CN111604044A - Preparation and application of tourmaline/titanium dioxide composite photocatalyst sol - Google Patents
Preparation and application of tourmaline/titanium dioxide composite photocatalyst sol Download PDFInfo
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- CN111604044A CN111604044A CN202010612556.1A CN202010612556A CN111604044A CN 111604044 A CN111604044 A CN 111604044A CN 202010612556 A CN202010612556 A CN 202010612556A CN 111604044 A CN111604044 A CN 111604044A
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- tourmaline
- titanium
- titanium dioxide
- aqueous solution
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052613 tourmaline Inorganic materials 0.000 title claims abstract description 105
- 229940070527 tourmaline Drugs 0.000 title claims abstract description 105
- 239000011032 tourmaline Substances 0.000 title claims abstract description 105
- 239000002131 composite material Substances 0.000 title claims abstract description 95
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 62
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 239000007864 aqueous solution Substances 0.000 claims abstract description 63
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims abstract description 54
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000000919 ceramic Substances 0.000 claims abstract description 45
- 239000000243 solution Substances 0.000 claims abstract description 41
- 230000002378 acidificating effect Effects 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 21
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000003608 titanium Chemical class 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 7
- 235000019441 ethanol Nutrition 0.000 claims abstract description 6
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims abstract description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 5
- -1 methyl titanate Chemical compound 0.000 claims abstract description 4
- 229910000349 titanium oxysulfate Inorganic materials 0.000 claims abstract description 4
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 64
- 239000010936 titanium Substances 0.000 claims description 64
- 229910052719 titanium Inorganic materials 0.000 claims description 64
- 238000003756 stirring Methods 0.000 claims description 42
- 239000011148 porous material Substances 0.000 claims description 32
- 239000000843 powder Substances 0.000 claims description 31
- 150000004703 alkoxides Chemical class 0.000 claims description 23
- 238000005507 spraying Methods 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 15
- 239000007788 liquid Substances 0.000 claims description 14
- 230000001699 photocatalysis Effects 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 238000000926 separation method Methods 0.000 claims description 8
- 150000002500 ions Chemical class 0.000 claims description 7
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 6
- 238000000576 coating method Methods 0.000 claims description 6
- 238000010335 hydrothermal treatment Methods 0.000 claims description 6
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000002739 metals Chemical class 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 5
- 230000001954 sterilising effect Effects 0.000 claims description 5
- 238000004659 sterilization and disinfection Methods 0.000 claims description 5
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- 229910010293 ceramic material Inorganic materials 0.000 abstract description 7
- 238000001179 sorption measurement Methods 0.000 abstract description 5
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000000354 decomposition reaction Methods 0.000 abstract 1
- 238000002604 ultrasonography Methods 0.000 description 12
- 239000001022 rhodamine dye Substances 0.000 description 11
- 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 8
- 230000015556 catabolic process Effects 0.000 description 6
- 238000006731 degradation reaction Methods 0.000 description 6
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000005520 cutting process Methods 0.000 description 4
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- 238000002791 soaking Methods 0.000 description 4
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- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
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- 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
- B01D—SEPARATION
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
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- 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
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Abstract
The invention relates to a preparation method and application of a tourmaline/titanium dioxide composite photocatalyst sol, wherein the composite sol is prepared from a titanium salt, tourmaline, an alcohol solution and an acidic aqueous solution; the titanium salt is any one of butyl titanate, methyl titanate, titanium tetrachloride and titanyl sulfate; the alcoholic solution is one or more of absolute ethyl alcohol, methanol and isopropanol; the acidic aqueous solution is a mixed solution of one or more of hydrochloric acid, nitric acid, acetic acid and sulfuric acid and deionized water. FIG. 1 is one of the composite sols. The photocatalyst sol with the composite function provided by the invention can be suitable for being sprayed on a hierarchical porous ceramic material or building and decorative materials, and can realize the adsorption and decomposition of organic pollutants such as dye, formaldehyde and the like by being matched with a lighting device. Fig. 2 is a picture of the applied ceramic substrate.
Description
Technical Field
The invention relates to a composite sol processing technology, in particular to preparation and application of a tourmaline/titanium dioxide composite photocatalyst sol.
Background
With the rapid development of global economy, the global environment is increasingly severe, and various toxic and harmful substances seriously pollute the living environment of people, thereby causing wide attention all over the world. Thus, the elimination of industrial waste and environmental pollutants has received a great deal of attention from researchers and scientists in academia and industry. TiO 22ZnO, CdS and Cu2Many semiconductor materials such as O have been used for catalytic oxidation to protect the environment. Among these semiconductors, TiO having excellent catalytic performance2It is recognized as one of the most effective and widely used photocatalysts because of its strong photoreactivity, high efficiency, chemical inertness, broad environmental potential, non-toxicity and low cost. TiO 22The photocatalytic effect of a semiconductor is induced by the absorption of photons of sufficient energy relative to the band gap (hv ≧ Eg), which results in the separation of charges from the Valence Band (VB) to the Conduction Band (CB) of an electron, separating the electron and the hole. The holes can directly oxidize organic contaminants, and can also react with H2The O molecules react to form OH radicals, which, due to their strong oxidizing properties, can degrade almost indiscriminately any organic chemical in solution. The photo-generated electrons can also be coupled with water-soluble oxygen and H+Reaction to form H2O2，H2O2Can be further decomposed into OH radicals by light. Unfortunately, such photogenerated electron-hole pairs can recombine rapidly, trapping a metastable state, which limits further expansion of the practical application of photocatalytic technology. Thus, preventing electron-hole recombination may be considered to enhance TiO2One of the strategies for photocatalytic activity.
Tourmaline is a cyclic crystalline silicate mineral containing Al, Na, Ca, Mg, B, Fe, water, fluoride and other elements. The tourmaline mineral material has natural electric polarity, pyroelectricity, piezoelectricity, infrared performance of radiation wavelength 4-14 μm, and capability of releasing negative ions, thus having very wide application in the field of environmental protectionAnd (5) landscape. Research on the management of heavy metal ion pollution in air or water using natural tourmaline minerals has been started. It can inhibit TiO due to strong electrostatic field on tourmaline particle surface2The photo-generated holes and electrons are compounded, so that the photocatalytic performance is improved. In this sense, TiO is expected2The combination with tourmaline can be used for treating TiO-based2Quantum efficiency and nanoparticle aggregation in photocatalysis.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a multifunctional tourmaline/titanium dioxide composite photocatalyst sol with low cost and good stability. Meanwhile, the preparation method of the composite sol is simple in process, convenient to popularize, easy for large-scale industry and low in cost; the multifunctional tourmaline/titanium dioxide composite photocatalyst sol is diluted by deionized water or isopropanol by 1-10 times as required to obtain a spraying liquid, and the spraying liquid is directly sprayed on the surfaces of various metals, ceramic products and multi-level pore materials to obtain the ceramic products with the capabilities of photocatalytically degrading organic pollutants and formaldehyde and releasing negative ions, sanitary wares with the function of sterilization and air purification materials. The multifunctional tourmaline/titanium dioxide composite photocatalyst sol can be subjected to solid-liquid separation, and the multifunctional composite micro powder containing nano titanium dioxide and tourmaline is prepared by adopting a method of hydrothermal treatment at 300 ℃ and freeze drying at 150 ℃ and a method of thermal treatment at 600 ℃ and 400 ℃.
The technical scheme for solving the technical problem of the composite sol is as follows: a tourmaline/titanium dioxide composite photocatalyst sol is prepared from titanium salt, tourmaline, alcohol solution and acidic aqueous solution; the titanium salt is any one of butyl titanate, methyl titanate, titanium tetrachloride and titanyl sulfate; the alcoholic solution is one or more of absolute ethyl alcohol, methanol and isopropanol; the acidic aqueous solution is a mixed solution of one or more of hydrochloric acid, nitric acid and acetic acid and deionized water.
The technical scheme for solving the technical problems of the preparation method is as follows: firstly, preparing an acidic aqueous solution: adding one or more of nitric acid, acetic acid, hydrochloric acid and sulfuric acid into deionized water to obtain an acidic aqueous solution;
further, the step of preparing a titanium solution: dispersing a titanium salt in isopropanol to obtain a titanium solution;
further, the step of mixing: dropwise adding the obtained titanium solution into an acidic aqueous solution under the conditions of stirring and room temperature to obtain a titanium-containing aqueous solution;
further, the step of adding tourmaline comprises the following steps: adding tourmaline powder into isopropanol solution, ultrasonically dispersing, and slowly adding tourmaline isopropanol solution uniformly ultrasonically dispersed into the titanium-containing aqueous solution.
Further, the aging step: aging at room temperature for 3-10 days under stirring to obtain photocatalyst sol, and stirring during aging process can prevent sol delamination to affect uniformity.
Further, the step of low-temperature preservation: packaging the photocatalytic sol, and storing at 5-40 deg.C.
Further, in the step of preparing an acidic aqueous solution, the pH of the acidic aqueous solution is 1.5 to 6.
Further, in the step of preparing the titanium solution, the titanium-containing alkoxide is selected from one or more of butyl titanate, titanium tetrachloride, titanium tetraisopropoxide and titanium isopropoxide, and the amount of the titanium-containing alkoxide is 1 to 30 g/L.
Further, in the mixing step, the stirring speed is 500-1500rpm, and the temperature condition is room temperature.
Further, in the step of adding tourmaline, the ultrasonic condition is 20-40 KHz; the dosage of the tourmaline is 0.4-12 g/L.
The technical scheme for solving the technical problem of the application of the composite sol is that the tourmaline/titanium dioxide composite photocatalyst sol is diluted by 1-10 times by deionized water or isopropanol according to needs to prepare a spraying solution; the spraying liquid is sprayed on the surfaces of various ceramics, metals and hierarchical porous materials by an ultrasonic spraying method to form a coating film, and then the stable and firm functional coating can be formed by heat treatment at the constant temperature of 400-600 ℃ for 10-30 min. The ceramic product with the capability of photocatalytic degradation of organic pollutants and formaldehyde and release of negative ions, the sanitary ware with the sterilization function and the air purification material are prepared. The tourmaline/titanium dioxide composite photocatalyst sol can be directly subjected to solid-liquid separation, namely, the solid-liquid separation can be carried out for 8 to 15 hours through hydrothermal treatment at the temperature of 150-; or drying at 80 deg.C for 6-12h, and heat treating at 400 deg.C and 600 deg.C for 5-120min to obtain composite functional micropowder containing tourmaline and nanometer titanium dioxide.
Compared with the prior art, the invention has the beneficial effects that:
(1) according to the invention, titanium dioxide and tourmaline are organically combined, on one hand, due to the natural permanent electric polarity of the tourmaline, the tourmaline can adsorb photoproduction electrons generated by a titanium dioxide photocatalyst under illumination, so that the recombination probability of the photoproduction electrons and holes is reduced, and the photocatalytic activity of the titanium dioxide photocatalyst can be improved; on the other hand, after the tourmaline is added, the specific surface area of the membrane is improved, so that more active sites can be formed on the surface of the composite photocatalyst, thereby improving the adsorption performance on pollutants and increasing the photocatalytic efficiency. Thereby obtaining the tourmaline/titanium dioxide composite material with high photocatalytic performance. The tourmaline/titanium dioxide composite material can decompose organic pollutants such as formaldehyde and the like into other small molecules under the conditions of ultraviolet light, visible light or ultraviolet-visible mixed illumination, and has the functions of sterilization and degradation of organic pollutants such as formaldehyde and the like. In addition, the tourmaline/titanium dioxide composite material also has the functions of radiating infrared rays, releasing negative ions and the like. Realizes the health, environmental protection and multifunction of the tourmaline/titanium dioxide composite material. Can be combined with ceramic products, can be used as wall decoration materials in indoor houses, hospitals, schools, nursing homes, office buildings and other occasions, can obviously improve the comfort level, and realizes high-quality healthy life.
(2) The preparation method of the material is simple and easy to control, the raw material quantity is high and low in price, the application range is wide, the industrial production is easy, the large-scale production is simple, and the material has a wide application prospect in various materials meeting the requirements of healthy home and low-carbon green environment-friendly life.
Drawings
FIG. 1 is one of the composite sols described in the abstract;
FIG. 2 is a drawing of the ceramic substrate in the abstract;
FIG. 3 is a decolorization curve of the composite functional micropowder degrading rhodamine dye aqueous solution under ultraviolet-visible light in example 5-8 of the present invention;
FIG. 4 is a decolorization curve of a rhodamine dye aqueous solution degraded by a hierarchical porous ceramic material in examples 9-10 of the present invention under ultraviolet-visible light;
FIG. 5 is a decolorization curve of a rhodamine dye aqueous solution degraded by a hierarchical porous ceramic material in examples 11-12 of the present invention under ultraviolet-visible light;
FIG. 6 is a nitrogen adsorption-desorption curve of the composite micropowder of example 5 of the present invention;
FIG. 7 is a pore size distribution curve of the composite fine powder of example 5 of the present invention;
FIG. 8 is a scanning electron micrograph of composite fine powder according to example 6 of the present invention;
FIG. 9 is a scanning electron micrograph of composite fine powder according to example 8 of the present invention;
FIG. 10 is an XRD photograph of composite fine powder of examples 5 to 9 of the present invention;
FIG. 11 is an infrared spectrum of the composite fine powder of examples 5 to 9 of the present invention;
FIG. 12 is a diagram showing an ultraviolet-visible diffuse reflection spectrum of the composite fine powder of examples 5 to 9 of the present invention;
FIG. 13 is a band gap spectrum of the composite fine powder of examples 5 to 9 of the present invention;
FIG. 14 is a photoluminescence spectrum of composite fine powder of examples 5 to 9 of the present invention;
FIG. 15 is a scanned graph of composite fine powder of examples 8 to 9 of the present invention.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and the detailed description, and it should be noted that any combination of the embodiments or technical features described below can be used to form a new embodiment without conflict.
In the present invention, all parts and percentages are by weight, unless otherwise specified, and the equipment and materials used are commercially available or commonly used in the art. The methods in the following examples are conventional in the art unless otherwise specified.
A tourmaline/titanium dioxide composite photocatalyst sol is prepared from titanium salt, tourmaline, alcohol solution and acidic aqueous solution; the titanium salt is any one of butyl titanate, methyl titanate, titanium tetrachloride and titanyl sulfate, and butyl titanate is preferred in the embodiment of the invention; the alcohol solution is one or more of absolute ethyl alcohol, methanol and isopropanol, and isopropanol is preferred in the embodiment of the invention; the acidic aqueous solution is a mixed solution of one or more of hydrochloric acid, nitric acid and acetic acid and deionized water, and acetic acid is preferred in the embodiment of the invention.
Butyl titanate, acetic acid and isopropanol are preferred as the tourmaline/titanium dioxide composite photocatalyst sol, and the cost of butyl titanate is lower than that of other titanium salts, the hydrolysis intensity is relatively weak, and the tourmaline/titanium dioxide composite photocatalyst sol is more favorable for large-scale production; acetic acid is cheap, safe and easily available, and the hydrolysis speed can be controlled by adjusting pH.
As a further embodiment, the tourmaline is a purified and ultrasonically sanded tourmaline.
As a further embodiment, the preparation method of the tourmaline/titanium dioxide composite photocatalyst sol comprises the following steps:
firstly, preparing an acidic aqueous solution: adding one or more of acetic acid, hydrochloric acid and sulfuric acid into deionized water to obtain an acidic aqueous solution;
preparing a titanium solution: dispersing a titanium salt in isopropanol to obtain a titanium solution;
and (3) mixing: dropwise adding the obtained titanium solution into an acidic aqueous solution under the conditions of stirring and room temperature to obtain a titanium-containing aqueous solution;
adding tourmaline: adding tourmaline powder into isopropanol solution, ultrasonically dispersing, and slowly adding tourmaline isopropanol solution uniformly ultrasonically dispersed into the titanium-containing aqueous solution.
Aging: aging at room temperature for 3-10 days under stirring to obtain photocatalyst sol, and stirring during aging process can prevent sol delamination to affect uniformity.
And (3) low-temperature preservation: packaging the photocatalytic sol, and storing at 5-40 deg.C.
As a further embodiment, in the step of preparing an acidic aqueous solution, the pH of the acidic aqueous solution is 1.5 to 6.
In a further embodiment, in the step of preparing the titanium solution, the titanium-containing alkoxide is one or more selected from butyl titanate, titanium tetrachloride, titanium tetraisopropoxide, and titanium isopropoxide, and the amount of the titanium-containing alkoxide is 1 to 30 g/L.
As a further embodiment, in the step of mixing, the stirring speed is 800-1500rpm, and the temperature condition is room temperature.
As a further embodiment, in the step of adding tourmaline, the ultrasonic condition is 20-40 KHz; the dosage of the tourmaline is 0.4-12 g/L.
As a further implementation mode, the application of the tourmaline/titanium dioxide composite photocatalyst sol is characterized in that deionized water or isopropanol is used for diluting 1-10 times according to needs to prepare spraying liquid; the spraying liquid is sprayed on the surfaces of various ceramics, metals and hierarchical porous materials by an ultrasonic spraying method to form a coating film, and then the stable and firm functional coating can be formed by constant-temperature heat treatment at 400-600 ℃ for 5-120 min. The ceramic product with the capability of photocatalytic degradation of organic pollutants and formaldehyde and release of negative ions, the sanitary ware with the sterilization function and the air purification material are prepared. The tourmaline/titanium dioxide composite photocatalyst sol can be directly subjected to solid-liquid separation, namely, the solid-liquid separation can be carried out for 8 to 15 hours through hydrothermal treatment at the temperature of 150-; or drying at 80 deg.C for 6-12h, and heat treating at 400 deg.C and 600 deg.C for 5-120min to obtain composite functional micropowder containing tourmaline and nanometer titanium dioxide.
The following are specific examples of the present invention, and raw materials, equipments and the like used in the following examples can be obtained by purchasing them unless otherwise specified.
Example 1:
preparing an aqueous solution with the pH value of 1.5-6 by acetic acid and deionized water to obtain an acidic aqueous solution; dispersing titanium-containing alkoxide in isopropanol to obtain a titanium solution; the titanium-containing alkoxide is butyl titanate, and the using amount of the titanium-containing alkoxide is 2.5 g/L. Slowly adding the obtained titanium solution into an acidic aqueous solution under the conditions of stirring and low temperature, wherein the stirring speed is 800r/min, and the room temperature is 25 ℃, so as to obtain a titanium-containing aqueous solution; under the conditions of stirring and ultrasound, the stirring speed is 800r/min, and the ultrasound condition is 35 KHz; the dosage of the tourmaline is 0.5g/L, tourmaline is added into the obtained titanium-containing aqueous solution, and aging treatment is carried out for 3-10 days under the stirring condition, so as to obtain tourmaline/titanium dioxide composite photocatalyst sol;
the tourmaline/titanium dioxide composite photocatalyst sol prepared by the method has stable performance, is convenient to store and apply, and has simple preparation process and low cost. The tourmaline/titanium dioxide composite photocatalyst sol is sprayed on the surfaces of ceramics, glass and hierarchical porous materials to prepare healthy, environment-friendly and green products with the functions of decontamination, degradation and antibiosis.
Example 2:
preparing an aqueous solution with the pH value of 1.5-6 by acetic acid and deionized water to obtain an acidic aqueous solution; dispersing titanium-containing alkoxide in isopropanol to obtain a titanium solution; the titanium-containing alkoxide is butyl titanate, and the using amount of the titanium-containing alkoxide is 4 g/L. Slowly adding the obtained titanium solution into an acidic aqueous solution under the conditions of stirring and low temperature, wherein the stirring speed is 1000r/min, and the room temperature is 25 ℃, so as to obtain a titanium-containing aqueous solution; under the conditions of stirring and ultrasound, the stirring speed is 1000r/min, and the ultrasound condition is 25 KHz; the dosage of the tourmaline is 0.6g/L, tourmaline is added into the obtained titanium-containing aqueous solution, and aging treatment is carried out for 3-10 days under the stirring condition, so as to obtain tourmaline/titanium dioxide composite photocatalyst sol;
example 3:
preparing an aqueous solution with the pH value of 1.5-6 by acetic acid and deionized water to obtain an acidic aqueous solution; dispersing titanium-containing alkoxide in isopropanol to obtain a titanium solution; the titanium-containing alkoxide is butyl titanate, and the using amount of the titanium-containing alkoxide is 4 g/L. Slowly adding the obtained titanium solution into an acidic aqueous solution under the conditions of stirring and low temperature, wherein the stirring speed is 1200r/min, and the room temperature is 25 ℃, so as to obtain a titanium-containing aqueous solution; under the conditions of stirring and ultrasound, the stirring speed is 1200r/min, and the ultrasound condition is 25 KHz; the dosage of the tourmaline is 0.6g/L, tourmaline is added into the obtained titanium-containing aqueous solution, and aging treatment is carried out for 3-10 days under the stirring condition, so as to obtain tourmaline/titanium dioxide composite photocatalyst sol;
example 4:
preparing an aqueous solution with the pH value of 1.5-6 by acetic acid and deionized water to obtain an acidic aqueous solution; dispersing titanium-containing alkoxide in isopropanol to obtain a titanium solution; the titanium-containing alkoxide is butyl titanate, and the using amount of the titanium-containing alkoxide is 20 g/L. Slowly adding the obtained titanium solution into an acidic aqueous solution under the conditions of stirring and low temperature, wherein the stirring speed is 600r/min, and the room temperature is 25 ℃, so as to obtain a titanium-containing aqueous solution; under the conditions of stirring and ultrasound, the stirring speed is 600r/min, and the ultrasound condition is 30 KHz; adding tourmaline into the obtained titanium-containing aqueous solution, and aging for 3-10 days under stirring to obtain tourmaline/titanium dioxide composite photocatalyst sol;
the tourmaline/titanium dioxide composite photocatalyst sol prepared by the method has stable performance, is convenient to store and apply, and has simple preparation process and low cost. The tourmaline/titanium dioxide composite photocatalyst sol is sprayed on the surfaces of ceramics, glass and hierarchical porous materials to prepare healthy, environment-friendly and green products with the functions of decontamination, degradation and antibiosis.
Example 5:
preparing an aqueous solution with the pH value of 1.5-6 by acetic acid and deionized water to obtain an acidic aqueous solution; dispersing titanium-containing alkoxide in isopropanol to obtain a titanium solution; the titanium-containing alkoxide is butyl titanate, and the using amount of the titanium-containing alkoxide is 15 g/L. Slowly adding the obtained titanium solution into an acidic aqueous solution under the conditions of stirring and low temperature, wherein the stirring speed is 1500r/min, and the room temperature is 25 ℃, so as to obtain a titanium-containing aqueous solution; under the conditions of stirring and ultrasound, the stirring speed is 1500r/min, and the ultrasound condition is 40 KHz; adding tourmaline into the obtained titanium-containing aqueous solution at a dosage of 3g/L, and aging for 3-10 days under stirring to obtain tourmaline/titanium dioxide composite photocatalyst sol;
the tourmaline/titanium dioxide composite photocatalyst sol prepared by the method is subjected to hydrothermal treatment at 220 ℃ for 8h, is washed and centrifuged to neutral pH, and is subjected to freeze drying treatment for 24h to obtain composite functional micro powder containing tourmaline and anatase phase nano titanium dioxide. The powder can be used as an additive to be added into a ceramic material to obtain an environment-friendly and healthy ceramic product.
Example 6:
the tourmaline/titanium dioxide composite photocatalyst sol in the example 1 is subjected to hydrothermal treatment at 200 ℃ for 12h, washed and centrifuged until the pH is neutral, and freeze-dried for 24h to obtain composite functional micro powder containing tourmaline and anatase phase nano titanium dioxide, as shown in figure 8.
Example 7:
preparing an aqueous solution with the pH value of 1.5-6 by acetic acid and deionized water to obtain an acidic aqueous solution; dispersing titanium-containing alkoxide in isopropanol to obtain a titanium solution; the titanium-containing alkoxide is butyl titanate, and the dosage of the titanium-containing alkoxide is 25 g/L. Slowly adding the obtained titanium solution into an acidic aqueous solution under the conditions of stirring and low temperature, wherein the stirring speed is 800r/min, and the room temperature is 25 ℃, so as to obtain a titanium-containing aqueous solution; under the conditions of stirring and ultrasound, the stirring speed is 800r/min, and the ultrasound condition is 25 KHz; adding tourmaline into the obtained titanium-containing aqueous solution at a dosage of 6g/L, and aging for 3-10 days under stirring to obtain tourmaline/titanium dioxide composite photocatalyst sol;
the tourmaline/titanium dioxide composite photocatalyst sol prepared by the method is dried in an oven at 80 ℃ for 12h, and is thermally treated at 500 ℃ for 20min to obtain composite functional micro powder containing tourmaline and anatase phase nano titanium dioxide.
Example 8:
drying the tourmaline/titanium dioxide composite photocatalyst sol in the embodiment 2 in an oven at 80 ℃ for 12h, and carrying out heat treatment at 400 ℃ for 30min to obtain composite functional micro powder containing tourmaline and anatase phase nano titanium dioxide, as shown in figure 9.
Example 9:
cutting a 5 x 5 cm-sized multi-level pore ceramic tile, soaking the ceramic tile with the multi-level pore ceramic tile with the size of 5 x 5cm in deionized water, carrying out ultrasonic cleaning treatment, heating to 200 ℃, spraying the sol obtained in the embodiment 1 onto the surface of the ceramic tile with the multi-level pore ceramic tile by using an ultrasonic spraying method, and carrying out heat treatment at 450 ℃ for 30min to obtain the multi-level pore ceramic tile with the photocatalytic degradation function, wherein the ceramic tile has a firm tourmaline/titanium dioxide composite film.
Example 10:
cutting a 5 x 5 cm-sized multi-level pore ceramic tile, soaking the ceramic tile with the multi-level pore ceramic tile with the size of 5 x 5cm by using deionized water, carrying out ultrasonic cleaning treatment, heating to 260 ℃, spraying the sol obtained in the embodiment 2 onto the surface of the ceramic tile with the multi-level pore ceramic tile by using an ultrasonic spraying method, and carrying out heat treatment at 6000 ℃ for 15min to obtain the ceramic tile with the multi-level pore ceramic tile with the photocatalytic degradation function, wherein the ceramic tile has a firm tourmaline/titanium dioxide composite film.
Example 11:
cutting a 5 x 5 cm-sized multi-level pore ceramic tile, soaking the ceramic tile with the multi-level pore ceramic tile with the size of 5 x 5cm by using deionized water, carrying out ultrasonic cleaning treatment, heating to 180 ℃, spraying the sol obtained in the embodiment 3 onto the surface of the ceramic tile with the multi-level pore ceramic tile by using an ultrasonic spraying method, and carrying out heat treatment at 550 ℃ for 5min to obtain the multi-level pore ceramic tile with the photocatalytic degradation function, wherein the ceramic tile has a firm tourmaline/titanium dioxide composite film.
Example 12:
cutting a 5 x 5 cm-sized multi-level pore ceramic tile, soaking the ceramic tile with the multi-level pore ceramic tile with the size of 5 x 5cm in deionized water, carrying out ultrasonic cleaning treatment, heating to 300 ℃, spraying the sol obtained in the embodiment 4 on the surface of the ceramic tile with the multi-level pore ceramic tile by using an ultrasonic spraying method, and carrying out heat treatment at 400 ℃ for 20min to obtain the multi-level pore ceramic tile with the photocatalytic degradation function, wherein the ceramic tile has a firm tourmaline/titanium dioxide composite film.
Effect evaluation and Performance detection
1. Taking examples 5-8 as verification examples, the ability of the hierarchical porous ceramic material to degrade rhodamine dye is observed, and the detection method is as follows: taking four groups of test tubes, each group of test tubes containing 7 test tubes, respectively adding the same amount of rhodamine dye and the same amount of water for dissolving, then correspondingly adding the same amount of the composite micro powder in the embodiment 5-8, irradiating for 0min, 10min, 20min, 30min, 40min, 50min and 60min under ultraviolet-visible light, observing the decoloring effect of the photocatalytic sol on the rhodamine dye after degradation, and drawing a decoloring curve, wherein the abscissa of the decoloring curve is the irradiation time, and the ordinate is the concentration of the rhodamine dye, and the result is shown in figure 3.
2. Taking examples 9-12 as verification examples, the ability of the hierarchical porous ceramic material to degrade rhodamine dye was observed, and the detection method was as follows: taking four beakers, respectively adding the same amount of rhodamine dye and the same amount of water for dissolving, then correspondingly adding ceramic tiles with the size of 5 x 5cm, irradiating for 0min, 10min, 20min, 30min, 40min, 50min and 60min under ultraviolet-visible light, observing the decoloring effect of the photocatalyst sol on the rhodamine dye after degradation, and describing a decoloring curve, wherein the abscissa of the decoloring curve is the irradiation time, and the ordinate is the rhodamine dye degradation rate, and the result is shown in fig. 4 and 5.
FIG. 6 is a nitrogen adsorption-desorption curve of the composite micropowder of example 5 of the present invention; as can be seen from Table 1, the specific surface area is approximately 112.245m2(ii) in terms of/g. The onset of hysteresis at a relative pressure of 0.6 indicates a larger orifice ratio. The adsorption capacity of the high-pressure area rises faster, which indicates that the large pores are more, belong to the IV-type adsorption isotherm, and the pore size is larger and the distribution is relatively wider.
FIG. 7 is a pore size distribution curve of the composite fine powder of example 5 of the present invention; it can be seen from FIG. 7 that the adsorption performance of the material is stronger when the pore size of the material is in the range of 8nm-10 nm. At this time, the main pore structure of the material is mesopores, and the pore diameter of the mesopores is not uniform.
FIG. 8 is a scanning electron micrograph of composite fine powder of example 6 of the present invention. It is apparent from FIG. 6 that the surface of the multi-level pore ceramic material has many pores with non-uniform sizes.
FIG. 9 is a scanning electron micrograph of composite fine powder of example 8 of the present invention.
FIG. 10 is an XRD photograph of the composite fine powder of examples 5 to 9 of the present invention. It is apparent from fig. 8 that the composite micro powders in the examples are typical anatase phase titanium dioxide.
Fig. 11 is an infrared spectrum of the composite fine powder of examples 5 to 9 of the present invention, from which it is apparent that there is no additional impurity except tourmaline and titanium dioxide.
FIG. 12 shows the UV-visible diffuse reflectance spectra of the composite micro powder of examples 5-9 of the present invention, which shows that the absorption band edge of the sample to light is red-shifted.
FIG. 13 is a band gap diagram of the composite fine powder of examples 5 to 9 of the present invention, in which the band gap of titanium dioxide in the sample is not significantly narrowed.
Fig. 14 is a photoluminescence spectrum of the composite micro powder of examples 5 to 9 of the present invention, and it can be seen that the photoluminescence intensity of the sample is reduced, which indicates that the micro powder prepared by the method can improve the photocatalytic activity.
Fig. 15 is a scanned view of the composite fine powder of examples 8 to 9 of the present invention, which shows that titanium dioxide is firmly present on the surface of tourmaline, which is advantageous for the photocatalytic activity of the composite fine powder.
The above embodiments are only preferred embodiments of the present invention, and the protection scope of the present invention is not limited thereby, and any insubstantial changes and substitutions made by those skilled in the art based on the present invention are within the protection scope of the present invention.
Claims (10)
1. A tourmaline/titanium dioxide composite photocatalyst sol is prepared from titanium salt, tourmaline, alcohol solution and acidic aqueous solution; the titanium salt is any one of butyl titanate, methyl titanate, titanium tetrachloride and titanyl sulfate; the alcoholic solution is one or more of absolute ethyl alcohol, methanol and isopropanol; the acidic aqueous solution is a mixed solution of one or more of hydrochloric acid, nitric acid, acetic acid and sulfuric acid and deionized water.
2. The tourmaline/titanium dioxide composite photocatalyst sol as defined in claim 1, wherein said titanium salt is butyl titanate, said alcohol solution is isopropanol, and said acidic aqueous solution is a mixed solution of acetic acid and deionized water.
3. The tourmaline/titanium dioxide composite photocatalyst sol as defined in claim 1, wherein the tourmaline is tourmaline which has been purified and subjected to ultrasonic sanding, and has good dispersibility.
4. The method for preparing the tourmaline/titanium dioxide composite photocatalyst sol according to any one of claims 1 to 3 comprises the following steps:
preparing an acidic aqueous solution: adding acetic acid into deionized water to obtain an acidic aqueous solution;
preparing a titanium solution: dispersing butyl titanate in isopropanol to obtain a titanium solution;
and (3) mixing: dropwise adding the obtained titanium solution into an acidic aqueous solution under the conditions of stirring and room temperature to obtain a titanium-containing aqueous solution;
adding tourmaline: adding tourmaline powder into isopropanol solution, ultrasonically dispersing, and slowly adding tourmaline isopropanol solution uniformly ultrasonically dispersed into the titanium-containing aqueous solution.
Aging: aging at room temperature for 3-10 days under stirring to obtain photocatalyst sol, and continuously stirring during aging to prevent sol delamination and uniformity influence.
And (3) low-temperature preservation: packaging the photocatalytic sol, and storing at 5-40 deg.C.
5. The method for preparing a tourmaline/titanium dioxide composite photocatalyst sol as defined in claim 4, wherein in the step of preparing an acidic aqueous solution, the pH of the acidic aqueous solution is 1.5 to 6; the dosage of the titanium-containing alkoxide is 1-30 g/L; the stirring speed is 500-1500 rpm. In the step of adding tourmaline, the ultrasonic condition is 20-40 KHz; the dosage of the tourmaline additive is 0.4-12 g/L.
6. The application of the tourmaline/titanium dioxide composite photocatalyst sol is characterized in that the tourmaline/titanium dioxide composite photocatalyst sol as claimed in claim 1, 2 or 3 is diluted by 1-10 times by deionized water or isopropanol according to the requirement to prepare spraying liquid; the spraying liquid is sprayed on the surfaces of various ceramics, metals and hierarchical porous materials by an ultrasonic spraying method to form a coating film, and then the stable and firm functional coating can be formed by constant-temperature heat treatment at 400-600 ℃ for 5-120 min.
7. The use of the tourmaline/titanium dioxide composite photocatalyst sol as claimed in claim 6, wherein the tourmaline/titanium dioxide composite photocatalyst sol is diluted 1-100 times with deionized water or isopropanol as required to prepare a spraying solution which can be sprayed on the inner and outer surfaces of various metals, ceramic products and hierarchical porous materials.
8. The use of the tourmaline/titanium dioxide composite photocatalyst sol as claimed in claim 6, wherein the tourmaline/titanium dioxide composite photocatalyst sol is prepared into a ceramic product having the ability of photocatalytically degrading organic pollutants, formaldehyde and releasing negative ions, a sanitary ware having a sterilization function, and an air purification material.
9. The application of the tourmaline/titanium dioxide composite photocatalyst sol is characterized in that the tourmaline/titanium dioxide composite photocatalyst sol as described in claim 1, 2 or 3 is subjected to solid-liquid separation, hydrothermal treatment at the temperature of 150 ℃ and 300 ℃ for 8-15h, then washed and centrifuged to be neutral, and then freeze-dried for 12-36h, so that composite functional micropowder containing tourmaline and nano titanium dioxide can be obtained.
10. The application of the tourmaline/titanium dioxide composite photocatalyst sol is characterized in that the tourmaline/titanium dioxide composite photocatalyst sol as described in claim 1, 2 or 3 is subjected to solid-liquid separation, dried at 80 ℃ for 6-12h and heat treated at 400 ℃ and 600 ℃ for 5-120min to obtain the composite functional micropowder containing tourmaline and nano titanium dioxide.
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