CN109569737B - Preparation method of molecular sieve photocatalyst for ceramic ink - Google Patents
Preparation method of molecular sieve photocatalyst for ceramic ink Download PDFInfo
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- CN109569737B CN109569737B CN201811606076.3A CN201811606076A CN109569737B CN 109569737 B CN109569737 B CN 109569737B CN 201811606076 A CN201811606076 A CN 201811606076A CN 109569737 B CN109569737 B CN 109569737B
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- molecular sieve
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- photocatalyst
- lanthanum
- ceramic ink
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- 239000000919 ceramic Substances 0.000 title claims abstract description 65
- 239000002808 molecular sieve Substances 0.000 title claims abstract description 63
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims description 58
- 229910052746 lanthanum Inorganic materials 0.000 claims description 48
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 26
- 239000002904 solvent Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 229910052720 vanadium Inorganic materials 0.000 claims description 22
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 22
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 20
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 16
- 238000000227 grinding Methods 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 15
- 230000001590 oxidative effect Effects 0.000 claims description 14
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 239000007800 oxidant agent Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000000498 ball milling Methods 0.000 claims description 5
- 239000012153 distilled water Substances 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 238000006116 polymerization reaction Methods 0.000 claims description 5
- 239000004576 sand Substances 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 4
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 claims description 4
- LXASOGUHMSNFCR-UHFFFAOYSA-D [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O Chemical compound [V+5].[V+5].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O LXASOGUHMSNFCR-UHFFFAOYSA-D 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- JLRJWBUSTKIQQH-UHFFFAOYSA-K lanthanum(3+);triacetate Chemical compound [La+3].CC([O-])=O.CC([O-])=O.CC([O-])=O JLRJWBUSTKIQQH-UHFFFAOYSA-K 0.000 claims description 4
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 4
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- 239000012286 potassium permanganate Substances 0.000 claims description 4
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 4
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 239000005720 sucrose Substances 0.000 claims description 4
- JTJFQBNJBPPZRI-UHFFFAOYSA-J vanadium tetrachloride Chemical compound Cl[V](Cl)(Cl)Cl JTJFQBNJBPPZRI-UHFFFAOYSA-J 0.000 claims description 4
- 229910021536 Zeolite Inorganic materials 0.000 claims description 3
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 3
- 239000010457 zeolite Substances 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 239000003086 colorant Substances 0.000 abstract description 9
- 239000007789 gas Substances 0.000 abstract description 5
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 2
- 239000000976 ink Substances 0.000 description 56
- 238000012360 testing method Methods 0.000 description 13
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 5
- 229920000414 polyfuran Polymers 0.000 description 5
- 238000011161 development Methods 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000007641 inkjet printing Methods 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000049 pigment Substances 0.000 description 3
- 238000007639 printing Methods 0.000 description 3
- 238000012795 verification Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000002932 luster Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000002341 toxic gas Substances 0.000 description 2
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 239000002518 antifoaming agent Substances 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000000975 dye Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- -1 praseodymium carboxylate Chemical class 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
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- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
- A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
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- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
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- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/10—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation
- A62D3/17—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by subjecting to electric or wave energy or particle or ionizing radiation to electromagnetic radiation, e.g. emitted by a laser
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/36—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of vanadium, niobium or tantalum
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- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
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Abstract
The invention belongs to the technical field of preparation of photocatalyst materials, and particularly relates to a preparation method of a molecular sieve photocatalyst for ceramic ink. The invention is applied to ceramic ink, can endow the ceramic ink with photocatalytic performance, and can effectively degrade organic pollutants on the surface of the ceramic and decompose organic harmful gases in the air; in addition, the coloring agent can stably develop color, and the color vividness of red and yellow is improved.
Description
[ technical field ] A method for producing a semiconductor device
The invention belongs to the technical field of preparation of photocatalyst materials, and particularly relates to a preparation method of a molecular sieve photocatalyst for ceramic ink.
[ background of the invention ]
With the development of science and technology and the modernization of industry, the living standard of people is obviously improved, but simultaneously, people are harmed by the environmental pollution. Water pollution, air pollution, indoor harmful gas and the like have caused serious harm to human health. Sewage treatment and air purification are therefore important research contents for researchers in various countries. How to effectively remove toxic substances such as surfactants, dyes, heavy metal ions and the like in industrial wastewater, and organic waste gas and toxic gas in the atmosphere becomes a hot topic in various research fields. Photocatalytic oxidation is an advanced oxidation technology, and is rapidly developed in the fields of sewage treatment and organic waste gas and toxic gas removal.
Ink jet printing is one of the most prominent plateless digital printing technologies at present, and the basic principle is to directly eject ink from a fine nozzle to a designated position on a printing material according to the instruction of a computer, so as to form a pre-designed pattern. The photocatalytic performance of the ink-jet printing ceramic ink for manufacturing decorative ceramics is disclosed, but the photocatalytic performance of the ink-jet printing ceramic ink is still to be improved; in addition, the colorant of the ceramic ink mainly comprises organic metal salt which can be dissolved in a solvent, and after the ceramic ink is printed and baked, part of the colorant undergoes chemical change under high temperature, so that the colorant becomes dark or even does not develop color, especially red and yellow.
[ summary of the invention ]
In view of the above, there is a need for a method for preparing a molecular sieve photocatalyst for ceramic ink, which can provide the ceramic ink with photocatalytic performance and can also improve the color vividness of red and yellow.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a molecular sieve photocatalyst for ceramic ink comprises the following steps:
(1) respectively taking a lanthanum source, a vanadium source and a solvent according to the mass volume ratio of the lanthanum source to the vanadium source to the solvent of 3-5g:4-6g:5-8ml, and mixing the materials to obtain a system I; slowly dripping the obtained system I into a nitric acid solution with the pH of 4-6 and the temperature of 50-80 ℃ for hydrolysis under the vigorous stirring with the stirring speed of 1700-1900r/min to obtain a system II, keeping the volume ratio of the total mass of the lanthanum source and the vanadium source to the water in the system II at 1:15-30, and carrying out hydrothermal reaction in a high-pressure kettle with the temperature of 120-150 ℃ for 3-24h to obtain lanthanum vanadate nano-particles;
(2) mixing the obtained lanthanum vanadate nanoparticles and furan at a molar ratio of 1:5-12 at 10-60 ℃, realizing oxidative polymerization by adopting a chemical oxidation method, wherein the molar ratio of an oxidant to furan is 1:1-3, continuously reacting for 20-25h at 30-80 ℃, filtering and drying until the water content is less than 10%, thus obtaining a polyfuran-lanthanum vanadate compound;
(3) mixing the polyfuran-lanthanum vanadate compound obtained in the step (2) with a molecular sieve according to the weight ratio of 1:2-7 to obtain a mixture A, and then adding a grinding aid into the mixture A to obtain a mixture B, wherein the mass ratio of the grinding aid to the mixture A is 5-15: 1; then ball milling the mixture B to 100-300nm to obtain a mixture C;
(4) and washing and drying the mixture C to obtain the molecular sieve photocatalyst.
In the invention, it is further explained that the lanthanum source in the step (1) is one or a mixture of several of lanthanum nitrate, lanthanum chloride and lanthanum acetate mixed in any proportion; the vanadium source is one of vanadium tetrachloride and vanadium oxalate or a mixture mixed in any proportion.
In the present invention, the solvent in step (1) is water or an aqueous solution of an organic acid.
In the invention, it is further specified that in the step (2), the oxidizing agent is one or a mixture of several of ferric chloride, potassium persulfate and potassium permanganate mixed in any proportion.
In this invention, it is further specified that in step (3) the molecular sieve is selected from at least one of ZSM-5, beta or Y zeolite molecular sieves.
In the invention, the grinding aid in the step (3) is one of NaCl and sucrose or a mixture mixed in any proportion.
In the present invention, further, in the step (3), the mixture B is ball-milled by a sand mill.
In the present invention, it is further explained that, in the step (3), the rotation speed of the ball mill is 2000-3000 r/min.
In the invention, further, in the step (4), the mixture C is washed for 2-3 times by using distilled water as a detergent, and then is dried in an oven at 25-60 ℃ until the water content is less than 7%.
The molecular sieve photocatalyst prepared by the method is applied to the preparation of ceramic ink.
In the invention, lanthanum vanadate is a vanadate photocatalyst and can generate active species such as hydroxyl radicals, superoxide radicals and the like under the irradiation of sunlight, so that the lanthanum vanadate has the effects of antibiosis, deodorization, oil stain decomposition, mildew and algae prevention and air purification; the polyfuran has strong absorption in a visible light area and a near red light area, and lanthanum vanadate is modified by a certain amount to enhance the light absorption of the lanthanum vanadate in the visible light area, so that the catalytic performance of the lanthanum vanadate can be improved.
In addition, the colorant of the ceramic ink mainly comprises organic metal salt which can be dissolved in a solvent, the colorant is baked after being printed by an ink-jet printer, the colorant is converted into metal oxide which can present colors at high temperature to form patterns, however, in the baking process of the ceramic tile, the metal oxide can generate a series of chemical reactions, so that the color development of the metal oxide is unstable, even the color development of the metal oxide can not be realized, particularly red and yellow.
The invention has the following beneficial effects:
1. the invention is applied to ceramic ink, can lead the ceramic ink to have photocatalysis performance, and can effectively degrade organic pollutants on the surface of the ceramic and decompose organic harmful gases in the air.
2. The invention is applied to ceramic ink, can stabilize the color development of the colorant and improve the color vividness of red and yellow.
[ detailed description ] embodiments
The invention provides a preparation method of a molecular sieve photocatalyst for ceramic ink, and the invention is further described in detail below in order to make the purpose, technical scheme and effect of the invention clearer and clearer. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
The molecular sieve photocatalyst for ceramic ink provided in this example was prepared as follows:
a preparation method of a molecular sieve photocatalyst for ceramic ink comprises the following steps:
(1) respectively taking a lanthanum source, a vanadium source and a solvent according to the mass-volume ratio of the lanthanum source to the vanadium source to the solvent of 3g:4g:5ml, and mixing the lanthanum source, the vanadium source and the solvent to obtain a system I, wherein the lanthanum source is lanthanum nitrate, the vanadium source is vanadium tetrachloride, and the solvent is water; slowly dropwise adding the obtained system I into a nitric acid solution with pH of 4 and temperature of 50 ℃ to hydrolyze under the vigorous stirring at the stirring speed of 1700r/min to obtain a system II, keeping the volume ratio of the total mass of a lanthanum source and a vanadium source to water in the system II at 1:15, and carrying out hydrothermal reaction in a high-pressure kettle at 120 ℃ for 3 hours to obtain lanthanum vanadate nanoparticles;
(2) mixing the obtained lanthanum vanadate nanoparticles and furan according to a molar ratio of 1:5 at 10 ℃, realizing oxidative polymerization by adopting a chemical oxidation method, adopting acetonitrile as a solvent, enabling the molar ratio of an oxidant to the furan to be 1:1, continuously reacting for 20 hours at 30 ℃, filtering and drying until the water content is less than 10%, and obtaining a polyfuran-lanthanum vanadate compound, wherein the oxidant is ferric chloride;
(3) mixing the polyfuran-lanthanum vanadate compound obtained in the step (2) with a molecular sieve according to the weight part ratio of 1:2 to obtain a mixture A, wherein the molecular sieve is selected from ZSM-5, then adding a grinding aid into the mixture A to obtain a mixture B, wherein the mass ratio of the grinding aid to the mixture A is 5:1, and the grinding aid is NaCl; then, ball milling the mixture B to 100-180nm by using a sand mill, wherein the rotating speed of the ball mill is 2000r/min, and obtaining a mixture C;
(4) and (3) washing the mixture C for 2 times by using distilled water as a washing agent, and then putting the mixture C into a drying oven at 25 ℃ for drying until the water content is less than 7%, thus obtaining the molecular sieve photocatalyst.
The molecular sieve photocatalyst prepared by the method is applied to the preparation of ceramic ink.
Example 2
The molecular sieve photocatalyst for ceramic ink provided in this example was prepared as follows:
a preparation method of a molecular sieve photocatalyst for ceramic ink comprises the following steps:
(1) respectively taking a lanthanum source, a vanadium source and a solvent according to the mass-volume ratio of the lanthanum source to the vanadium source to the solvent of 4g:5g:7ml, and mixing the lanthanum source, the vanadium source and the solvent to obtain a system I, wherein the lanthanum source is a mixture of lanthanum chloride and lanthanum acetate which are mixed in any proportion, the vanadium source is in vanadium oxalate, and the solvent is an organic acid aqueous solution; slowly dropwise adding the obtained system I into a nitric acid solution with pH of 5 and temperature of 65 ℃ to hydrolyze under the vigorous stirring at the stirring speed of 1800r/min to obtain a system II, keeping the volume ratio of the total mass of a lanthanum source and a vanadium source to water in the system II at 1:24, and carrying out hydrothermal reaction in a high-pressure kettle at 135 ℃ for 10 hours to obtain lanthanum vanadate nanoparticles;
(2) mixing the obtained lanthanum vanadate nanoparticles and furan according to a molar ratio of 1:8 at 40 ℃, realizing oxidative polymerization by adopting a chemical oxidation method, adopting acetonitrile as a solvent, enabling the molar ratio of an oxidant to the furan to be 1:2, continuously reacting for 23 hours at 40 ℃, filtering and drying until the water content is less than 10%, and obtaining a polyfuran-lanthanum vanadate compound, wherein the oxidant is a mixture of potassium persulfate and potassium permanganate which are mixed according to any ratio;
(3) mixing the polyfuran-lanthanum vanadate compound obtained in the step (2) with a molecular sieve according to the weight part ratio of 1:5 to obtain a mixture A, wherein the molecular sieve is selected from a mixture of ZSM-5 and beta mixed in any ratio, and then adding a grinding aid into the mixture A to obtain a mixture B, wherein the mass ratio of the grinding aid to the mixture A is 10:1, and the grinding aid is sucrose; then, ball milling the mixture B to 220nm at the rotation speed of 2500r/min by using a sand mill to obtain a mixture C;
(4) and (3) washing the mixture C for 2 times by using distilled water as a washing agent, and then putting the mixture C into a 45 ℃ oven to be dried until the water content is less than 7%, thus obtaining the molecular sieve photocatalyst.
The molecular sieve photocatalyst prepared by the method is applied to the preparation of ceramic ink.
Example 3
The molecular sieve photocatalyst for ceramic ink provided in this example was prepared as follows:
a preparation method of a molecular sieve photocatalyst for ceramic ink comprises the following steps:
(1) respectively taking a lanthanum source, a vanadium source and a solvent according to the mass-volume ratio of the lanthanum source to the solvent of 5g:6g:8ml, and mixing the lanthanum source, the vanadium source and the solvent to obtain a system I, wherein the lanthanum source is a mixture of lanthanum nitrate, lanthanum chloride and lanthanum acetate which are mixed in any proportion, the vanadium source is a mixture of vanadium tetrachloride and vanadium oxalate which are mixed in any proportion, and the solvent is an organic acid aqueous solution; slowly dropwise adding the obtained system I into a nitric acid solution with the pH value of 6 and the temperature of 80 ℃ to hydrolyze under the vigorous stirring with the stirring speed of 1900r/min to obtain a system II, keeping the volume ratio of the total mass of a lanthanum source and a vanadium source to water in the system II to be 1:30, and carrying out hydrothermal reaction in a high-pressure kettle at the temperature of 150 ℃ for 24 hours to obtain lanthanum vanadate nanoparticles;
(2) mixing the obtained lanthanum vanadate nanoparticles and furan according to a molar ratio of 1:12 at 60 ℃, realizing oxidative polymerization by adopting a chemical oxidation method, adopting acetonitrile as a solvent, enabling the molar ratio of an oxidant to the furan to be 1:3, continuously reacting for 25 hours at 80 ℃, filtering and drying until the water content is less than 10%, and obtaining a polyfuran-lanthanum vanadate compound, wherein the oxidant is a mixture of ferric chloride, potassium persulfate and potassium permanganate which are mixed according to any ratio;
(3) mixing the polyfuran-lanthanum vanadate compound obtained in the step (2) with a molecular sieve according to the weight part ratio of 1:7 to obtain a mixture A, wherein the molecular sieve is a mixture of ZSM-5, beta and Y zeolite molecular sieves in any ratio, and then adding a grinding aid into the mixture A to obtain a mixture B, wherein the mass ratio of the grinding aid to the mixture A is 15:1, and the grinding aid is a mixture of NaCl and sucrose in any ratio; then, ball milling the mixture B to 220-300nm by using a sand mill, wherein the rotating speed of the ball mill is 3000r/min, so as to obtain a mixture C;
(4) and (3) washing the mixture C for 3 times by using distilled water as a washing agent, and then putting the mixture C into a 60 ℃ oven to be dried until the water content is less than 7%, thus obtaining the molecular sieve photocatalyst.
The molecular sieve photocatalyst prepared by the method is applied to the preparation of ceramic ink.
Comparative example 1
The molecular sieve photocatalyst for ceramic ink provided in this example was prepared as follows:
a method for preparing a molecular sieve photocatalyst for ceramic ink, wherein the molecular sieve is not modified with polyfuran, and the rest is the same as in example 1.
The molecular sieve photocatalyst prepared by the method is applied to the preparation of ceramic ink.
Comparative example 2
The molecular sieve photocatalyst for ceramic ink provided in this example was prepared as follows:
a method for preparing a molecular sieve photocatalyst for ceramic ink, wherein the molecular sieve is not modified with polyfuran, and the rest is the same as in example 2.
The molecular sieve photocatalyst prepared by the method is applied to the preparation of ceramic ink.
Comparative example 3
The molecular sieve photocatalyst for ceramic ink provided in this example was prepared as follows:
a method for preparing a molecular sieve photocatalyst for ceramic ink, wherein the molecular sieve is not modified with polyfuran, and the rest is the same as in example 3.
The molecular sieve photocatalyst prepared by the method is applied to the preparation of ceramic ink.
Effect verification
(I) photocatalytic assay
After the finished products of examples 1-3 and comparative examples 1-3 are prepared, the finished products are used as 6 test finished products and are respectively applied to the manufacture of ceramic ink, the preparation method, the amount of the test finished products and the types and the amounts of other reagents of each group of ceramic ink are the same, wherein the formula of the ceramic ink comprises 25% of pigment, 8% of photocatalyst, 2% of magnesium carbonate, 30% of D100 solvent oil and 10% of propylene glycol monomethyl ether; 3% of hyperdispersant; 0.8% of a binding agent; 2% of surfactant, 0.3% of defoaming agent and 1.2% of glycerol, wherein the photocatalyst corresponds to 6 molecular sieve photocatalyst test finished products in each group of formula, 6 ceramic ink samples are prepared and are sequentially marked as samples 1-6, then ceramic tiles of the same material are printed and roasted by using the samples 1-6, the 6 ceramic tiles are respectively put into 6 glass test boxes of 50cm × 50cm × 100cm, the test samples corresponding to the test boxes are labeled one by one, formaldehyde is used as a simulation photocatalytic substrate, 6ml of formaldehyde is injected into each test box, the ceramic tiles are respectively taken out after standing for 24 days, the formaldehyde degradation rate in the 6 test boxes is respectively detected by using a phenol reagent spectrophotometer, and the results are recorded in table 1. The detection results are shown in table 1:
TABLE 1 photocatalytic verification and detection results of molecular sieve photocatalysts
| Test finished product | Examples1 | Example 2 | Example 3 | Comparative example 1 | Comparative example 2 | Comparative example 3 |
| Rate of degradation | 91.5％ | 92.7％ | 91.9％ | 35.7％ | 34.8％ | 33.9％ |
In the data, the example 1 and the comparative example 1, the example 2 and the comparative example 2, and the example 3 and the comparative example 3 are comparative examples respectively, and the data shows that the degradation rate of formaldehyde after being applied to the preparation of ceramic ink is obviously lower than that of the 3 examples of the invention because the finished products of the 3 comparative examples are not modified by polyfuran, and the experiment shows that the invention greatly improves the photocatalytic performance of the finished products.
(II) verification of effect of improving color vividness
After the finished products of examples 1 to 3 are used as 3 test finished products, the test finished products are respectively applied to the preparation of ceramic ink, wherein each test finished product is used for preparing a red ink and a yellow ink, the ink formula is the same as the above (1), the pigment in the red ink formula is nano iron oxide, the pigment in the yellow ink formula is praseodymium carboxylate, 3 red ink samples and 3 yellow inks are respectively prepared by the same preparation method, a red ink and a yellow ink are respectively prepared by the same preparation method of the red ink and the yellow ink to be used as comparison samples, the difference is that no molecular sieve catalyst of any type is added in the raw materials, then ceramic tiles of the same material are printed and roasted by using the ink samples prepared by the above, wherein the ink quantity printed on each ceramic tile is the same, the color and luster of the printed ceramic tiles are respectively evaluated, and the results are shown in the following table 2:
TABLE 2 influence of molecular sieve photocatalyst on color and luster vividness of ink
In the above table, the samples 1 to 3 correspond to the finished products prepared in the examples 1 to 3, and the data in the above table show that the ink in the control group has dark color and obviously less bright color than the other 3 test groups after printing and roasting the ceramic tile because no molecular sieve catalyst of any type is added, so that the application of the invention to the ceramic ink has the effect of improving the brightness of the color.
Although the invention has been described in detail hereinabove with respect to a general description and specific embodiments thereof, it will be apparent to those skilled in the art that modifications or improvements may be made thereto based on the invention. Accordingly, such modifications and improvements are intended to be within the scope of the invention as claimed.
Claims (10)
1. A preparation method of a molecular sieve photocatalyst for ceramic ink is characterized by comprising the following steps:
(1) respectively taking a lanthanum source, a vanadium source and a solvent according to the mass volume ratio of the lanthanum source to the vanadium source to the solvent of 3-5g:4-6g:5-8ml, and mixing the materials to obtain a system I; slowly dripping the obtained system I into a nitric acid solution with the pH of 4-6 and the temperature of 50-80 ℃ for hydrolysis under the vigorous stirring with the stirring speed of 1700-1900r/min to obtain a system II, keeping the volume ratio of the total mass of the lanthanum source and the vanadium source to the water in the system II at 1:15-30, and carrying out hydrothermal reaction in a high-pressure kettle with the temperature of 120-150 ℃ for 3-24h to obtain lanthanum vanadate nano-particles;
(2) mixing the obtained lanthanum vanadate nanoparticles and furan at a molar ratio of 1:5-12 at 10-60 ℃, realizing oxidative polymerization by adopting a chemical oxidation method, wherein the molar ratio of an oxidant to furan is 1:1-3, continuously reacting for 20-25h at 30-80 ℃, filtering and drying until the water content is less than 10%, thus obtaining a polyfuran-lanthanum vanadate compound;
(3) mixing the polyfuran-lanthanum vanadate compound obtained in the step (2) with a molecular sieve according to the weight ratio of 1:2-7 to obtain a mixture A, and then adding a grinding aid into the mixture A to obtain a mixture B, wherein the mass ratio of the grinding aid to the mixture A is 5-15: 1; then ball milling the mixture B to 100-300nm to obtain a mixture C;
(4) and washing and drying the mixture C to obtain the molecular sieve photocatalyst.
2. The method for preparing the molecular sieve photocatalyst for the ceramic ink according to claim 1, wherein the lanthanum source in the step (1) is one or a mixture of lanthanum nitrate, lanthanum chloride and lanthanum acetate which are mixed in any proportion; the vanadium source is one of vanadium tetrachloride and vanadium oxalate or a mixture mixed in any proportion.
3. The method for preparing the molecular sieve photocatalyst for ceramic ink according to claim 1, wherein the solvent in the step (1) is water or an aqueous solution of an organic acid.
4. The method for preparing the molecular sieve photocatalyst for ceramic ink according to claim 1, wherein the oxidant in step (2) is one or a mixture of iron chloride, potassium persulfate and potassium permanganate mixed in any proportion.
5. The method for preparing a molecular sieve photocatalyst for ceramic ink according to claim 1, wherein the molecular sieve in step (3) is at least one molecular sieve selected from ZSM-5, beta and Y zeolite molecular sieves.
6. The method for preparing the molecular sieve photocatalyst for the ceramic ink is characterized in that the grinding aid in the step (3) is one of NaCl and sucrose or a mixture mixed in any proportion.
7. The method for preparing a molecular sieve photocatalyst for ceramic ink according to claim 1, wherein in the step (3), the mixture B is ball-milled by a sand mill.
8. The method for preparing a molecular sieve photocatalyst for ceramic ink as claimed in claim 1, wherein in the step (3), the rotation speed of the ball mill is 2000-3000 r/min.
9. The method for preparing the molecular sieve photocatalyst for ceramic ink according to claim 1, wherein in the step (4), the mixture C is washed for 2-3 times by using distilled water as a detergent, and then is dried in an oven at 25-60 ℃ until the water content is less than 7%.
10. A molecular sieve photocatalyst for ceramic ink made by the method of any one of claims 1-9.
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| CN101624206A (en) * | 2009-08-07 | 2010-01-13 | 南开大学 | Preparation method and application of rare earth metal hydroxide or vanadate nano material |
| CN102008964A (en) * | 2010-11-08 | 2011-04-13 | 浙江师范大学 | Lanthanum vanadate-based visible light responsive photocatalyst and preparation method thereof |
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| CN101624206A (en) * | 2009-08-07 | 2010-01-13 | 南开大学 | Preparation method and application of rare earth metal hydroxide or vanadate nano material |
| CN102008964A (en) * | 2010-11-08 | 2011-04-13 | 浙江师范大学 | Lanthanum vanadate-based visible light responsive photocatalyst and preparation method thereof |
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