₂O₃12%, Fe₂O₃15%, MgO 12%, Na₂O10%, MnO₂1%, put into PUHLER It is ground in the big flow circulation horizontal sand mill of company's exploitation, control particle diameter between 10 ~ 300nm, obtain inorganic oxide； Diatomite is dispersed in the aqueous solution of 100 ~ 200ml, adds inorganic oxide, wherein said diatomite and inorganic oxide Weight is than for 1:1,150W ultrasonic 150rpm stirs 2h, allows nano material well in diatom soil pores, multiple suction filtration cleans； It is placed in confined space, carry out vacuumizing → heat pressurized circulation 5 times（Pumpdown time is 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 0.5Mpa, pressurize 30min）, obtain deodorant；

（8）Antibacterial powder, noctilucence compound and deodorant is taken to be scattered in 150ml ultra-pure water, ultrasonic agitation 2h obtains all even steady The weight of fixed dispersion liquid, wherein antibacterial powder, noctilucence compound and deodorant is than for 3:4:1；To have carbon nanotube mesh film Substrate when being placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, make this dispersion liquid equal Even be scattered in this carbon nanotube mesh film, due to 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 hydrophobicity and drives most of moisture away Leave absorption antibacterial powder, noctilucence compound and deodorant in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in close Close in space, carry out vacuumizing → heat pressurized circulation 4 times（Pumpdown time is 30min；It is pressurised into and be passed through HTHP Gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, then will be adsorbed with antibacterial powder, noctilucence multiple The carbon nanotube mesh film of compound and deodorant scrapes off this substrate, obtains antibacterial-deodorant-noctilucent function agent.

Embodiment 2

Step A, prepares low temperature frit：By mass percentage, by 8% potassium nitrate, 8% quartz, 10% potassium feldspar, 6% albite, 11% spodumene, 32% boric acid, 4% brium carbonate, 7% fluorite, 2% kaolin, 4% sodium fluoride and 8% functional agent mix, and pass through Quick quenching after calcining at 1250～1300 DEG C after sieve, ground and mixed, the low temperature having obtained 650～800 DEG C of melt temperature melts Block；

Step B, prepares the deodorant glaze slip of noctilucence：By mass percentage, by 25% low temperature frit, 35% potassium feldspar, 15% quartz, 3% calcite, 5% talcum, 4% calcium phosphate, 3% kaolin, 10% calcined earth are mixed to get mixed-powder, add in mixed-powder Enter functional agent and mix, be finely ground to 300 ~ 350 mesh, be subsequently adding water and obtain glaze slip and modulate glaze slip proportion for 1.6 ~ 1.7g/ cm³, obtain final product noctilucence deodorization ceramic glaze slip；Wherein, the addition of functional agent is the 6% of mixed-powder quality；

Wherein, described functional agent 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 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；

（6）Prepare noctilucence compound：Under nitrogen environment, the protonic acid solution for 0.3mol/L for the concentration and concentration are 0.3mol/L DBSA with volume ratio 3:2 mixing, are simultaneously introduced luminescent powder, add aniline, luminescent powder after magnetic agitation 90min It is 1 with aniline mass ratio: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 be vacuum dried afterwards for several times, mill nano polyaniline/luminescent powder is multiple Compound；5g nano polyaniline/noctilucence 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/noctilucence 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/noctilucence flour complexes/SiO₂；By nano polyaniline/ Noctilucence flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1.5h, remove polyaniline, obtain luminescent powder/porous SiO₂, i.e. noctilucence compound.Described luminescent powder is less than the long afterglow Sr of 10nm for average grain diameter₄Al₁₄O₂₅Nano-phosphor；

（7）Prepare deodorant：Mix the raw material of following percentage by weight：ZrO₂6%, TiO₂8%, SiO₂15%, V₂O₅3%, K₂O 2%, SnO₂3%, Cr₂O₃4%, Al₂O₃15%, Fe₂O₃10%, MgO 20%, Na₂O 6%, MnO₂8%, put into PUHLER company It is ground in the big flow circulation horizontal sand mill of exploitation, control particle diameter between 10 ~ 300nm, obtain inorganic oxide；By silicon Diatomaceous earth is dispersed in the aqueous solution of 100 ~ 200ml, adds the weight of inorganic oxide, wherein said diatomite and inorganic oxide Than for 1:3,150W ultrasonic 150rpm stir 2h, allow nano material well in diatom soil pores, multiple suction filtration cleans；It is placed in In confined space, carry out vacuumizing → heat pressurized circulation 5 times（Pumpdown time is 30min；It is pressurised into and be passed through high temperature height Calm the anger body, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, obtain deodorant；

（8）Antibacterial powder, noctilucence compound and deodorant is taken to be scattered in 150ml ultra-pure water, ultrasonic agitation 2h obtains all even steady The weight of fixed dispersion liquid, wherein antibacterial powder, noctilucence compound and deodorant is than for 4:3:5；To have carbon nanotube mesh film Substrate when being placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, make this dispersion liquid equal Even be scattered in this carbon nanotube mesh film, due to 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 hydrophobicity and drives most of moisture away Leave absorption antibacterial powder, noctilucence compound and deodorant in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in close Close in space, carry out vacuumizing → heat pressurized circulation 4 times（Pumpdown time is 30min；It is pressurised into and be passed through HTHP Gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, then will be adsorbed with antibacterial powder, noctilucence multiple The carbon nanotube mesh film of compound and deodorant scrapes off this substrate, obtains antibacterial-deodorant-noctilucent function agent.

Embodiment 3

Step A, prepares low temperature frit：By mass percentage, by 6% potassium nitrate, 10% quartz, 15% potassium feldspar, 8% albite, 11% spodumene, 31% boric acid, 3% brium carbonate, 5% fluorite, 1% kaolin, 5% sodium fluoride and 5% functional agent mix, and pass through Quick quenching after calcining at 1250～1300 DEG C after sieve, ground and mixed, the low temperature having obtained 650～800 DEG C of melt temperature melts Block；

Step B, prepares the deodorant glaze slip of noctilucence：By mass percentage, by 20% low temperature frit, 40% potassium feldspar, 20% quartz, 1% calcite, 3% talcum, 5% calcium phosphate, 3% kaolin, 8% calcined earth are mixed to get mixed-powder, add in mixed-powder Enter functional agent and mix, be finely ground to 300 ~ 350 mesh, be subsequently adding water and obtain glaze slip and modulate glaze slip proportion for 1.6 ~ 1.7g/ cm³, obtain final product noctilucence deodorization ceramic glaze slip；Wherein, the addition of functional agent is the 10% of mixed-powder quality；

Wherein, described functional agent 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 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；

（6）Prepare noctilucence compound：Under nitrogen environment, the protonic acid solution for 0.3mol/L for the concentration and concentration are 0.3mol/L DBSA with volume ratio 1:1 mixing, is simultaneously introduced luminescent powder, adds aniline, luminescent powder after magnetic agitation 90min It is 1 with aniline mass ratio:5；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 be vacuum dried afterwards for several times, mill nano polyaniline/luminescent powder is multiple Compound；10g nano polyaniline/noctilucence 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/noctilucence flour complexes is 5:1）, 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/noctilucence flour complexes/SiO₂；By nano polyaniline/ Noctilucence flour complexes/SiO₂It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1.5h, remove polyaniline, obtain luminescent powder/porous SiO₂, i.e. noctilucence compound.Described luminescent powder is less than the long afterglow Sr of 10nm for average grain diameter₄Al₁₄O₂₅Nano-phosphor；

（7）Prepare deodorant：Mix the raw material of following percentage by weight：ZrO₂8%, TiO₂10%, SiO₂18%, V₂O₅2%, K₂O 5%, SnO₂1%, Cr₂O₃5%, Al₂O₃10%, Fe₂O₃12%, MgO 16%, Na₂O 3%, MnO₂10%, put into PUHLER It is ground in the big flow circulation horizontal sand mill of company's exploitation, control particle diameter between 10 ~ 300nm, obtain inorganic oxide； Diatomite is dispersed in the aqueous solution of 100 ~ 200ml, adds inorganic oxide, wherein said diatomite and inorganic oxide Weight is than for 1:6,150W ultrasonic 150rpm stir 2h, allow nano material well in diatom soil pores, multiple suction filtration cleans； It is placed in confined space, carry out vacuumizing → heat pressurized circulation 5 times（Pumpdown time is 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 0.5Mpa, pressurize 30min）, obtain deodorant；

（8）Antibacterial powder, noctilucence compound and deodorant is taken to be scattered in 150ml ultra-pure water, ultrasonic agitation 2h obtains all even steady The weight of fixed dispersion liquid, wherein antibacterial powder, noctilucence compound and deodorant is than for 6:4:3；To have carbon nanotube mesh film Substrate when being placed in about 8 DEG C, dispersion liquid is added in the substrate of concave shape, meanwhile, rolls around roller, make this dispersion liquid equal Even be scattered in this carbon nanotube mesh film, due to 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 hydrophobicity and drives most of moisture away Leave absorption antibacterial powder, noctilucence compound and deodorant in multiple net holes of carbon nanotube mesh film；Remove moisture, be placed in close Close in space, carry out vacuumizing → heat pressurized circulation 4 times（Pumpdown time is 30min；It is pressurised into and be passed through HTHP Gas, gas heating-up temperature is 80 ~ 90 DEG C, is forced into 0.5Mpa, pressurize 30min）, then will be adsorbed with antibacterial powder, noctilucence multiple The carbon nanotube mesh film of compound and deodorant scrapes off this substrate, obtains antibacterial-deodorant-noctilucent 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, it the difference is that only：Described antibacterial powder is metal antibacterial agent；Described luminescent powder Compound is less than the long afterglow Sr of 10nm for average grain diameter₄Al₁₄O₂₅Nano-phosphor；Without deodorant.

Comparative example 2

Based on the preparation method of embodiment 4, it the difference is that only：Described antibacterial powder is zinc oxide antiseptic；Described deodorant Agent comprises the following raw materials by weight percent：ZrO₂8%, TiO₂10%, SiO₂18%, V₂O₅2%, K₂O 5%, SnO₂1%, Cr₂O₃5%, Al₂O₃10%, Fe₂O₃12%, MgO 16%, Na₂O 3%, MnO₂10%.

The ceramic glaze that embodiment 1 ~ 6, comparative example 1 ~ 2 are obtained carries out anti-microbial property test, and test result is as follows：

Sterilization rate：Take 10⁵The Escherichia coli 0.1ml of individual/ml, is spread evenly across on ceramic glaze, 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 on ceramic glaze uses 2 imitating paving 1000 times Effect after year, tests its sterilization rate.

Heat stability testing：Ceramic glaze is placed in electric furnace, is 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 material and carries out sterilizing test, to the data recording Carry out 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 it is labeled as ☆；When the uniformity is less than 90%, then it is labeled as.

Deodorizing test：Prepare two 51PVF resin airbags, an air bag is put into one piece of sample print, another tree Fat air bag not setting-out piece.Then it is blown into 500ppmNH3- air gas mixture in two air bags respectively and seals, make after 60min Measure the concentration of NH3 in air bag with gas detecting tube, calculate deodorizing rate.

Radiation performance：Detection indicate that, the ceramic glaze of the present invention all meets GB6566-2001《Radioactive material core Element 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 noctilucence deodorization ceramic glaze, it comprises the following steps：First prepare the deodorant glaze slip of noctilucence, then through applying Glaze, sintering are obtained noctilucence deodorization ceramic glaze；Wherein, the preparation method of the deodorant glaze slip of noctilucence is as follows：By mass percentage, by 25 ~ 35% low temperature frit, 30 ~ 40% potassium feldspars, 10 ~ 20% quartz, 3 ~ 6% calcites, 3 ~ 6% talcums, 2 ~ 5% calcium phosphate, 1 ~ 5% kaolin, 5 ~ 10% calcined earths are mixed to get mixed-powder, add functional agent and mix, wherein institute in mixed-powder The addition stating functional agent is the 3 ~ 10% of mixed-powder quality, is finely ground to 300 ~ 350 mesh, is subsequently adding water and obtains glaze slip and modulate Glaze slip proportion is 1.6 ~ 1.7g/cm³, obtain final product noctilucence deodorization ceramic glaze slip；Described functional agent include noctilucence compound, deodorant and GQDs/Ag₂O/Ag-Zn-Ce/SiO₂/ Graphene antibiosis powder.

2. the preparation method of noctilucence deodorization ceramic glaze according to claim 1 is it is characterised in that the matter of described low temperature frit Amount percentage consists of：6～10% potassium nitrate, 5～10% quartz, 12～15% potassium feldspars, 3～8% albites, 10～12% lithium brightness Stone, 30～35% boric acid, 3～5% brium carbonates, 5～8% fluorites, 1～3% kaolin, 2～5% sodium fluorides and 5 ~ 10% functional agents.

3. the preparation method of noctilucence deodorization ceramic glaze 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, noctilucence compound and deodorant 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, noctilucence compound and deodorant are than for 3 ~ 6:2~4:1~5；To have carbon When the substrate of nanotube reticular membrane is placed in 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 this carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophily, this point 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 and by big portion Divide hydrone to drive away and leave absorption antibacterial powder, noctilucence compound and deodorant in multiple net holes of carbon nanotube mesh film；Go Fall moisture, be placed in confined space, carry out vacuumizing → heat pressurized circulation 3 ~ 5 times, then will be adsorbed with antibacterial powder, noctilucence multiple The carbon nanotube mesh film of compound and deodorant scrapes off this substrate, obtains antibacterial-deodorant-noctilucent function agent.

4. a kind of preparation method of noctilucence deodorization ceramic glaze, it comprises the following steps：First prepare the deodorant glaze slip of noctilucence, then through applying Glaze, sintering are obtained noctilucence deodorization ceramic glaze；Wherein, the preparation method of the deodorant glaze slip of noctilucence is as follows：By mass percentage, by 25 ~ 35% low temperature frit, 30 ~ 40% potassium feldspars, 10 ~ 20% quartz, 3 ~ 6% calcites, 3 ~ 6% talcums, 2 ~ 5% calcium phosphate, 1 ~ 5% kaolin, 5 ~ 10% calcined earths are mixed to get mixed-powder, add functional agent and mix, wherein institute in mixed-powder The addition stating functional agent is the 3 ~ 10% of mixed-powder quality, is finely ground to 300 ~ 350 mesh, is subsequently adding water and obtains glaze slip and modulate Glaze slip proportion is 1.6 ~ 1.7g/cm³, obtain final product noctilucence deodorization ceramic glaze slip；Described functional agent include noctilucence compound, deodorant and GQDs/Ag₂O/ZnO/ Graphene antibiosis powder.

5. the preparation method of noctilucence deodorization ceramic glaze according to claim 4 is it is characterised in that the matter of described low temperature frit Amount percentage consists of：6～10% potassium nitrate, 5～10% quartz, 12～15% potassium feldspars, 3～8% albites, 10～12% lithium brightness Stone, 30～35% boric acid, 3～5% brium carbonates, 5～8% fluorites, 1～3% kaolin, 2～5% sodium fluorides and 5 ~ 10% functional agents.

6. the preparation method of noctilucence deodorization ceramic glaze 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, noctilucence compound and deodorant 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, noctilucence compound and deodorant are than for 3 ~ 6:2~4:1~5；To have carbon When the substrate of nanotube reticular membrane is placed in 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 this carbon nanotube mesh film, due to when CNT is near 8 DEG C, there is hydrophily, this point 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 and by big portion Divide hydrone to drive away and leave absorption antibacterial powder, noctilucence compound and deodorant in multiple net holes of carbon nanotube mesh film；Go Fall moisture, be placed in confined space, carry out vacuumizing → heat pressurized circulation 3 ~ 5 times, then will be adsorbed with antibacterial powder, noctilucence multiple The carbon nanotube mesh film of compound and deodorant scrapes off this substrate, obtains antibacterial-deodorant-noctilucent function agent.

7. the preparation method of the noctilucence deodorization ceramic glaze 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 noctilucence deodorization ceramic glaze according to claim 3 or 6 is it is characterised in that described noctilucence is combined The preparation method of thing 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 luminescent powder, after magnetic agitation 60 ~ 120min Add aniline, luminescent powder 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/noctilucence flour complexes；1 ~ 10g nano polyaniline/noctilucence flour complexes ultrasonic agitation is scattered in water In solution；Add volume ratio 4 afterwards:1 water and ammoniacal liquor, are stirring evenly and then adding into tetraethyl orthosilicate, and adjusting pH value is 9 ~ 10, instead Answer temperature to be 20 ~ 25 DEG C, react 60 ~ 90min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；Should Precipitation drying, to obtain nano polyaniline/noctilucence flour complexes/SiO₂；By nano polyaniline/noctilucence flour complexes/SiO₂It is placed in Carry out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h under argon gas atmosphere, remove polyaniline, obtain luminescent powder/porous SiO₂.

9. the preparation method of the noctilucence deodorization ceramic glaze according to claim 3 or 6 is it is characterised in that described deodorant system Preparation Method is as follows：Mix the raw material of following percentage by weight：ZrO₂2 ~ 8%, TiO₂5 ~ 15%, SiO₂10 ~ 20%, V₂O₅1 ~ 5%, K₂O 1 ~ 5%, SnO₂1 ~ 5%, Cr₂O₃1 ~ 5%, Al₂O₃10 ~ 15%, Fe₂O₃10 ~ 15%, MgO 10 ~ 20%, Na₂O 1 ~ 10%, MnO₂1 ~ 10%, be ground in the big flow circulation horizontal sand mill putting into the exploitation of PUHLER company, control particle diameter 10 ~ Between 300nm, obtain inorganic oxide；Diatomite is dispersed in the aqueous solution of 100 ~ 200ml, adds inorganic oxide, wherein The weight of described diatomite and inorganic oxide is than for 1:Ultrasonic 100 ~ the 300rpm of 1 ~ 6,100 ~ 200W stirs 1 ~ 2h, allows a nanometer material Well in diatom soil pores, multiple suction filtration cleans material；Be placed in confined space, carry out vacuumizing → heat pressurized circulation 3 ~ 8 times, obtain deodorant.

10. a kind of noctilucence deodorization ceramic glaze is it is characterised in that it presses described preparation method system as arbitrary in claim 1 to 8 ?.