CN115212865A - Titanium dioxide-based photocatalyst, preparation method thereof and application thereof in fabric photocatalytic deodorization - Google Patents
Titanium dioxide-based photocatalyst, preparation method thereof and application thereof in fabric photocatalytic deodorization Download PDFInfo
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- CN115212865A CN115212865A CN202210933231.2A CN202210933231A CN115212865A CN 115212865 A CN115212865 A CN 115212865A CN 202210933231 A CN202210933231 A CN 202210933231A CN 115212865 A CN115212865 A CN 115212865A
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 134
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 57
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 57
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 35
- 238000004332 deodorization Methods 0.000 title claims abstract description 33
- 239000004744 fabric Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 96
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 31
- 239000002904 solvent Substances 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 12
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000004519 manufacturing process Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011701 zinc Substances 0.000 claims description 7
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 5
- 229910044991 metal oxide Inorganic materials 0.000 claims description 5
- 150000004706 metal oxides Chemical class 0.000 claims description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 4
- 230000001877 deodorizing effect Effects 0.000 claims description 4
- 229910021472 group 8 element Inorganic materials 0.000 claims description 3
- 125000006527 (C1-C5) alkyl group Chemical group 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 30
- 230000007547 defect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 109
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 32
- 239000012298 atmosphere Substances 0.000 description 30
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 26
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 25
- 239000004246 zinc acetate Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 229910021529 ammonia Inorganic materials 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 238000002156 mixing Methods 0.000 description 13
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 10
- -1 methyl titanate Chemical compound 0.000 description 10
- 238000001354 calcination Methods 0.000 description 8
- 239000002781 deodorant agent Substances 0.000 description 7
- 239000003431 cross linking reagent Substances 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 125000000217 alkyl group Chemical group 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 150000003751 zinc Chemical class 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 4
- 238000010304 firing Methods 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001768 carboxy methyl cellulose Substances 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 3
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 3
- 239000004753 textile Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000013538 functional additive Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920000515 polycarbonate Polymers 0.000 description 2
- 239000004417 polycarbonate Substances 0.000 description 2
- 229920002635 polyurethane Polymers 0.000 description 2
- 239000004814 polyurethane Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002562 thickening agent Substances 0.000 description 2
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 description 1
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 description 1
- QUVMSYUGOKEMPX-UHFFFAOYSA-N 2-methylpropan-1-olate;titanium(4+) Chemical compound [Ti+4].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-].CC(C)C[O-] QUVMSYUGOKEMPX-UHFFFAOYSA-N 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000006255 coating slurry Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 229910001849 group 12 element Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- ONJQDTZCDSESIW-UHFFFAOYSA-N polidocanol Chemical compound CCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ONJQDTZCDSESIW-UHFFFAOYSA-N 0.000 description 1
- 229920000166 polytrimethylene carbonate Polymers 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- JMXKSZRRTHPKDL-UHFFFAOYSA-N titanium ethoxide Chemical compound [Ti+4].CC[O-].CC[O-].CC[O-].CC[O-] JMXKSZRRTHPKDL-UHFFFAOYSA-N 0.000 description 1
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical group 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002759 woven fabric Substances 0.000 description 1
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J23/75—Cobalt
-
- 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
- B01J23/755—Nickel
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
- D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
- D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
- D06M11/46—Oxides or hydroxides of elements of Groups 4 or 14 of the Periodic Table; Titanates; Zirconates; Stannates; Plumbates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/01—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with natural macromolecular compounds or derivatives thereof
- D06M15/03—Polysaccharides or derivatives thereof
- D06M15/05—Cellulose or derivatives thereof
- D06M15/09—Cellulose ethers
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention relates to a titanium dioxide base photocatalyst, a preparation method thereof and application in fabric photocatalytic deodorization, which mainly solves the defect that the fabric photocatalytic deodorization effect is poor after being finished by the titanium dioxide base photocatalyst in the prior art, and the technical scheme of the invention is as follows: a titanium dioxide-based photocatalyst comprising titanium dioxide and a doped metal element comprising at least one selected from the group consisting of elements of groups IIB and VIII. By adopting the technical scheme, the photocatalytic deodorization effect of the fabric is obviously improved.
Description
Technical Field
The invention relates to a titanium dioxide-based photocatalyst, a preparation method thereof and application thereof in fabric photocatalytic deodorization.
Background
Solar energy is continuously sprayed to the earth, and the solar energy received by the earth every year is about 3 multiplied by 10 24 J, research and utilization of solar energy can make important contribution to the social and economic development of human beings, and hopefully become the strategy of breaking ice for solving the problem of world environmental pollution. In the 30's of the 20 th century, researchers found that titanium dioxide, under conditions of oxygen and ultraviolet light irradiation, could decompose dyes and degrade fibers. By the 80 s in the 20 th century, people research and discover that the photocatalyst can catalyze and degrade organic matters in sewage.
By the late 20 th century, people pay more and more attention to the reaction mechanism of the photocatalyst, and some metal oxides also become research hotspots. TiO 2 2 It is a transition metal semiconductor photocatalyst, and has high biocompatibility and high chemical stability, so that it may be used in photocatalytic deodorizing treatment of fabric. But not TiO doped with other elements 2 The photocatalytic deodorization effect needs to be enhanced.
Disclosure of Invention
The invention provides a novel titanium dioxide-based photocatalyst, which aims to solve the technical problem that the photocatalytic deodorization effect of fabrics finished by the titanium dioxide-based photocatalyst is poor in the prior art, and the photocatalyst has the characteristic of good photocatalytic deodorization effect of the fabrics after the fabric deodorization is finished.
In order to solve the technical problem, the technical scheme is as follows:
a titanium dioxide-based photocatalyst comprising titanium dioxide and a doped metal element comprising at least one element selected from the group consisting of group IIB elements and group VIII elements.
The invention adopts the metal element doped titanium dioxide, and obviously improves the photocatalytic deodorization effect of the fabric after deodorization finishing.
In the above technical solution, preferably, the IIB element is selected from zinc.
In the above technical solution, preferably, the group VIII element is selected from iron, cobalt or nickel.
In the above-described aspect, the content of the doping metal element in the titania-based photocatalyst is preferably more than 0% and 10% or less in terms of the doping metal oxide by weight. For example, but not limited to, the doped metal element content in the titania-based photocatalyst is 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 8.5%, 9%, 9.5%, etc. in terms of doped metal oxide. In comparison, when the titania-based photocatalyst of examples and comparative examples is doped with a metal element, the content of the doped metal element in the titania-based photocatalyst is generally 3% in terms of the doped metal oxide.
In the technical scheme, when the doped metal elements simultaneously comprise zinc and iron, the zinc and the iron have mutual enhancement effect on the aspect of improving the photocatalytic deodorization effect of the fabric. At this time, the ratio between zinc and iron is not particularly limited, for example, but not limited to, znO and Fe 2 O 3 0.1-10 as ZnO and Fe 2 O 3 More specific non-limiting examples of weight ratios therebetween are 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.75, 0.8, 0.9, 1,2, 3, 4, 5, 6, 7, 8, 9, etc., and more preferably the weight ratio between ZnO and Fe2O3 is 1 to 6.
The second technical problem to be solved by the invention is to provide a preparation method of the photocatalyst, which comprises the following technical scheme:
the method for producing a titanium dioxide-based photocatalyst described in any one of the above-mentioned technical problems comprises:
(1) Obtaining a titanate solution I;
(2) Obtaining a solution II doped with metal element ions, wherein the solvent adopted by the solution II comprises water and acetic acid;
(3) Adding the solution II into the solution I under stirring to obtain sol, and continuing stirring until the sol is converted into gel;
(4) And roasting the gel to obtain the titanium dioxide-based photocatalyst.
In the above technical solution, preferably, the titanate in step (1) conforms to the following formula 1:
wherein R is 1 ～R 4 Independently is C1-C5 alkyl. Such as but not limited to R 1 ～R 4 Independently C1 alkyl, C2 alkyl, C3 alkyl, C4 alkyl, C5 alkyl. By way of non-limiting examples of specific titanates, the titanate can be (tetra) methyl titanate, (tetra) ethyl titanate, (tetra) n-propyl titanate, (tetra) isopropyl titanate, (tetra) n-butyl titanate, (tetra) isobutyl titanate, (tetra) t-butyl titanate, (tetra) n-pentyl titanate, (tetra) isoamyl titanate, and the like or mixtures thereof. In the examples and comparative examples, only, the titanate ester is generally n-butyl titanate.
In the above technical solution, the solvent used in the solution I in the step (1) is not particularly limited as long as the titanate can be dissolved and the solvent in the step (2) can be mutually soluble. For example, the solvent used in the solution I in the step (1) is a lower alcohol, preferably, the lower alcohol is a C1-C3 alcohol. By way of non-limiting example, the lower alcohol may be a monohydric alcohol, a dihydric alcohol, or a trihydric alcohol. Examples of such lower alcohols include, but are not limited to, methanol, ethanol, ethylene glycol, n-propanol, isopropanol, 1,2-propanediol, 1,3-propanediol, and the like. However, from the viewpoint of facilitating mass transfer, monohydric alcohols may be generally selected because monohydric alcohols have lower viscosities than dihydric and trihydric alcohols. In the examples and comparative examples, ethanol is generally used as the lower alcohol.
In the above technical solution, preferably, in step (1), the weight concentration of the titanium dioxide in the solution I is 5-20% based on the titanium dioxide, for example, but not limited to, the weight concentration of the titanium dioxide in the solution I is 6.0%, 7.0%, 8.0%, 9.0%, 10%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, and the like. By way of example only, the titania weight concentration in solution I in the examples and comparative examples was generally 12.0%.
In the above technical solution, preferably, the weight ratio of water to acetic acid in the solvent in the step (2) is 0.5 to 1.5. For example, but not limited to, the ratio is 0.55, 0.6, 0.65, 0.7, 0.75, 0.8, 0.85, 0.9, 0.95, 1.0, 1.05, 1.1, 1.15, 1.2, 1.25, 1.3, 1.35, 1.4, 1.45, and the like. The weight ratio of water to acetic acid in the mixed solvent described in examples and comparative examples was generally 1.0, only by the same ratio.
In the above technical solution, preferably, the doped metal element ions in step (2) are provided by a salt of the doped metal, and preferably, the salt of the doped metal is acetate, nitrate or chloride.
In the above technical solution, preferably, when the doped metal element in step (2) includes iron, the iron ion is preferably a ferric iron ion, and further preferably, the ferric iron ion is provided by a ferric iron salt, and preferably, the ferric iron salt is acetate, nitrate or chloride.
In the above technical solution, preferably, when the doping metal element in step (2) includes zinc, the zinc ion is preferably a divalent zinc ion, more preferably, the divalent zinc ion is provided by a divalent zinc salt, and even more preferably, the divalent zinc salt is acetate, nitrate or chloride.
In the above technical scheme, the manner of obtaining the solution II is not particularly limited, and those skilled in the art can reasonably select the solution II all of which can achieve comparable technical effects without creative efforts. By way of example only, the manner of obtaining solution II may be, for example and without limitation: dissolving the metal-doped salt in water, and then adding acetic acid; or dissolving the salt of the doping metal in the solvent; when the doped metal comprises both iron and zinc, the ferric and ferrous salts may be dissolved in any order (e.g. sequentially or simultaneously) in water, followed by the addition of acetic acid; or dissolving the trivalent iron salt and the divalent zinc salt in the solvent in any order (e.g., sequentially or simultaneously); or dissolving ferric salt and divalent zinc salt in water respectively, adding acetic acid respectively, and mixing; or dissolving trivalent ferric salt and divalent zinc salt in the solvent respectively, and then mixing; and so on. We have not found how these ways are significantly different to achieve the technical effect of the present invention.
In the above technical solution, the weight ratio of the solution I to the solution II in the step (3) is not particularly limited, but it is recommended that the weight ratio of the solution I to the solution II is 2 to 20. For example, but not limited to, the weight ratio of the solution I to the solution II is 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, etc., and it is further recommended that the ratio is 5 to 10. The weight ratio of the solution I to the solution II in the step (3) in the examples and comparative examples was 8.1, only by the same ratio.
In the above technical scheme, the temperature required for obtaining the sol and converting the sol into gel in the step (3) is not particularly limited, and particularly has little influence on obtaining the sol, and a person skilled in the art can reasonably select the sol which can achieve the comparable technical effect of the invention. However, the longer the time required for the transition from sol to gel, the higher the temperature, the shorter the gelation time. It is preferable that the temperature of step (3) is 10 to 50 deg.C, for example, but not limited to, the temperature controlled in step (3) is 15 deg.C, 20 deg.C, 25 deg.C, 30 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, etc. The temperature employed in step (3) in the examples and comparative examples is generally 35 ℃ by comparison only.
In the technical scheme, the gel in the step (4) can be subjected to an unnecessary drying stage before roasting, and the dried gel can reduce the release amount of gas in the roasting process due to the removal of a large amount of solvent, so that the roasting process in mass production is easier to control. But the drying process does not bring obvious influence on the deodorization effect of the invention.
In the above technical scheme, the drying temperature in the step (4) is not particularly limited, and the drying temperature may be, for example only, 50 to 90 ℃, such as, but not limited to, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃ and the like. Just by comparison, the temperature for drying in step (4) in examples and comparative examples was generally 70 ℃.
In the above technical solution, if the step (4) is dried, the drying time is not particularly limited, and the drying time may be, for example only, 5 to 48 hours, such as, but not limited to, 5 hours, 10 hours, 15 hours, 20 hours, 25 hours, 30 hours, 35 hours, 40 hours, 45 hours, and the like. In comparison only, the drying time of step (4) in examples and comparative examples is generally 24 hours.
In the above technical scheme, the temperature of the calcination in the step (4) is preferably 350 to 650 ℃, such as, but not limited to, 400 ℃, 420 ℃, 440 ℃, 460 ℃, 480 ℃, 500 ℃, 520 ℃, 540 ℃, 560 ℃, 580 ℃, 600 ℃, 620 ℃, 640 ℃, and the like, preferably 400 to 600 ℃. In comparison only, the firing temperature in step (4) in examples and comparative examples was generally 500 ℃.
In the above technical scheme, the time for the calcination in step (4) is preferably 3 to 12 hours, such as but not limited to 4, 4.5, 5, 5.5, 6, 6.5, 7, 7.5, 8, 8.5, 9, 9.5, 10, 10.5, 11, 11.5, and the like. Just by comparison, the baking time in step (4) in examples and comparative examples was generally 5 hours.
In the above technical scheme, the atmosphere for the calcination in the step (4) is not particularly limited. But from an economic point of view, air roasting is sufficient. However, the calcination in the step (4) is preferably carried out in the air ammonia gas mixed gas atmosphere, and the photocatalyst obtained by calcination in the air ammonia gas mixed gas atmosphere has a better photocatalytic deodorization effect. More preferably, the volume percentage of ammonia in the air ammonia mixed atmosphere is 0.1-5%. For example, but not limited to, 0.2%, 0.4%, 0.6%, 0.8%, 1.0%, 1.1%, 1.2%, 1.4%, 1.6%, 1.8%, 2.0%, 2.2%, 2.4%, 2.6%, 2.8%, 3.0%, 3.2%, 3.6%, 3.8%, 4.0%, 4.2%, 4.4%, 4.6%, 4.8%, etc., more preferably 0.5 to 2.5%. In comparison, the volume content of ammonia gas in the step (4) of calcination in the examples and comparative examples is 2.0% when an air-ammonia gas mixture atmosphere is used.
In a specific embodiment of the present invention, the composition of the titania-based photocatalyst is measured by the ICP method.
The invention provides a photocatalytic deodorizing fabric, which solves the third technical problem and adopts the technical scheme that:
a photocatalytic deodorizing fabric comprising the titanium oxide-based photocatalyst described in any one of the above-mentioned technical problems or the titanium oxide-based photocatalyst obtained by the production method described in any one of the two technical problems.
The fourth technical problem to be solved by the invention is to provide the application of the photocatalyst, and the technical scheme is as follows:
use of a titanium dioxide-based photocatalyst as defined in any one of the preceding technical problems or obtained by a process according to any one of the preceding technical problems or a process for the preparation thereof for the photocatalytic deodorization of textiles.
The technical key point of the invention is the selection of the components of the photocatalyst, and the technicians in the field can reasonably select a specific method for loading the photocatalyst on the surface of the fabric and reasonably select the material and specification of the required fabric on the basis of the prior art, so that the comparable photocatalytic deodorization effect can be achieved without creative labor.
By way of example only, fabric can be finished with a fabric deodorizer finishing liquor containing a photocatalyst of the present invention to impart a photocatalytic deodorization function to the fabric.
The evaluation method of the photocatalyst of the invention comprises the following steps:
1. preparation of finishing liquor for preparing fabric deodorant
The fabric deodorant finishing liquid comprises the following components in parts by weight:
10 parts of the titanium dioxide-based photocatalyst in one of the technical problems;
10 parts of a surfactant;
0.5 part of thickening agent;
5 parts of a crosslinking agent;
250 portions of water.
The photocatalyst is particles which are crushed and pass through a 600-mesh sieve.
The surfactant is lauryl polyoxyethylene (9) ether, AEO9 for short.
The thickener was sodium carboxymethylcellulose having a viscosity of 740mPa.s (2% strength by weight aqueous solution, 25 ℃).
The cross-linking agent is a thermal cross-linking type cross-linking agent which is produced by Shanghai Jiejikang chemical engineering Co., ltd and has the brand number of JYK FIX-DI. JYK FIX-DI is a polyurethane crosslinking agent (i.e., a crosslinking agent having polyurethane as a skeleton in the molecular structure of the crosslinking agent). Suitable for use in formulating textile coating and foam coating slurries; the high wet rubbing fastness can be improved when the high wet rubbing fastness is matched and used in pigment printing paste. Can also be used in functional additives for improving the washing fastness of functional finishing. The JYK FIX-DI has good compatibility with various functional additives, can be mixed with deionized water in any proportion, and can be treated for 2 to 5 minutes at the temperature of between 130 and 150 ℃ under the condition of heat treatment and crosslinking. As a general rule, the higher the temperature is, the shorter the required heat treatment time is, and based on this rule, a person skilled in the art can reasonably adjust the heat treatment temperature and the heat treatment time, and all the possible technical effects can be obtained without creative labor.
The preparation method of the fabric deodorant finishing liquid comprises the following steps:
placing 250 parts of water in a blending kettle, scattering powdery sodium carboxymethylcellulose on the surface of the water at ambient temperature under the condition of not starting stirring, standing overnight to ensure that the sodium carboxymethylcellulose is fully swollen by absorbing water, starting stirring, heating to dissolve at 60 ℃, and cooling to room temperature; then adding titanium dioxide based photocatalyst, AEO-9 and JYK FIX-DI, and stirring uniformly.
2. Finishing with fabric deodorant
Raw material fabric (pure cotton woven fabric, warp density: 133 pieces/10 cm, weft density: 100 pieces/10 cm, breadth 58cm, gram weight: 125g/m 2 ) Soaking in the fabric deodorant finishing liquid for 5min, extruding out the redundant fabric deodorant finishing liquid to ensure that the liquid holdup of the fabric is 90%, drying at 100 ℃ for 5min, and then baking at 150 ℃ for 3min to obtain the deodorant fabric.
3. Determination of photocatalytic deodorization effect
The photocatalytic deodorization effect of the titanium dioxide-based photocatalyst of the present invention was measured according to the inspection tube method in the standard JEC301-2013 established by the Japan society for functional textile evaluation (JAFET), and the specification of the sample fabric sample was 100cm 2 The sample was left to stand in a laboratory atmosphere for 24 hours, and the odor component used was ammonia gas. In the standard method, the photocatalytic deodorization effect is expressed by V (%) value, and the calculation method thereofThe method comprises the following steps:
V＝R L -R B
wherein R is L Is the reduction ratio (%) of the bright condition, R B Is a dark condition reduction rate (%).
The present invention will be described in detail below with reference to specific embodiments.
Detailed Description
[ example 1 ]
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I of n-butyl titanate with the weight concentration of 12.0 percent and equivalent to titanium dioxide;
(2) Dissolving ferric nitrate in water, adding acetic acid, and mixing uniformly to obtain ferric nitrate solution II, wherein the solution contains Fe by weight 2 O 3 3.0 percent, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) Drying the gel at 70 ℃ for 24 hours, and roasting the gel at 500 ℃ for 5 hours in air atmosphere to obtain the titanium dioxide-based photocatalyst, wherein Fe 2 O 3 The weight content is 3.0%.
And V =41% of the photocatalytic deodorization effect.
[ example 2 ]
The operation was the same as in example 1 except that the air atmosphere was replaced with an air-ammonia mixed gas (ammonia gas volume content: 2.0%) in the firing atmosphere of step (4), specifically:
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I of the n-butyl titanate with the weight concentration of 12.0 percent and the titanium dioxide;
(2) Dissolving ferric nitrate in water, adding acetic acid, and mixing uniformly to obtain ferric nitrate solution II, wherein the solution contains Fe by weight 2 O 3 3.0 percent, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) Drying the gel at 70 ℃ for 24 hours, and roasting the gel at 500 ℃ for 5 hours in an air-ammonia gas mixed gas (the volume content of ammonia gas is 2.0 percent) atmosphere to obtain the titanium dioxide-based photocatalyst, wherein Fe 2 O 3 The weight content is 3.0%.
And V =52% by measuring the photocatalytic deodorization effect.
[ example 3 ]
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I of the n-butyl titanate with the weight concentration of 12.0 percent and the titanium dioxide;
(2) Dissolving zinc acetate in water, adding acetic acid, and mixing uniformly to obtain a zinc acetate solution II, wherein the solution contains 3.0% of ZnO by weight, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel is dried for 24 hours at 70 ℃, and is roasted for 5 hours at 500 ℃ in the air atmosphere to obtain the titanium dioxide-based photocatalyst, wherein the weight content of ZnO is 3.0 percent.
And V =45% by measuring the photocatalytic deodorization effect.
[ example 4 ]
The operation was the same as in example 3 except that the air atmosphere was replaced with an air-ammonia mixed gas (ammonia gas content by volume: 2.0%) in the baking atmosphere of step (4), specifically:
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I of the n-butyl titanate with the weight concentration of 12.0 percent and the titanium dioxide;
(2) Dissolving zinc acetate in water, adding acetic acid, and uniformly mixing to obtain a zinc acetate solution II, wherein the solution contains ZnO of 3.0% by weight, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel is dried for 24 hours at 70 ℃, and is roasted for 5 hours at 500 ℃ in the atmosphere of air and ammonia gas mixed gas (the volume content of ammonia gas is 2.0 percent), so that the titanium dioxide-based photocatalyst is obtained, wherein the weight content of ZnO is 3.0 percent.
And V =57% of the photocatalytic deodorization effect.
[ example 5 ] A method for producing a polycarbonate
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I of n-butyl titanate with the weight concentration of 12.0 percent and equivalent to titanium dioxide;
(2) Dissolving ferric nitrate and zinc acetate in water, adding acetic acid, and mixing uniformly to obtain a ferric nitrate zinc acetate mixed solution II, wherein the solution contains Fe by weight 2 O 3 1.5 percent and 1.5 percent of ZnO, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) Drying the gel at 70 ℃ for 24 hours, and roasting the gel at 500 ℃ for 5 hours in air atmosphere to obtain the titanium dioxide-based photocatalyst, wherein Fe 2 O 3 The weight content was 1.5% and the ZnO content was 1.5%.
And V =74% of the odor removal effect of photocatalysis.
[ example 6 ]
The same operation as in example 5 was carried out except that the air atmosphere was replaced by an air-ammonia mixture (ammonia gas content by volume: 2.0%) in the firing atmosphere of step (4), specifically:
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I of n-butyl titanate with the weight concentration of 12.0 percent and equivalent to titanium dioxide;
(2) Dissolving ferric nitrate and zinc acetate in water, adding acetic acid, and uniformly mixing to obtain a ferric nitrate zinc acetate mixed solution II, wherein the solution contains Fe by weight 2 O 3 1.5 percent and ZnO 1.5 percent, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) Drying the gel at 70 ℃ for 24 hours, and roasting the gel at 500 ℃ for 5 hours in an air-ammonia mixed gas (the volume content of ammonia is 2.0 percent) atmosphere to obtain the titanium dioxide-based photocatalyst, wherein Fe 2 O 3 The weight content was 1.5% and the ZnO content was 1.5%.
And V =79% of the photocatalytic deodorization effect.
[ example 7 ]
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I of the n-butyl titanate with the weight concentration of 12.0 percent and the titanium dioxide;
(2) Dissolving ferric nitrate and zinc acetate in water, adding acetic acid, and mixing uniformly to obtain a ferric nitrate zinc acetate mixed solution II, wherein the solution contains Fe by weight 2 O 3 1.0 percent and ZnO 2.0 percent, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) Drying the gel at 70 ℃ for 24 hours, and roasting the gel at 500 ℃ for 5 hours in air atmosphere to obtain the titanium dioxide-based photocatalyst, wherein Fe 2 O 3 The weight content was 1.0%, and the weight content of ZnO was 2.0%.
And V =83% measured by photocatalytic deodorization effect.
[ example 8 ]
The same operation as in example 7 was carried out except that the air atmosphere was replaced with an air-ammonia mixed gas (ammonia gas content by volume: 2.0%) in the calcination atmosphere in step (4), specifically:
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I of n-butyl titanate with the weight concentration of 12.0 percent and equivalent to titanium dioxide;
(2) Dissolving ferric nitrate and zinc acetate in water, adding acetic acid, and uniformly mixing to obtain a ferric nitrate zinc acetate mixed solution II, wherein the solution contains Fe by weight 2 O 3 1.0 percent and ZnO 2.0 percent, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) Drying the gel at 70 ℃ for 24 hours, and roasting the gel at 500 ℃ for 5 hours in an air-ammonia mixed gas (the volume content of ammonia is 2.0 percent) atmosphere to obtain the titanium dioxide-based photocatalyst, wherein Fe 2 O 3 The weight content is 1.0 percent, and the weight content of ZnO is 2.0 percent.
And V =89% by measuring the photocatalytic deodorization effect.
[ example 9 ]
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I of the n-butyl titanate with the weight concentration of 12.0 percent and the titanium dioxide;
(2) Dissolving ferric nitrate and zinc acetate in water, adding acetic acid, and uniformly mixing to obtain a ferric nitrate zinc acetate mixed solution II, wherein the solution contains Fe by weight 2 O 3 0.5 percent and ZnO 2.5 percent, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) Drying the gel at 70 ℃ for 24 hours, and roasting the gel at 500 ℃ for 5 hours in air atmosphere to obtain the titanium dioxide-based photocatalyst, wherein Fe 2 O 3 The weight content is 0.5 percent, and the weight content of ZnO is 2.5 percent.
And V =81% by measuring the photocatalytic deodorization effect.
[ example 10 ] A method for producing a polycarbonate
The same operation as in example 9 was carried out except that the air atmosphere was replaced with an air-ammonia mixed gas (ammonia gas content by volume: 2.0%) in the calcination atmosphere in step (4), specifically:
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I of n-butyl titanate with the weight concentration of 12.0 percent and equivalent to titanium dioxide;
(2) Dissolving ferric nitrate and zinc acetate in water, adding acetic acid, and mixing uniformly to obtain a ferric nitrate zinc acetate mixed solution II, wherein the solution contains Fe by weight 2 O 3 0.5 percent and ZnO 2.5 percent, and the weight ratio of water to acetic acid in the solvent is 1.0;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) Drying the gel at 70 ℃ for 24 hours, and roasting the gel at 500 ℃ for 5 hours in an air-ammonia mixed gas (the volume content of ammonia is 2.0 percent) atmosphere to obtain the titanium dioxide-based photocatalyst, wherein Fe 2 O 3 The weight content is 0.5 percent and the weight content of ZnO is 2.5 percent.
And V =85% by measuring the photocatalytic deodorization effect.
[ COMPARATIVE EXAMPLE 1 ]
The operation is the same as that of example 1 except that the solution II does not adopt doped metal element ions, specifically:
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I of n-butyl titanate with the weight concentration of 12.0 percent and equivalent to titanium dioxide;
(2) Taking an acetic acid aqueous solution with the weight ratio of water to acetic acid being 1 as a solution II;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) And drying the gel at 70 ℃ for 24 hours, and roasting the gel at 500 ℃ for 5 hours in an air atmosphere to obtain the titanium dioxide-based photocatalyst.
And V =24% by measuring the photocatalytic deodorization effect.
[ COMPARATIVE EXAMPLE 2 ]
The same operation as in comparative example 1 was carried out except that the air atmosphere was replaced with an air-ammonia mixed gas (ammonia gas content by volume: 2.0%) in the firing atmosphere of step (4), specifically:
(1) Dissolving n-butyl titanate in ethanol to obtain an ethanol solution I of n-butyl titanate with the weight concentration of 12.0 percent and equivalent to titanium dioxide;
(2) Taking an acetic acid aqueous solution with the weight ratio of water to acetic acid being 1 as a solution II;
(3) Adding the solution II into the solution I under stirring according to the weight ratio of the solution I to the solution II of 8.1 to obtain sol, and continuing stirring at 35 ℃ until the sol is converted into gel;
(4) The gel is dried for 24 hours at 70 ℃, and is roasted for 5 hours at 500 ℃ in the atmosphere of air ammonia gas mixture (the volume content of ammonia gas is 2.0 percent), so as to obtain the titanium dioxide-based photocatalyst.
And V =31% measured by photocatalytic deodorization effect.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A titanium dioxide-based photocatalyst comprising titanium dioxide and a doped metal element comprising at least one selected from the group consisting of elements of groups IIB and VIII.
2. The titanium dioxide-based photocatalyst as claimed in claim 1, wherein the element IIB is selected from the group consisting of zinc.
3. The titania-based photocatalyst of claim 1, wherein the group VIII element is selected from the group consisting of iron, cobalt and nickel.
4. The titanium dioxide-based photocatalyst as claimed in claim 1, wherein the content of said doping metal element in the titanium dioxide-based photocatalyst is more than 0% and 10% or less by weight in terms of the doping metal oxide.
5. The process for producing the titanium dioxide-based photocatalyst as claimed in any one of claims 1 to 4, which comprises:
(1) Obtaining a titanate solution I;
(2) Obtaining a solution II doped with metal element ions, wherein the solvent adopted by the solution II comprises water and acetic acid;
(3) Adding the solution II into the solution I under stirring to obtain sol, and continuing stirring until the sol is converted into gel;
(4) And roasting the gel to obtain the titanium dioxide-based photocatalyst.
6. The process according to claim 1, wherein the titanate of step (1) corresponds to the formula 1:
wherein R is 1 ～R 4 Independently is C1-C5 alkyl. And/or the solvent adopted by the solution I in the step (1) is a lower alcohol, and the lower alcohol is more preferably C1-C3 alcohol. And/or in the step (1), the weight concentration of titanium dioxide in the solution I is 5-20% by weight of titanium dioxide.
7. The method according to claim 1, wherein the weight ratio of water to acetic acid in the solvent in the step (2) is 0.5 to 1.5. And/or the doping metal element ions of step (2) are provided by a salt of the doping metal, preferably the salt of the doping metal is an acetate, a nitrate or a chloride.
8. The production method according to claim 1, characterized in that the weight ratio of the solution I to the solution II in step (3) is not particularly limited, but we recommend the weight ratio of the solution I to the solution II to be 2 to 20, further preferably 5 to 10. And/or the temperature in the step (3) is 10-50 ℃. And/or the gel of step (4) is first subjected to a drying stage; and/or the temperature of drying is 50 to 90 ℃. And/or the drying time is 5 to 48 hours. And/or the roasting temperature in the step (4) is 350-650 ℃. And/or the roasting time in the step (4) is 3 to 12 hours.
9. Photocatalytic deodorizing fabric comprising the titania-based photocatalyst described in any one of claims 1 to 4 or the titania-based photocatalyst obtained by the production method described in any one of claims 5 to 9.
10. Use of the titanium dioxide-based photocatalyst according to any one of claims 1 to 4 or the titanium dioxide-based photocatalyst obtained by the production process according to any one of claims 5 to 9 for photocatalytic deodorization of fabrics.
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