CN112758981A - Nano material for self-cleaning ceramic tile and preparation method and application thereof - Google Patents
Nano material for self-cleaning ceramic tile and preparation method and application thereof Download PDFInfo
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- CN112758981A CN112758981A CN202011537968.XA CN202011537968A CN112758981A CN 112758981 A CN112758981 A CN 112758981A CN 202011537968 A CN202011537968 A CN 202011537968A CN 112758981 A CN112758981 A CN 112758981A
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- 239000000919 ceramic Substances 0.000 title claims abstract description 90
- 238000004140 cleaning Methods 0.000 title claims abstract description 62
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title abstract description 6
- 239000002135 nanosheet Substances 0.000 claims abstract description 17
- 239000002071 nanotube Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 4
- 229910052802 copper Inorganic materials 0.000 claims abstract description 3
- 229910052742 iron Inorganic materials 0.000 claims abstract description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 3
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 3
- 239000002243 precursor Substances 0.000 claims description 35
- 239000007789 gas Substances 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000001301 oxygen Substances 0.000 claims description 16
- 229910052760 oxygen Inorganic materials 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 15
- 239000010936 titanium Substances 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 230000032683 aging Effects 0.000 claims description 9
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 7
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 7
- 229910052719 titanium Inorganic materials 0.000 claims description 7
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 claims description 6
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 238000000354 decomposition reaction Methods 0.000 abstract description 10
- 230000003115 biocidal effect Effects 0.000 abstract description 2
- 239000002131 composite material Substances 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract description 2
- 239000007921 spray Substances 0.000 abstract 1
- 230000000844 anti-bacterial effect Effects 0.000 description 18
- 230000000694 effects Effects 0.000 description 10
- 238000011049 filling Methods 0.000 description 9
- 239000010410 layer Substances 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000005034 decoration Methods 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 4
- 229960000907 methylthioninium chloride Drugs 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011701 zinc Substances 0.000 description 4
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 3
- 238000004375 physisorption Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000001112 coagulating effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- 229920001817 Agar Polymers 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000008272 agar Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229960000892 attapulgite Drugs 0.000 description 1
- 230000001580 bacterial effect Effects 0.000 description 1
- 239000000440 bentonite Substances 0.000 description 1
- 229910000278 bentonite Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 1
- 230000003670 easy-to-clean Effects 0.000 description 1
- 239000003480 eluent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960002413 ferric citrate Drugs 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- NPFOYSMITVOQOS-UHFFFAOYSA-K iron(III) citrate Chemical compound [Fe+3].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NPFOYSMITVOQOS-UHFFFAOYSA-K 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 229910052863 mullite Inorganic materials 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052625 palygorskite Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000003870 refractory metal Substances 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000008223 sterile water Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/08—Drying; Calcining ; After treatment of titanium oxide
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
-
- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
- C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
- C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
- C01P2004/13—Nanotubes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
Abstract
The invention belongs to the technical field of functional nano materials, and particularly relates to a nano material for a self-cleaning ceramic tile and a preparation method thereofAnd applications. The nano material for the self-cleaning ceramic tile has a structural formula of MxTiyOzWherein M is one or more of Zn, Cu, Fe, Ag, Ce, La, Co or Ni; the nano material is a nano sheet or a nano tube. The composite oxide nano material with the mesoporous structure is synthesized by a flame spray decomposition method, has the advantages of large specific surface area, rich pore structure, more active sites and the like, and is added on the surface of a ceramic tile glaze layer, so that the ceramic tile has the functions of self-cleaning and antibiosis.
Description
Technical Field
The invention belongs to the technical field of functional nano materials, and particularly relates to a nano material for a self-cleaning ceramic tile, and a preparation method and application thereof.
Background
Floor tiles and wall tiles for architectural decoration have been widely used for a long time, and compared with other ground decoration materials, the floor tiles have obvious advantages in the aspects of decoration effect, sanitation and the like, and the decoration patterns, textures and colors of the floor tiles are more vivid and lively, so that the pursuit of consumers for the decoration effect is greatly met. The ceramic tile is made up by using refractory metal oxide and semimetal oxide through the processes of grinding, mixing, pressing, glazing and sintering, and is an acid-alkali-resistant building or decorative material made of porcelain or stone, etc. its raw material is made up by mixing clay and quartz sand, etc.
The ceramic tile is used in a plurality of places, and when the ceramic tile is used on a kitchen or a building outer wall, due to frequent contact with oil stains or other substances, the oil stains and the like are easily adhered to the surface of the ceramic tile, the ceramic tile is not easy to clean, the attractiveness of the ceramic tile is reduced, bacteria are easily bred, and the use safety is reduced.
Chinese patent CN 109437853A discloses a ceramic tile with self-cleaning function, which is prepared from the following raw materials by weight: 200 parts of 180-part kaolin, 45-50 parts of quartz stone, 35-40 parts of attapulgite, 8-10 parts of bentonite, 30-40 parts of mullite fiber and 10-15 parts of nano zinc oxide-nano titanium dioxide compound. The patent adds more nano zinc oxide and nano titanium oxide, obviously raises the production cost of the ceramic tile.
Chinese patent CN 208518244U discloses a building outer wall ceramic tile with a surface self-cleaning function, which comprises a glaze layer, a steel wire reinforced layer and a paving surface layer; the steel wire reinforced layer is fixedly adhered between the glaze layer and the paving surface layer; the interior of the glaze layer penetrates through the left side and the right side of the glaze layer and is arranged in a plurality of first filling holes with hexagonal structures; the outer surface array of the glaze layer is provided with a plurality of second filling holes matched with the first filling holes, the second filling holes are of hexagonal hole structures with the same cross section size as the first filling holes, and the second filling holes are communicated with the first filling holes; transparent nanometer super-hydrophobic particles are filled in the first filling hole and the second filling hole, and the outer surface of the glaze layer is coated with a layer of super-hydrophobic particles.
At present, a nano material for self-cleaning ceramic tiles, which has a self-cleaning function and a good antibacterial effect, is needed to be provided.
Disclosure of Invention
The invention aims to provide a nano material for a self-cleaning ceramic tile, which has a self-cleaning function and a good antibacterial effect; the invention also provides a preparation method and application of the nano material for the self-cleaning ceramic tile.
The invention relates to a nano material for self-cleaning ceramic tiles, which has a structural formula of MxTiyOzWherein M is a doping metal, x is the mole fraction of M in the nanomaterial, y is the mole fraction of Ti, and z is the mole fraction of O; m is one or more of Zn, Cu, Fe, Ag, Ce, La, Co or Ni; the nano material is a nano sheet or a nano tube.
X is 0.04-0.5, y is 1-x, and z is 1-3.
The length of the nano sheet is 100-900nm, and the diameter of the nano tube is 100-900 nm.
The preparation method of the nano material for the self-cleaning ceramic tile comprises the following steps:
(1) dissolving a template agent in a solvent, uniformly stirring, adding a precursor of titanium and a precursor of M, stirring and aging to obtain a precursor solution;
(2) dispersing the precursor solution by high-pressure gas, introducing the dispersed precursor solution into methane-oxygen flame for reaction, condensing and crystallizing to prepare the nano material for the self-cleaning ceramic tile.
The template agent in the step (1) is one or more of cetyl trimethyl ammonium bromide, n-butanol, n-pentanol, n-hexanol or n-heptanol.
The solvent in the step (1) is one or more of water, ethanol or propanol.
The ratio of the template agent to the solvent in the step (1) is 100-800: 1, wherein the template agent is calculated by mmol and the solvent is calculated by L.
The precursor of titanium in the step (1) is tetrabutyl titanate or titanium tetrachloride, and the mass ratio of the precursor of titanium to the solvent is 5-80: 100.
the precursor of M in the step (1) is one or more of nitrate, acetate or citrate of M.
The stirring and aging time in the step (1) is 10-240 min.
The high-pressure gas in the step (2) is oxygen, and the pressure of the high-pressure gas is 0.2-3 MPa.
The speed of introducing the precursor solution dispersed by high-pressure gas into the methane-oxygen flame in the step (2) is 2-20 mL/min.
Collecting the nano materials for the self-cleaning ceramic tiles in the step (2) by using a collector with a filter screen.
The application of the nano material for the self-cleaning ceramic tile is that the nano material for the self-cleaning ceramic tile is mixed into ceramic glaze, and a ceramic blank is fired after glazing to obtain the self-cleaning ceramic tile.
The content of the nano material for the self-cleaning ceramic tile in the ceramic glaze is 0.05-10 wt.%.
According to the invention, oil-water amphiphilic molecules are used as a template agent, micelles can be formed when the template agent is added into a solvent, the added titanium precursor is hydrolyzed in a solution to form crystal nuclei, and the crystal nuclei are self-assembled into a nanotube or nanosheet precursor under the guidance of the template agent. When the template agent is cetyl trimethyl ammonium bromide and tetrabutyl titanate is used as a precursor, the nanotube is prepared; when n-butyl alcohol, n-amyl alcohol, n-hexyl alcohol or n-heptyl alcohol is used as a template agent, and titanium tetrachloride or tetrabutyl titanate is used as a precursor, the nano sheet is prepared. In the flame spray pyrolysis process, the template agent in the nanotube or nanosheet precursor is oxidized and eliminated to form the nanotube or nanosheet-shaped nanomaterial. The obtained nano material has photocatalytic activity, can catalyze oxygen and water in the air to generate free radicals in the spectral range from ultraviolet light to visible light, and the free radicals can remove organic pollutants and microorganisms attached to the surface of the ceramic tile, so that the purposes of self-cleaning and antibiosis are achievedIn (1). The prepared nano material has rich pore structure and large specific surface area (both at 130 m)2More/g) and thus has more active sites, while the large specific surface area is favorable for adsorbing pollutants on the surface for oxidative degradation.
The invention relates to a method for preparing nano-sheets or nano-tubes by using a flame jet decomposition method.
The invention has the following beneficial effects:
the composite oxide nano material with a mesoporous structure is obtained by adding a template agent into a precursor, aging, dispersing by high-pressure gas, introducing into methane-oxygen flame, and performing combustion reaction.
Detailed Description
The present invention is further described below with reference to examples.
Example 1
(1) Dissolving 0.5g of hexadecyl trimethyl ammonium bromide in 50mL of water, uniformly stirring, adding 25g of tetrabutyl titanate and 5g of zinc nitrate, stirring and aging for 10min to obtain a precursor solution;
(2) dispersing the precursor solution by high-pressure gas, introducing the dispersed precursor solution into methane-oxygen flame for reaction, introducing the high-pressure gas at a rate of 2mL/min, introducing the high-pressure gas as oxygen and under a pressure of 0.2MPa, and coagulating and crystallizing to obtain the nano tube (Ti) with the average diameter of 16nm for the self-cleaning ceramic tile0.826Zn0.174O1.826)。
And doping the nanotube for the self-cleaning ceramic tile into a ceramic glaze, and firing the ceramic blank after glazing to obtain the self-cleaning ceramic tile, wherein the content of the nanotube for the self-cleaning ceramic tile in the ceramic glaze is 1 wt.%.
The self-cleaning performance of the ceramic tile is detected by a national standard JC/T2210-2014 self-cleaning performance test method of the building ceramic, 6 self-cleaning ceramic tiles of 6 multiplied by 6cm are taken, and 1 self-cleaning ceramic tile without adding the functional nano material is taken as a comparison sample. Repeatedly scrubbing the tested sample with ethanol and acetone, and then irradiating with an ultraviolet lamp for 24h to remove residual organic matters. Putting the ceramic chip sample into an experiment groove, sealing and fixing the ceramic chip sample by using silicone ester, then adding 0.02mmol/L methylene blue solution into the experiment groove, enabling the ceramic chip to fully adsorb the methylene blue under the condition of keeping out of the sun, then adding 0.01mmol/L methylene blue solution, irradiating for 20min under 664nm ultraviolet light, measuring the concentration of the methylene blue solution, then calculating the decomposition activity index according to the measured data, and measuring the water contact angle of the ceramic chip by using a water contact angle tester.
The antibacterial detection of the ceramic tile is carried out according to the national standard JC/T897-2014 antibacterial ceramic product antibacterial performance, and the detection is carried out by utilizing staphylococcus aureus and escherichia coli, wherein 12 ceramic tiles with 5 multiplied by 5cm and added with antibacterial nano materials and 2 ceramic tiles without added with the antibacterial nano materials are firstly sterilized by a steam boiler at high temperature, then 70% alcohol is used for further sterilization, the glaze faces are upward, the blank is placed downwards and is soaked in sterile water for 24 hours, the blank is ensured to fully absorb water, then the strains are uniformly inoculated on the surfaces of the ceramic tiles by a film method, the strains are cultured for 24 hours in a constant temperature incubator at 37 ℃, bacterial colonies on the ceramic tiles in an experimental group and a control group are eluted by lotion, then the strains in the eluent are inoculated in plate counting agar, the strains are cultured for 24 hours in the constant temperature incubator at 37 ℃, and then viable bacteria are counted. The antibacterial rate calculation method comprises the following steps:
R＝(B-C)/B×100％
r is antibacterial rate, B is the number of average colony count after blank control sample is cultured for 24h, and the unit is colony count; c is the value of the average colony count of the antibacterial ceramic sample after 24h of culture, and the unit is the colony count.
The detection shows that the prepared self-cleaning ceramic tile has the decomposition activity index of 115%, the water contact angle of 7.5% and the antibacterial rate of 98.3%.
The specific surface area of the nanotube was 162m as measured by nitrogen physisorption2/g。
Example 2
(1) Dissolving 1g of n-butanol in 100mL of ethanol, stirring uniformly, adding 20g of titanium tetrachloride and 2g of copper acetate, stirring and aging for 240min to obtain a precursor solution;
(2) dispersing the precursor solution by high-pressure gas, introducing the dispersed precursor solution into methane-oxygen flame for reaction, wherein the introduction rate is 20mL/min, the high-pressure gas is oxygen, the pressure of the high-pressure gas is 1MPa, and solidifying and crystallizing to obtain nano sheets (Ti) with the average length of 73nm for the self-cleaning ceramic tile0.725Cu0.245O1.725)。
The nanosheets for the self-cleaning ceramic tile are doped into a ceramic glaze, and the ceramic blank is fired after glazing to obtain the self-cleaning ceramic tile, wherein the content of the nanosheets for the self-cleaning ceramic tile in the ceramic glaze is 0.5 wt.%.
The self-cleaning and antibacterial properties of the tiles were tested as in example 1.
The detection shows that the prepared self-cleaning ceramic tile has the decomposition activity index of 113%, the water contact angle of 7.4% and the antibacterial rate of 97.8%.
The specific surface area of the nanosheet is 147m measured by nitrogen physical adsorption2/g。
Example 3
(1) Dissolving 1g of n-amyl alcohol in 50mL of propanol, uniformly stirring, adding 25g of tetrabutyl titanate and 0.8g of ferric citrate, stirring and aging for 160min to obtain a precursor solution;
(2) dispersing the precursor solution by high-pressure gas, introducing the dispersed precursor solution into methane-oxygen flame for reaction, wherein the introduction rate is 15mL/min, the high-pressure gas is oxygen, the pressure of the high-pressure gas is 3MPa, and solidifying and crystallizing to obtain nano sheets (Ti) with the average length of 86nm for the self-cleaning ceramic tiles0.96Fe0.04O1.94)。
The nanosheets for the self-cleaning ceramic tile are doped into a ceramic glaze, and the ceramic blank is fired after glazing to obtain the self-cleaning ceramic tile, wherein the content of the nanosheets for the self-cleaning ceramic tile in the ceramic glaze is 3 wt.%.
The self-cleaning and antibacterial properties of the tiles were tested as in example 1.
Through detection, the prepared self-cleaning ceramic tile has the decomposition activity index of 117%, the water contact angle of 6.3% and the antibacterial rate of 98.9%.
The specific surface area of the nanosheet was 174m as measured by nitrogen physisorption2/g。
Comparative example 1
The ceramic tile without the nano material has the decomposition activity index of 32 percent, the water contact angle of 19.5 degrees and the antibacterial rate of 23.4 percent.
Comparative example 2
(1) Adding 25g of tetrabutyl titanate and 5g of zinc nitrate into 50mL of water, stirring and aging for 10min to obtain a precursor solution;
(2) dispersing the precursor solution with high-pressure gas, introducing into methane-oxygen flame for reaction at a flow rate of 2mL/min, introducing oxygen as high-pressure gas under a pressure of 0.2MPa, coagulating, and crystallizing to obtain nanoparticles (Ti) with a particle size of 167nm0.826Zn0.174O1.826)。
And (3) doping the nano particles into the ceramic glaze, and firing the ceramic blank after glazing to obtain the ceramic tile, wherein the content of the nano particles in the ceramic glaze is 1 wt.%.
The self-cleaning and antibacterial properties of the tiles were tested as in example 1.
The detection shows that the prepared ceramic tile has the decomposition activity index of 103%, the water contact angle of 9.9% and the antibacterial rate of 83.5%.
The specific surface area of the nanoparticles was 53m as measured by nitrogen physisorption2/g。
The higher the decomposition activity index is, the better the self-cleaning capability is, the smaller the water contact angle is, the better the hydrophilicity is, and the more beneficial to the self-cleaning of the ceramic tile is. The decomposition activity index of the example is higher than that of the comparative example, and the contact angle of water of the example is lower than that of the comparative example, which shows that the self-cleaning performance of the ceramic tile prepared by the example is better than that of the comparative example.
Claims (10)
1. A nano material for self-cleaning ceramic tile is characterized by having a structural formula of MxTiyOzWherein M is a doping metal, x is the mole fraction of M in the nanomaterial, y is the mole fraction of Ti, and z is the mole fraction of O;m is one or more of Zn, Cu, Fe, Ag, Ce, La, Co or Ni; the nano material is a nano sheet or a nano tube.
2. Nanomaterial for self-cleaning ceramic tiles according to claim 1, characterised in that x is between 0.04 and 0.5, y is between 1 and x and z is between 1 and 3.
3. The nanomaterial for self-cleaning ceramic tiles as claimed in claim 1, wherein the length of the nano sheets is 100-900nm and the diameter of the nano tubes is 100-900 nm.
4. A method for preparing nano-materials for self-cleaning tiles as claimed in any one of claims 1 to 3, characterized by comprising the following steps:
(1) dissolving a template agent in a solvent, uniformly stirring, adding a precursor of titanium and a precursor of M, stirring and aging to obtain a precursor solution;
(2) dispersing the precursor solution by high-pressure gas, introducing the dispersed precursor solution into methane-oxygen flame for reaction, condensing and crystallizing to prepare the nano material for the self-cleaning ceramic tile.
5. The method for preparing nano-materials for self-cleaning ceramic tiles as claimed in claim 4, wherein the template agent in step (1) is one or more of cetyl trimethyl ammonium bromide, n-butanol, n-pentanol, n-hexanol or n-heptanol, the solvent is one or more of water, ethanol or propanol, and the ratio of the template agent to the solvent is 100-: 1, wherein the template agent is calculated by mmol and the solvent is calculated by L.
6. The method for preparing nano-materials for self-cleaning ceramic tiles according to claim 4, wherein the precursor of titanium in step (1) is tetrabutyl titanate or titanium tetrachloride, and the mass ratio of the precursor of titanium to the solvent is 5-80: 100, the precursor of M is one or more of nitrate, acetate or citrate of M.
7. The method for preparing nano-materials for self-cleaning ceramic tiles according to claim 4, wherein the stirring aging time in the step (1) is 10-240 min.
8. The method for preparing nano-materials for self-cleaning ceramic tiles as claimed in claim 4, wherein the high pressure gas in step (2) is oxygen, the pressure of the high pressure gas is 0.2-3MPa, the rate of introducing the precursor solution into the methane-oxygen flame after the high pressure gas is dispersed is 2-20mL/min, and the nano-materials for self-cleaning ceramic tiles are collected by a collector with a filter screen.
9. Use of the nanomaterial for self-cleaning tiles according to any one of claims 1 to 3, wherein the nanomaterial for self-cleaning tiles is incorporated into a ceramic glaze, and a ceramic body is fired after glazing to obtain the self-cleaning tile.
10. Use of a nanomaterial for self-cleaning tiles according to claim 9, characterised in that the nanomaterial for self-cleaning tiles is present in the ceramic glaze in an amount of 0.05-10 wt.%.
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