CN111099918A - Nano photocatalytic ceramic material - Google Patents
Nano photocatalytic ceramic material Download PDFInfo
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- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 22
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 19
- 239000011941 photocatalyst Substances 0.000 claims abstract description 37
- 239000000843 powder Substances 0.000 claims abstract description 31
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000002131 composite material Substances 0.000 claims abstract description 23
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000002078 nanoshell Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000919 ceramic Substances 0.000 claims abstract description 7
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 239000002270 dispersing agent Substances 0.000 claims abstract description 7
- 239000004094 surface-active agent Substances 0.000 claims abstract description 7
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 7
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000003756 stirring Methods 0.000 claims description 24
- 238000001354 calcination Methods 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 229910002915 BiVO4 Inorganic materials 0.000 claims description 12
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 238000000227 grinding Methods 0.000 claims description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- PAJMKGZZBBTTOY-UHFFFAOYSA-N 2-[[2-hydroxy-1-(3-hydroxyoctyl)-2,3,3a,4,9,9a-hexahydro-1h-cyclopenta[g]naphthalen-5-yl]oxy]acetic acid Chemical compound C1=CC=C(OCC(O)=O)C2=C1CC1C(CCC(O)CCCCC)C(O)CC1C2 PAJMKGZZBBTTOY-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- 238000005406 washing Methods 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 6
- 229910052681 coesite Inorganic materials 0.000 claims description 3
- 229910052906 cristobalite Inorganic materials 0.000 claims description 3
- 238000001704 evaporation Methods 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000007873 sieving Methods 0.000 claims description 3
- 239000000377 silicon dioxide Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910052682 stishovite Inorganic materials 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 229910052905 tridymite Inorganic materials 0.000 claims description 3
- 239000003814 drug Substances 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 239000002041 carbon nanotube Substances 0.000 abstract description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 230000007797 corrosion Effects 0.000 abstract description 3
- 238000005260 corrosion Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000012528 membrane Substances 0.000 abstract description 3
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 238000000034 method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000010865 sewage Substances 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
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Abstract
The invention discloses a nano photocatalytic ceramic material which is prepared from the following raw materials in parts by weight: SiO 226-10 parts of Al2O32-8 parts of CaO1-5 parts of MgO1-3 parts of TiO23-6 parts of K2O1-3 parts, Na2The composite photocatalyst comprises, by weight, O2-4 parts, diatomite 40-60 parts, nano shell powder 15-20 parts, a composite photocatalyst 6-12 parts, a surfactant 2-4 parts, a dispersant 1-3 parts, and a proper amount of deionized water. Directly realizes the immobilization of the photocatalyst on the ceramicThe photocatalytic performance is improved; TiO2 is directly added on the nano ceramic, so that the preparation method is simple; the composite material has the advantages of high catalytic efficiency, corrosion resistance, cleaning resistance, high mechanical strength, stable structure, no deformation and long service life due to the enrichment adsorption effect of the porous inorganic ceramic membrane and the unique charge transmission performance of the carbon nano tube.
Description
Technical Field
The invention relates to the technical field of ceramic materials, in particular to a nano photocatalytic ceramic material.
Background
Photocatalytic oxidation technology is a new water treatment technology which appears in 20 years. The application of the photocatalytic oxidation method in environmental protection has attracted high attention from all countries in the world, and the investment of China is enhanced in this respect. In recent years, the photocatalytic oxidation method for treating COD has been generally accepted by people for the outstanding advantages of low cost and no secondary pollution. The photocatalytic oxidation-reduction mechanism is mainly characterized in that the catalyst absorbs light energy under the irradiation of light to generate electron transition to generate an electron-hole pair, so that the pollutants adsorbed on the surface are directly subjected to oxidation-reduction or the hydroxyl adsorbed on the surface is oxidized to generate hydroxyl radicals with strong oxidizing property to oxidize the pollutants.
In the sewage treatment process, because a large amount of granular and flocculent sludge exists in the sewage, the sludge is easy to agglomerate or precipitate on the lamp tube in the photocatalytic oxidation process, thereby causing light to be shielded, reducing the photocatalytic effect and being not beneficial to the sewage treatment efficiency.
The existing common photocatalyst is TiO2, the TiO2 photocatalyst has self limitation, the band gap energy is larger and is 3.2eV, only when ultraviolet light with the wavelength of less than 387.5nm irradiates the surface of the photocatalyst, electrons can be excited, the ultraviolet part in sunlight is less than 5%, and the utilization rate of indoor visible light is lower. In addition, the photo-generated electrons and holes generated by exciting TiO2 are easy to recombine, and the hydroxyl free radicals with higher excited oxidation activity are reduced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a nano photocatalytic ceramic material, which has the advantages of high catalytic efficiency, corrosion resistance, cleaning resistance, high mechanical strength, stable structure, no deformation and long service life, and the enrichment adsorption effect of a porous inorganic ceramic membrane contained in the composite material and the unique charge transmission performance of a carbon nano tube.
In order to achieve the aim of the invention, the invention adopts the specific scheme that:
a nano photocatalytic ceramic material is prepared from the following raw materials in parts by weight: SiO 226-10 parts of Al2O32-8 parts of CaO1-5 parts of MgO1-3 parts of TiO23-6 parts of K2O1-3 parts, Na2The composite photocatalyst comprises, by weight, O2-4 parts, diatomite 40-60 parts, nano shell powder 15-20 parts, a composite photocatalyst 6-12 parts, a surfactant 2-4 parts, a dispersant 1-3 parts, and a proper amount of deionized water.
Further, the composite photocatalyst is a Zr-BiVO4 photocatalyst, and the preparation method of the Zr-BiVO4 photocatalyst comprises the following steps:
(1) dissolving bismuth nitrate in 55-60% concentrated nitric acid, adding water to dilute to 5-7mol/L while stirring, and uniformly stirring to obtain a bismuth nitrate acid solution;
(2) dissolving potassium metavanadate in 5-7mol/L potassium hydroxide solution, and uniformly stirring to obtain potassium metavanadate solution;
(3) dripping the potassium metavanadate solution into the bismuth nitrate acid solution while stirring, and stirring for 15-20min after dripping;
(4) adding zirconium nitrate into the mixed solution obtained in the step (3), stirring and dissolving completely, adding dilute nitric acid or dilute potassium hydroxide solution to adjust the pH of the solution to be neutral, and continuing stirring for 20-30 min;
(5) and (3) transferring the mixed solution obtained in the step (4) into a stainless steel hot kettle with a polytetrafluoroethylene lining for sealing reaction, taking out the reaction kettle after the reaction is finished, cooling to room temperature, removing a supernatant, centrifuging, washing and drying to obtain Zr-BiVO4 photocatalyst powder, wherein the particle size of the Zr-BiVO4 photocatalyst powder is 10-100 nm.
Further, the preparation method of the nano photocatalytic ceramic material comprises the following steps:
(1)SiO2、Al2O3、CaO、MgO、TiO2、K2O、Na2adding O into a ball mill, adding a proper amount of water, and stirring to obtain paste;
(2) adding diatomite into a ball mill, grinding and crushing, soaking for 2-5h by using 10% nitric acid, filtering, washing to be neutral, drying, then putting into a muffle furnace for gradient calcination, naturally cooling to room temperature after calcination, grinding and sieving to obtain activated diatomite, wherein the particle size of the activated diatomite is 7-80 nm;
(3) preparation of shell powder: cleaning shell with clear water, drying, and pulverizing into 0.1-0.6mm coarse shell powder in ball mill; soaking the shell coarse micro powder in 10% nitric acid for 2-5h, filtering, washing to neutrality, drying, gradient calcining in a muffle furnace, and naturally cooling to room temperature after calcining; grinding and crushing the calcined shell powder to obtain activated nano shell powder, wherein the particle size of the activated nano shell powder is 8-75 nm;
(3) preparing a nano ceramic material: adding the composite photocatalyst and deionized water into a ball mill, uniformly mixing, adding the paste prepared in the step (1), the activated diatomite prepared in the step (2) and the nano shell powder prepared in the step (3), mechanically mixing for 2-4h to enable the composite photocatalyst to be fully adsorbed in the interlamination of the diatomite, adding a surfactant and a dispersing agent, uniformly mixing, evaporating to remove water, calcining in a muffle furnace at 400-550 ℃ for 3-5h, and grinding to obtain the porous-based nano ceramic material fixedly supported by the composite photocatalyst, wherein the particle size of the porous-based nano ceramic material is 11-120 nm.
The invention has the beneficial effects that:
the immobilization of the photocatalyst is directly realized on the ceramic, and the photocatalytic performance is improved; TiO2 is directly added on the nano ceramic, so that the preparation method is simple; the composite material has the advantages of high catalytic efficiency, corrosion resistance, cleaning resistance, high mechanical strength, stable structure, no deformation and long service life due to the enrichment adsorption effect of the porous inorganic ceramic membrane and the unique charge transmission performance of the carbon nano tube.
Detailed Description
The present invention is further described below by way of specific examples, but the present invention is not limited to only the following examples. Variations, combinations, or substitutions of the invention, which are within the scope of the invention or the spirit, scope of the invention, will be apparent to those of skill in the art and are within the scope of the invention.
A nano photocatalytic ceramic material is prepared from the following raw materials in parts by weight: SiO 226-10 parts of Al2O32-8 parts of CaO1-5 parts of MgO1-3 parts of TiO23-6 parts of K2O1-3 parts, Na2The composite photocatalyst comprises, by weight, O2-4 parts, diatomite 40-60 parts, nano shell powder 15-20 parts, a composite photocatalyst 6-12 parts, a surfactant 2-4 parts, a dispersant 1-3 parts, and a proper amount of deionized water.
The composite photocatalyst is a Zr-BiVO4 photocatalyst, and the preparation method of the Zr-BiVO4 photocatalyst comprises the following steps:
(1) dissolving bismuth nitrate in 55-60% concentrated nitric acid, adding water to dilute to 5-7mol/L while stirring, and uniformly stirring to obtain a bismuth nitrate acid solution;
(2) dissolving potassium metavanadate in 5-7mol/L potassium hydroxide solution, and uniformly stirring to obtain potassium metavanadate solution;
(3) dripping the potassium metavanadate solution into the bismuth nitrate acid solution while stirring, and stirring for 15-20min after dripping;
(4) adding zirconium nitrate into the mixed solution obtained in the step (3), stirring and dissolving completely, adding dilute nitric acid or dilute potassium hydroxide solution to adjust the pH of the solution to be neutral, and continuing stirring for 20-30 min;
(5) and (3) transferring the mixed solution obtained in the step (4) into a stainless steel hot kettle with a polytetrafluoroethylene lining for sealing reaction, taking out the reaction kettle after the reaction is finished, cooling to room temperature, removing a supernatant, centrifuging, washing and drying to obtain Zr-BiVO4 photocatalyst powder, wherein the particle size of the Zr-BiVO4 photocatalyst powder is 10-100 nm.
The preparation method of the nano photocatalytic ceramic material comprises the following steps:
(1)SiO2、Al2O3、CaO、MgO、TiO2、K2O、Na2adding O into a ball mill, adding a proper amount of water, and stirring to obtain paste;
(2) adding diatomite into a ball mill, grinding and crushing, soaking for 2-5h by using 10% nitric acid, filtering, washing to be neutral, drying, then putting into a muffle furnace for gradient calcination, naturally cooling to room temperature after calcination, grinding and sieving to obtain activated diatomite, wherein the particle size of the activated diatomite is 7-80 nm;
(3) preparation of shell powder: cleaning shell with clear water, drying, and pulverizing into 0.1-0.6mm coarse shell powder in ball mill; soaking the shell coarse micro powder in 10% nitric acid for 2-5h, filtering, washing to neutrality, drying, gradient calcining in a muffle furnace, and naturally cooling to room temperature after calcining; grinding and crushing the calcined shell powder to obtain activated nano shell powder, wherein the particle size of the activated nano shell powder is 8-75 nm;
(3) preparing a nano ceramic material: adding the composite photocatalyst and deionized water into a ball mill, uniformly mixing, adding the paste prepared in the step (1), the activated diatomite prepared in the step (2) and the nano shell powder prepared in the step (3), mechanically mixing for 2-4h to enable the composite photocatalyst to be fully adsorbed in the interlamination of the diatomite, adding a surfactant and a dispersing agent, uniformly mixing, evaporating to remove water, calcining in a muffle furnace at 400-550 ℃ for 3-5h, and grinding to obtain the porous-based nano ceramic material fixedly supported by the composite photocatalyst, wherein the particle size of the porous-based nano ceramic material is 11-120 nm.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (3)
1. A nano-class photocatalytic ceramic materialCharacterized in that the medicine is prepared from the following raw materials in parts by weight: SiO 226-10 parts of Al2O32-8 parts of CaO1-5 parts of MgO1-3 parts of TiO23-6 parts of K2O1-3 parts, Na2The composite photocatalyst comprises, by weight, O2-4 parts, diatomite 40-60 parts, nano shell powder 15-20 parts, a composite photocatalyst 6-12 parts, a surfactant 2-4 parts, a dispersant 1-3 parts, and a proper amount of deionized water.
2. The nano photocatalytic ceramic material as set forth in claim 1, wherein the composite photocatalyst is a Zr-BiVO4 photocatalyst, and the preparation method of the Zr-BiVO4 photocatalyst is:
(1) dissolving bismuth nitrate in 55-60% concentrated nitric acid, adding water to dilute to 5-7mol/L while stirring, and uniformly stirring to obtain a bismuth nitrate acid solution;
(2) dissolving potassium metavanadate in 5-7mol/L potassium hydroxide solution, and uniformly stirring to obtain potassium metavanadate solution;
(3) dripping the potassium metavanadate solution into the bismuth nitrate acid solution while stirring, and stirring for 15-20min after dripping;
(4) adding zirconium nitrate into the mixed solution obtained in the step (3), stirring and dissolving completely, adding dilute nitric acid or dilute potassium hydroxide solution to adjust the pH of the solution to be neutral, and continuing stirring for 20-30 min;
(5) and (3) transferring the mixed solution obtained in the step (4) into a stainless steel hot kettle with a polytetrafluoroethylene lining for sealing reaction, taking out the reaction kettle after the reaction is finished, cooling to room temperature, removing a supernatant, centrifuging, washing and drying to obtain Zr-BiVO4 photocatalyst powder, wherein the particle size of the Zr-BiVO4 photocatalyst powder is 10-100 nm.
3. The nano-photocatalytic ceramic material as set forth in claim 1, wherein the preparation method of the nano-photocatalytic ceramic material comprises the steps of:
(1)SiO2、Al2O3、CaO、MgO、TiO2、K2O、Na2adding O into a ball mill, adding a proper amount of water, and stirring to obtain paste;
(2) adding diatomite into a ball mill, grinding and crushing, soaking for 2-5h by using 10% nitric acid, filtering, washing to be neutral, drying, then putting into a muffle furnace for gradient calcination, naturally cooling to room temperature after calcination, grinding and sieving to obtain activated diatomite, wherein the particle size of the activated diatomite is 7-80 nm;
(3) preparation of shell powder: cleaning shell with clear water, drying, and pulverizing into 0.1-0.6mm coarse shell powder in ball mill; soaking the shell coarse micro powder in 10% nitric acid for 2-5h, filtering, washing to neutrality, drying, gradient calcining in a muffle furnace, and naturally cooling to room temperature after calcining; grinding and crushing the calcined shell powder to obtain activated nano shell powder, wherein the particle size of the activated nano shell powder is 8-75 nm;
(3) preparing a nano ceramic material: adding the composite photocatalyst and deionized water into a ball mill, uniformly mixing, adding the paste prepared in the step (1), the activated diatomite prepared in the step (2) and the nano shell powder prepared in the step (3), mechanically mixing for 2-4h to enable the composite photocatalyst to be fully adsorbed in the interlamination of the diatomite, adding a surfactant and a dispersing agent, uniformly mixing, evaporating to remove water, calcining in a muffle furnace at 400-550 ℃ for 3-5h, and grinding to obtain the porous-based nano ceramic material fixedly supported by the composite photocatalyst, wherein the particle size of the porous-based nano ceramic material is 11-120 nm.
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| CN112316743A (en) * | 2020-10-22 | 2021-02-05 | 哈尔滨工业大学（威海） | Preparation method of low-cost low-density catalytic functional ceramic membrane |
| CN114195482A (en) * | 2021-12-31 | 2022-03-18 | 安徽世倾环保科技有限公司 | Shell powder-based porous high-temperature-resistant material and preparation method and application thereof |
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| CN109019964A (en) * | 2018-08-17 | 2018-12-18 | 盛世瑶兰（深圳）科技有限公司 | A kind of nano ceramic material based on environmental protection |
| CN109233455A (en) * | 2018-08-30 | 2019-01-18 | 深圳市南硕明泰科技有限公司 | A kind of diatom ooze coating with catharsis |
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| CN109019964A (en) * | 2018-08-17 | 2018-12-18 | 盛世瑶兰（深圳）科技有限公司 | A kind of nano ceramic material based on environmental protection |
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| CN112316743A (en) * | 2020-10-22 | 2021-02-05 | 哈尔滨工业大学（威海） | Preparation method of low-cost low-density catalytic functional ceramic membrane |
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| CN114195482A (en) * | 2021-12-31 | 2022-03-18 | 安徽世倾环保科技有限公司 | Shell powder-based porous high-temperature-resistant material and preparation method and application thereof |
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