CN110075822B - Integral visible light catalytic material and preparation method thereof - Google Patents
Integral visible light catalytic material and preparation method thereof Download PDFInfo
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- CN110075822B CN110075822B CN201910340852.8A CN201910340852A CN110075822B CN 110075822 B CN110075822 B CN 110075822B CN 201910340852 A CN201910340852 A CN 201910340852A CN 110075822 B CN110075822 B CN 110075822B
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims abstract description 44
- 239000002243 precursor Substances 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 31
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 29
- 239000008103 glucose Substances 0.000 claims abstract description 29
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 22
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 13
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052726 zirconium Inorganic materials 0.000 claims abstract description 12
- 238000002791 soaking Methods 0.000 claims abstract description 11
- 239000002904 solvent Substances 0.000 claims abstract description 11
- 238000000034 method Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 235000019441 ethanol Nutrition 0.000 claims abstract 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 28
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 28
- 239000004327 boric acid Substances 0.000 claims description 28
- 238000003756 stirring Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 239000000243 solution Substances 0.000 abstract 8
- UUYKGYZJARXSGB-UHFFFAOYSA-N ethanol;ethoxy(trihydroxy)silane Chemical compound CCO.CCO[Si](O)(O)O UUYKGYZJARXSGB-UHFFFAOYSA-N 0.000 abstract 2
- NZMOWCJQSARWIV-UHFFFAOYSA-N [Si].[Zr].[B] Chemical compound [Si].[Zr].[B] NZMOWCJQSARWIV-UHFFFAOYSA-N 0.000 abstract 1
- AWZXLSSFNBRFCI-UHFFFAOYSA-N boric acid ethanol Chemical compound B(O)(O)O.C(C)O.C(C)O.C(C)O AWZXLSSFNBRFCI-UHFFFAOYSA-N 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 description 16
- 230000015556 catabolic process Effects 0.000 description 13
- 238000006731 degradation reaction Methods 0.000 description 13
- 239000011941 photocatalyst Substances 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 5
- 230000005284 excitation Effects 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000004064 recycling Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 206010070834 Sensitisation Diseases 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
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- A—HUMAN NECESSITIES
- 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
-
- 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
- B01J21/08—Silica
-
- 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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J35/39—
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- B01J35/60—
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
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- A—HUMAN NECESSITIES
- 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
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/26—Organic substances containing nitrogen or phosphorus
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- A—HUMAN NECESSITIES
- 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
- A62D2101/00—Harmful chemical substances made harmless, or less harmful, by effecting chemical change
- A62D2101/20—Organic substances
- A62D2101/28—Organic substances containing oxygen, sulfur, selenium or tellurium, i.e. chalcogen
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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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
Abstract
The invention discloses an integral visible light catalytic material and a preparation method thereof. The preparation method comprises the following steps: (1) preparing zirconium oxychloride precursor solution by using zirconium oxychloride, acetylacetone, hydrogen peroxide and absolute ethyl alcohol as raw materials; preparing a boric acid ethanol mixed solution by using ethanol as a solvent; preparing a glucose solution by using water as a solvent; preparing an ethyl orthosilicate ethanol solution by taking ethanol as a solvent, and uniformly mixing the ethyl orthosilicate ethanol solution and the solution to obtain a zirconium borosilicate precursor solution; (2) heating the boron-silicon-zirconium precursor solution in a water bath, soaking the sponge in the solution, taking out and drying the sponge, repeating the soaking and drying, and then carrying out high-temperature heat treatment to obtain the integral visible light catalytic material. The invention has the advantages of cheap and easily obtained raw materials, simple and easily controlled process, designable sample shape, larger specific surface area, high-efficiency and stable photocatalytic performance in the visible light range and cyclic utilization.
Description
Technical Field
The invention belongs to the technical field of preparation of photocatalysts, and particularly relates to an integral visible light catalytic material and a preparation method thereof.
Background
Environmental and energy issues are the biggest challenges facing humans. At present, the semiconductor material photocatalysis technology provides an effective way for treating environmental pollution and efficiently utilizing solar energy. Among them, TiO most representative2The photocatalyst has the advantages of no toxicity, good stability and low costLow catalytic activity, and the like, and is widely applied in the field of catalysis. However, TiO2Is a wide-band-gap semiconductor material, can be excited by ultraviolet light accounting for 3-4% of the total amount of sunlight, has low utilization rate of the sunlight and low photocatalytic efficiency, and seriously restricts TiO2Further development and application of the photocatalyst are provided. Therefore, research on novel photocatalysts and improvement of the utilization rate of sunlight and photocatalytic efficiency of the photocatalysts have become important research points of researchers in various countries.
In the published research reports, the composite photocatalyst is prepared by element doping, precious metal deposition, dye sensitization, morphological structure regulation and supported nano photocatalyst to improve the photocatalytic efficiency in the research, but the method mainly takes nano-scale materials and powder materials as main materials, is not beneficial to recycling, and is difficult to maintain higher photocatalytic activity. Different from the powder photocatalyst which is difficult to recycle, the monolithic photocatalytic material can be reused and has excellent cyclic degradation effect, so the method has great application prospect in the field of photocatalytic degradation and purification in the future.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an integral visible light catalytic material and a preparation method thereof, and the integral visible light catalytic material has the characteristics of cheap and easily-obtained raw materials, simple and easily-controlled process, designable sample shape, large specific surface area, high adsorption efficiency, high-efficiency and stable photocatalytic performance in a visible light range and excellent recycling performance.
In order to achieve the purpose, the invention adopts the technical scheme that:
an integral visible light catalytic material and a preparation method thereof, the steps are as follows:
(1) preparing a zirconium oxychloride precursor solution: weighing a certain amount of zirconium oxychloride, weighing acetylacetone and hydrogen peroxide with certain volumes, taking absolute ethyl alcohol as a solvent, dissolving the zirconium oxychloride, the acetylacetone and the hydrogen peroxide in the absolute ethyl alcohol, and uniformly stirring to obtain a zirconium oxychloride precursor solution.
(2) Preparing a boric acid solution: weighing a certain mass of boric acid according to the molar ratio of zirconium oxychloride to the boric acid of 1:5-1:8, dissolving the boric acid in absolute ethyl alcohol, and heating and stirring in a water bath at 60 ℃ for 5-15min to obtain a boric acid solution.
(3) Preparing a glucose solution: weighing a certain mass of glucose according to the mass ratio of zirconium oxychloride to glucose of 1:1-4:1, and dissolving the glucose in deionized water to obtain a glucose solution.
(4) Preparing an ethyl orthosilicate solution: according to the molar ratio of zirconium oxychloride to tetraethoxysilane of 1:3-1.5:3, calculating the required amount of ethyl orthosilicate, respectively measuring a certain volume of ethyl orthosilicate and absolute ethyl alcohol according to the volume ratio of 1:2-1:5, and uniformly mixing to obtain an ethyl orthosilicate solution.
(5) Preparing a zirconium borosilicate precursor solution: under the condition of continuous magnetic stirring, ethyl orthosilicate solution, boric acid solution and glucose solution are sequentially dripped into zirconium oxychloride precursor solution, magnetic stirring is carried out for 1-2h, and then zirconium borosilicate precursor solution is prepared, and heating and stirring are carried out for 6-8h for standby application at 60-80 ℃ in a water bath.
(6) Preparation of monolithic visible-light catalytic material: soaking sponge with certain shape and size in the precursor solution prepared in the step 5, drying at 60-80 ℃, and repeatedly soaking and drying for 1-5 times. And (3) placing the dried sponge in a muffle furnace, and carrying out heat treatment for 2h at the temperature of 500-900 ℃ to obtain the integral visible light catalytic material.
Compared with the prior art, the invention has the beneficial effects that:
1. the integral visible light catalytic material and the preparation method thereof have the advantages of cheap and easily-obtained raw materials, simple and easily-controlled process, sponge serving as a template, designable shape and easy satisfaction of actual production and use requirements.
2. The integral visible light catalytic material and the preparation method thereof have a porous structure, have high specific surface area, show strong dye adsorption capacity, and have visible light degradation capacity obviously superior to that of a commercial photocatalyst.
3. According to the integral visible light catalytic material and the preparation method thereof, the high-efficiency stable photocatalytic performance and the excellent recycling performance are achieved within the visible light range, in a reusability verification test, after adsorption and degradation are completed, the material is dried in the air, and an adsorption and degradation test is performed again, so that the adsorption and degradation performance is not obviously reduced.
Drawings
Fig. 1 is a macroscopic photograph and a scanning electron micrograph of the monolithic visible light catalytic material obtained in example 1.
Fig. 2 is a graph of the adsorption performance of the monolithic visible light catalytic material obtained in example 1.
Fig. 3 is a graph of the degradation of dye under visible light excitation of the multiple monolithic visible light catalytic material obtained in example 1.
Fig. 4 is a graph of the degradation of dye by visible light excitation of the monolithic visible light catalytic material in a repeated experiment.
Detailed Description
The embodiments of the present invention will be described in detail below with reference to the drawings and examples. The technical solution of the present invention is not limited to the following embodiments, but includes any combination of the embodiments.
Example 1
An integral visible light catalytic material and a preparation method thereof are realized according to the following steps:
(1) preparing a zirconium oxychloride precursor solution: weighing 1.5g of zirconium oxychloride, weighing 5mL of acetylacetone and 2mL of hydrogen peroxide, taking 20mL of absolute ethyl alcohol as a solvent, dissolving the zirconium oxychloride, the acetylacetone and the hydrogen peroxide in the absolute ethyl alcohol, and uniformly stirring to obtain a zirconium oxychloride precursor solution;
(2) preparing a boric acid solution: weighing a certain mass of boric acid according to the molar ratio of zirconium oxychloride to the boric acid of 1:6, dissolving the boric acid in 20mL of absolute ethanol, and heating and stirring in a water bath at 60 ℃ for 15min to obtain a boric acid solution.
(3) Preparing a glucose solution: weighing a certain mass of glucose according to the mass ratio of zirconium oxychloride to glucose of 3:1, and dissolving the glucose in 20mL of deionized water to obtain a glucose solution.
(4) Preparing an ethyl orthosilicate solution: calculating the required ethyl orthosilicate amount according to the molar ratio of zirconium oxychloride to ethyl orthosilicate of 1.5:3, respectively measuring a certain volume of ethyl orthosilicate and anhydrous ethanol according to the volume ratio of 1:3, and uniformly mixing to obtain an ethyl orthosilicate solution.
(5) Preparing a zirconium borosilicate precursor solution: under the condition of continuous magnetic stirring, ethyl orthosilicate solution, boric acid solution and glucose solution are sequentially dripped into zirconium oxychloride precursor solution, the solution is magnetically stirred for 2 hours to prepare zirconium borosilicate precursor solution, and the solution is continuously heated and stirred for 8 hours in a water bath at 60 ℃ for standby.
(6) Preparation of monolithic visible-light catalytic material: soaking sponge with certain shape and size in the precursor solution prepared in the step 5, drying at 60 ℃, and repeating soaking and drying for 5 times. And (3) placing the dried sponge in a muffle furnace, and carrying out heat treatment for 2h at 750 ℃ to obtain the integral visible light catalytic material.
FIG. 1 is a photomicrograph and a scanning electron micrograph of the monolithic visible light catalytic material obtained in example 1; as can be seen, the monolithic material can be successfully prepared by the method, and the pore size of the material is uniform and the distribution of the pore size is uniform.
Fig. 2 is a graph of the adsorption performance of the monolithic visible light catalytic material obtained in example 1. The concentration of rhodamine B is 10mg/L, the concentration of rhodamine B is continuously reduced along with the prolonging of the dark reaction time, the adsorption rate reaches 70% after the dark reaction for 90min, and the material has excellent adsorption performance.
Fig. 3 is a graph of the degradation of dye under visible light excitation of the multiple monolithic visible light catalytic material obtained in example 1. The concentration of rhodamine B is continuously reduced along with the prolonging of the photoreaction time, the degradation rate of rhodamine B reaches more than 90% after 120min of photoreaction, and the material has excellent visible light degradation performance.
Fig. 4 is a graph of the degradation of dye by visible light excitation of the monolithic visible light catalytic material in a repeated experiment. The concentration of rhodamine B is continuously reduced along with the prolonging of the photoreaction time, the degradation rate of rhodamine B basically reaches more than 90% after 120min of photoreaction, and the visible light degradation performance of the material is stable.
Example 2
An integral visible light catalytic material and a preparation method thereof are realized according to the following steps:
(1) preparing a zirconium oxychloride precursor solution: weighing 1g of zirconium oxychloride, weighing 2mL of acetylacetone and 1.5mL of hydrogen peroxide, taking 15mL of absolute ethyl alcohol as a solvent, dissolving the zirconium oxychloride, the acetylacetone and the hydrogen peroxide in the absolute ethyl alcohol, and uniformly stirring to obtain a zirconium oxychloride precursor solution;
(2) preparing a boric acid solution: weighing a certain mass of boric acid according to the molar ratio of zirconium oxychloride to the boric acid of 1:5, dissolving the boric acid in 20mL of absolute ethanol, and heating and stirring in a water bath at 60 ℃ for 15min to obtain a boric acid solution.
(3) Preparing a glucose solution: weighing a certain mass of glucose according to the mass ratio of zirconium oxychloride to glucose of 1:1, and dissolving the glucose in 10mL of deionized water to obtain a glucose solution.
(4) Preparing an ethyl orthosilicate solution: calculating the required ethyl orthosilicate amount according to the molar ratio of zirconium oxychloride to ethyl orthosilicate of 1:3, respectively measuring a certain volume of ethyl orthosilicate and anhydrous ethanol according to the volume ratio of 1:2, and uniformly mixing to obtain an ethyl orthosilicate solution.
(5) Preparing a zirconium borosilicate precursor solution: under the condition of continuous magnetic stirring, ethyl orthosilicate solution, boric acid solution and glucose solution are sequentially dripped into zirconium oxychloride precursor solution, the solution is magnetically stirred for 2 hours to prepare zirconium borosilicate precursor solution, and the zirconium borosilicate precursor solution is continuously heated and stirred for 6 hours in a water bath at the temperature of 80 ℃ for later use.
(6) Preparation of monolithic visible-light catalytic material: soaking sponge with certain shape and size in the precursor solution prepared in the step 5, drying at 60 ℃, and repeating soaking and drying for 5 times. And (3) placing the dried sponge in a muffle furnace, and carrying out heat treatment for 2h at 800 ℃ to obtain the integral visible light catalytic material.
Example 3
An integral visible light catalytic material and a preparation method thereof are realized according to the following steps:
(1) preparing a zirconium oxychloride precursor solution: weighing 1.2g of zirconium oxychloride, weighing 3mL of acetylacetone and 2mL of hydrogen peroxide, taking 20mL of absolute ethyl alcohol as a solvent, dissolving the zirconium oxychloride, the acetylacetone and the hydrogen peroxide in the absolute ethyl alcohol, and uniformly stirring to obtain a zirconium oxychloride precursor solution;
(2) preparing a boric acid solution: weighing a certain mass of boric acid according to the molar ratio of zirconium oxychloride to the boric acid of 1:8, dissolving the boric acid in 25mL of absolute ethanol, and heating and stirring in a water bath at 60 ℃ for 15min to obtain a boric acid solution.
(3) Preparing a glucose solution: weighing a certain mass of glucose according to the mass ratio of zirconium oxychloride to glucose of 4:1, and dissolving the glucose in 20mL of deionized water to obtain a glucose solution.
(4) Preparing an ethyl orthosilicate solution: calculating the required ethyl orthosilicate amount according to the molar ratio of zirconium oxychloride to ethyl orthosilicate of 1.5:3, respectively measuring a certain volume of ethyl orthosilicate and anhydrous ethanol according to the volume ratio of 1:5, and uniformly mixing to obtain an ethyl orthosilicate solution.
(5) Preparing a zirconium borosilicate precursor solution: under the condition of continuous magnetic stirring, ethyl orthosilicate solution, boric acid solution and glucose solution are sequentially dripped into zirconium oxychloride precursor solution, the solution is magnetically stirred for 2 hours to prepare zirconium borosilicate precursor solution, and the solution is continuously heated and stirred for 6 hours in a water bath at 60 ℃ for standby.
(6) Preparation of monolithic visible-light catalytic material: soaking sponge with certain shape and size in the precursor solution prepared in the step 5, drying at 80 ℃, and repeating soaking and drying for 5 times. And (3) placing the dried sponge in a muffle furnace, and carrying out heat treatment for 2h at 900 ℃ to obtain the integral visible light catalytic material.
Claims (5)
1. A preparation method of an integral visible light catalytic material is characterized by comprising the following steps:
(1) zirconium oxychloride precursor solution is prepared by taking zirconium oxychloride, acetylacetone and hydrogen peroxide as raw materials and absolute ethyl alcohol as a solvent; preparing a boric acid solution by using ethanol as a solvent; preparing a glucose solution by using deionized water as a solvent; preparing ethyl orthosilicate solution by taking ethanol as a solvent; uniformly mixing a zirconium oxychloride precursor solution, a boric acid solution, a glucose solution and an ethyl orthosilicate solution to obtain a zirconium borosilicate precursor solution, wherein the molar ratio of zirconium oxychloride to boric acid is 1:5-1:8, the molar ratio of zirconium oxychloride to ethyl orthosilicate is 1:3-1.5:3, and the mass ratio of zirconium oxychloride to glucose is 1:1-4: 1;
(2) and heating and stirring the obtained zirconium borosilicate precursor solution in a water bath, soaking the sponge in a certain shape in the solution, taking out and drying the sponge, and performing high-temperature heat treatment to obtain the integral visible light catalytic material, wherein the heat treatment temperature is 500-900 ℃, and the heat treatment time is 1.5-2.5 h.
2. The preparation method of the integral visible light catalytic material of claim 1, characterized in that the concentration of the prepared zirconium oxychloride precursor solution is 0.005-0.1g/mL, the volume ratio of acetylacetone to the zirconium oxychloride precursor solution is 0.5:6-1.5:6, the volume ratio of hydrogen peroxide to the zirconium oxychloride precursor solution is 1:10-1:15, the volume ratio of absolute ethyl alcohol to the zirconium oxychloride precursor solution is 2:3-2.5:3, the concentration of the boric acid solution is 0.0125-0.02 g/mL, the concentration of the ethyl orthosilicate solution is 0.065-0.195g/mL, and the concentration of the glucose solution is 0.025 g/mL.
3. The method for preparing the monolithic visible light catalytic material as claimed in claim 1, wherein in the step (2), the water bath heating temperature is 60-80 ℃ and the heating time is 6-8 h.
4. The method for preparing the monolithic visible light catalytic material as claimed in claim 1, wherein in the step (2), the drying temperature is 60-80 ℃ and the drying time is 12-24 h.
5. A monolithic visible light catalytic material obtained by the production method according to any one of claims 1 to 4.
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| CN103435766A (en) * | 2013-08-30 | 2013-12-11 | 西北工业大学 | Boron-zirconium-silicon ternary modified phenolic resin and preparation method thereof |
| CN104445381A (en) * | 2014-11-25 | 2015-03-25 | 辽宁大学 | Preparation method for mesoporous multi-element metal oxide |
| CN109225169A (en) * | 2018-09-19 | 2019-01-18 | 陕西科技大学 | A kind of preparation method and the photochemical catalyst aoxidizing the agent of zirconium base adsorption photochemical catalysis |
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| CN1956927A (en) * | 2004-05-21 | 2007-05-02 | 德古萨股份公司 | Ternary metal mixed oxide powder |
| CN101497003A (en) * | 2009-01-24 | 2009-08-05 | 大连理工大学 | Multifunctional photocatalysis composite ceramic separation membrane as well as preparation method and use thereof |
| CN103435766A (en) * | 2013-08-30 | 2013-12-11 | 西北工业大学 | Boron-zirconium-silicon ternary modified phenolic resin and preparation method thereof |
| CN104445381A (en) * | 2014-11-25 | 2015-03-25 | 辽宁大学 | Preparation method for mesoporous multi-element metal oxide |
| CN109225169A (en) * | 2018-09-19 | 2019-01-18 | 陕西科技大学 | A kind of preparation method and the photochemical catalyst aoxidizing the agent of zirconium base adsorption photochemical catalysis |
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