CN111229194A - (TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2Preparation and use of catalysts - Google Patents
(TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2Preparation and use of catalysts Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 229910052681 coesite Inorganic materials 0.000 title claims abstract description 75
- 229910052906 cristobalite Inorganic materials 0.000 title claims abstract description 75
- 229910052682 stishovite Inorganic materials 0.000 title claims abstract description 75
- 229910052905 tridymite Inorganic materials 0.000 title claims abstract description 75
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 73
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 239000011941 photocatalyst Substances 0.000 claims abstract description 24
- 239000002131 composite material Substances 0.000 claims abstract description 21
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- TWWPCKXWXDAZOR-UHFFFAOYSA-N [Zr].[Ti].[Si] Chemical compound [Zr].[Ti].[Si] TWWPCKXWXDAZOR-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 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 claims abstract description 8
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 7
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims abstract description 7
- 231100000719 pollutant Toxicity 0.000 claims abstract description 7
- 229910000348 titanium sulfate Inorganic materials 0.000 claims abstract description 7
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 238000000967 suction filtration Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 21
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000010936 titanium Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000004793 Polystyrene Substances 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 229910052726 zirconium Inorganic materials 0.000 claims description 10
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 9
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 9
- 229920002223 polystyrene Polymers 0.000 claims description 9
- 239000002243 precursor Substances 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052719 titanium Inorganic materials 0.000 claims description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 7
- 229940043267 rhodamine b Drugs 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003760 magnetic stirring Methods 0.000 claims description 6
- 239000000356 contaminant Substances 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000011022 opal Substances 0.000 claims description 5
- 230000000593 degrading effect Effects 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000007858 starting material Substances 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000001179 sorption measurement Methods 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000012512 characterization method Methods 0.000 abstract 1
- VZJJZMXEQNFTLL-UHFFFAOYSA-N chloro hypochlorite;zirconium;octahydrate Chemical compound O.O.O.O.O.O.O.O.[Zr].ClOCl VZJJZMXEQNFTLL-UHFFFAOYSA-N 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 14
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 12
- 239000013078 crystal Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000969 carrier Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 239000004038 photonic crystal Substances 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
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- 230000005484 gravity Effects 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 229920005553 polystyrene-acrylate Polymers 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
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- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
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- 238000002791 soaking Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- 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
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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Abstract
The invention discloses a (TiO)2‑ZrO2‑SiO2) @ inverse opal structure SiO2The preparation and application of the catalyst are characterized in that zirconium oxychloride octahydrate, ethyl orthosilicate and titanium sulfate are used as starting raw materials to prepare titanium-silicon-zirconium sol, and the titanium-silicon-zirconium sol is filled into SiO (silicon dioxide) with a pre-prepared inverse opal structure through a suction filtration method2In (1). Finally, titanium-silicon-zirconium sol @ inverse opal structure SiO2The compound is thermally treated in a muffle furnace to obtain TiO2‑ZrO2‑SiO2@ inverse opal structure SiO2A catalyst. Characterization of the light of the prepared catalyst by the degradation rate of rhodamine BAnd (3) catalytic activity. The TiO prepared by the invention is due to the synergistic effect between the porous ordered inverse opal structure and different oxides2‑ZrO2‑SiO2@ inverse opal structure SiO2The composite photocatalyst has good adsorption and photocatalysis performances, and the pollutant degradation efficiency is greatly improved. The invention has the characteristics of simple process, short period, low energy consumption and low cost.
Description
Technical Field
The invention belongs to the technical field of inorganic non-metallic materials, relates to a preparation method of core-shell three-dimensional ordered inverse opal structure powder, and particularly relates To (TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2Preparation and application of the catalyst.
Background
TiO has been used2The powder is always a hot point of research of scientists due to the excellent characteristics of the powder, has the characteristics of low cost, environmental friendliness, good physical stability and chemical stability and the like, and is a material with great potential for photocatalytic degradation of organic pollutants. Due to pure phase of TiO2The powder has larger forbidden band width, low utilization rate of visible light, small specific surface area, serious agglomeration, difficult recovery and other defects, and influences the application of the powder in the field of environmental management. More and more researchers today place the center of gravity of work on TiO2The powder modification was studied. Research shows that the inverse opal structure TiO is prepared by regulating and controlling the microstructure and the components2The composite powder can effectively widen TiO2The response range to visible light improves the photocatalytic efficiency. This is because the co-action of the different components can reduce TiO2The forbidden band width effectively inhibits the recombination rate of photon-generated carriers. Meanwhile, the special shape of the inverse opal structure can improve TiO2Absorption of light.
Currently prepared inverse opal structure TiO2The common method for composite powder is colloid crystal template method, and the common template agent is SiO2Polystyrene and polymethylmethacrylate microspheres. The specific process is to fill the precursor compound into a photonic crystal template and remove the template agent to obtain the inverse opal structure TiO2And (3) composite powder. The method can be used for preparing reversed eggsWhite stone structure TiO2The ordered structure of (A) is easily destroyed in the process of removing the template agent, and the pore diameter is also shrunk to a great extent. And the organic matter can affect TiO in the process of removing2If the calcination time is prolonged to completely remove the organic template, the crystallinity and the crystal phase of the organic template can also lead TiO2And (4) growing crystal grains.
Disclosure of Invention
In order to overcome the disadvantages of the prior art, the invention aims to provide (TiO) with simple process, short period, low energy consumption, low cost and good product structural integrity2-ZrO2-SiO2) @ inverse opal structure SiO2The preparation method of the catalyst is used for researching the adsorption and photocatalysis performance of the catalyst, and the application direction is provided.
In order to achieve the purpose, the invention adopts the technical scheme that:
(TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2The preparation method of the catalyst comprises the following steps:
the method comprises the following steps: preparing SiO by using tetraethoxysilane as a starting material, absolute ethyl alcohol and deionized water as solvents and ammonia water to regulate and control hydrolysis rate2Sol;
step two: taking the obtained SiO2Mixing sol and polystyrene emulsion, ultrasonic treating, pouring into crystallizing dish, depositing in oven, and removing polystyrene template to obtain SiO with inverse opal structure2；
Step three: under the condition of continuous magnetic stirring, adding ammonia water into deionized water, and adding zirconium oxychloride and citric acid to prepare a zirconium precursor solution; dissolving ethyl orthosilicate in absolute ethyl alcohol to prepare ethyl orthosilicate solution; dissolving titanium sulfate in deionized water to prepare a titanium solution;
step four: under the condition of continuous magnetic stirring, adding an ethyl orthosilicate solution and a titanium solution into a zirconium precursor solution in sequence to prepare titanium-silicon-zirconium sol;
step five: rapidly filling the obtained titanium-silicon-zirconium sol into SiO with inverse opal structure by a suction filtration method2Drying, placing in a crucible, and performing heat treatment to obtain (TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2A catalyst.
In the first step, the volume ratio of ethyl orthosilicate, absolute ethyl alcohol, deionized water to ammonia water is 2 (5-10): (0.5-5.5): (0.1-1), continuously stirring the mixture until the mixed solution is clarified to obtain SiO2Sol, SiO2The volume ratio of the sol to the polystyrene emulsion is (0.5-3): 3.
and in the second step, performing ultrasonic treatment for 30-60 min, pouring into a crystallizing dish, and putting into a drying oven at 35-60 ℃ for deposition.
In the third step, the zirconium ion concentration in the zirconium precursor solution is 0.05 +/-0.1 moL/L, the pH value is adjusted to 7-10 by ammonia water, the mass ratio of zirconium oxychloride to citric acid is 0.5:2, and the adding amount of the raw materials of titanium sulfate, zirconium oxychloride and tetraethoxysilane is determined according to the following formula, wherein n (Ti), n (Zr), n (Si) and (3-6): 1: (2-4).
And fifthly, carrying out heat treatment for 1-2 h at 450-850 ℃ in a muffle furnace.
The (TiO) prepared by the invention2-ZrO2-SiO2) @ inverse opal structure SiO2The catalyst can be used as a composite photocatalyst for degrading pollutants.
Preferably, the contaminant is an organic contaminant, such as rhodamine B.
Compared with the prior art, the invention has the beneficial effects that:
1. (TiO) produced by the invention2-ZrO2-SiO2) @ inverse opal structure SiO2The composite photocatalyst is SiO with inverse opal structure with good mechanical property2The titanium-silicon-zirconium sol is quickly filled into the gap for supporting the structure, and the TiO with the inverse opal structure with the complete structure can be obtained after calcination at 500-800 DEG C2-ZrO2-SiO2And (3) powder. In the temperature range, the SiO with the inverse opal structure can not be calcined2The skeleton is influenced, so that the TiO with the inverse opal structure with complete structure can be easily obtained2-ZrO2-SiO2Powder with almost no significant shrinkage of pore diameterThe porous structure is kept to have the advantage of large specific surface area.
2、ZrO2The composite material is the only oxide with acid and alkaline sites, is an excellent adsorption material, and Zr and Ti belong to the same family, have similar properties, have good matching property after being compounded, can keep respective advantages, and generate a new catalytic active site through the synergistic action of titanium and zirconium; at the same time, TiO can be reduced2The forbidden band width of the composite catalyst improves the response of the composite catalyst to visible light. Thus The (TiO) prepared by the present invention2-ZrO2-SiO2) @ inverse opal structure SiO2The composite photocatalyst has excellent adsorption performance and good photocatalytic degradation performance, and can improve the efficiency of pollutant degradation to a great extent.
3、SiO2Has large specific surface area, high mechanical strength, and no absorption to ultraviolet light and visible light, and is a very good photocatalyst carrier. SiO with inverse opal structure2The catalyst can be used repeatedly to maintain the integrity of the inverse opal structure.
4、SiO2The introduction of the crystal can effectively inhibit the growth of crystal grains and the transformation of crystal forms. ZrO (ZrO)2The best photocatalytic performance in the tetragonal phase, and research shows that ZrO has the best photocatalytic performance2-SiO2In the system, metastable tetragonal phase ZrO2Can exist over a wide temperature range. SiO 22Will hinder the TiO2Growth of grains resulting in TiO2The lattice is distorted, more defects are generated, and the active sites of the photocatalytic surface are increased. Due to the mesoporous structure, photo-generated carriers are easy to migrate to the surface to participate in the oxidation-reduction reaction in the process of photocatalytic reaction, and the photocatalytic efficiency is effectively improved.
5. Ordinary TiO2The powder has small specific surface area, so that a photon-generated carrier is easy to compound, and the photocatalytic efficiency is low; nano TiO 22The surface energy of the photocatalyst is large and easy to agglomerate, and the play of the photocatalytic activity is influenced. (TiO) produced by the invention2-ZrO2-SiO2) @ inverse opal structure SiO2The composite photocatalyst has good photocatalytic activity. Because the existence of the inverse opal structure can not only increase the specific surface area of the photocatalyst and provide more adsorption active sites, but also the photon local effect and the slow photon effect of the photonic crystal with the inverse opal structure are beneficial to the absorption and utilization of the photocatalyst to light.
Drawings
FIG. 1 is The (TiO) prepared in example 12-ZrO2-SiO2) @ inverse opal structure SiO2SEM photograph of the composite photocatalyst.
FIG. 2 is The (TiO) prepared in example 12-ZrO2-SiO2) @ inverse opal structure SiO2And (3) a photocatalytic degradation diagram of the composite photocatalyst for rhodamine B.
Detailed Description
The invention is further described with reference to the following figures and detailed description, without limiting its scope.
Example 1
(TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2The preparation process of the composite photocatalyst comprises the following specific processes:
the method comprises the following steps: SiO with inverse opal structure2And (4) preparing. Measuring 2mL of tetraethoxysilane, and then, according to the volume ratio of the raw materials: mixing ethyl orthosilicate, absolute ethyl alcohol, deionized water and ammonia water in a ratio of 2:8:5:0.1, continuously stirring the raw materials until the mixed solution is clear to obtain SiO2And (3) sol. Measuring a certain amount of SiO2The sol is mixed with the polystyrene emulsion. Wherein the volume ratio of the two is SiO2Sol polystyrene emulsion 1: 3. Ultrasonic treating for 30min, pouring into crystallizing dish, and oven-drying at 40 deg.C for deposition. Finally removing the polystyrene template to obtain the SiO with the inverse opal structure2And (5) standby.
Step two: and (3) preparing titanium-silicon-zirconium sol. Under the condition of continuous magnetic stirring, dissolving zirconium oxychloride and citric acid in 20mL of deionized water, adding ammonia water, adjusting the pH value to 7-10, and preparing a uniform and transparent solution with the zirconium ion concentration of 0.05moL/L, namely a zirconium precursor solution. Wherein the mass ratio of the zirconium oxychloride to the citric acid is 0.5: 2. Dissolving ethyl orthosilicate in absolute ethyl alcohol to prepare ethyl orthosilicate solution. Dissolving titanium sulfate in deionized water to prepare a titanium solution. Wherein the addition amount of the raw materials of the titanium sulfate, the zirconium oxychloride and the tetraethoxysilane is determined according to the following formula, wherein n (Ti), n (Zr), n (Si) and 1: 4. Under the condition of continuous magnetic stirring, adding an ethyl orthosilicate solution and a titanium solution into a zirconium precursor solution in sequence to prepare the titanium-silicon-zirconium sol.
(3) Step three: (TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2And (3) preparing the composite photocatalyst. The SiO with the inverse opal structure obtained in the step one2Soaking in titanium-zirconium-silicon sol for 30min, rapidly removing excessive titanium-zirconium-silicon sol by suction filtration, drying at certain temperature, placing in a crucible, and heat treating in a muffle furnace at 800 deg.C for 2 hr to obtain (TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2A composite photocatalyst is provided.
As can be seen from FIG. 1, the prepared sample has a complete structure and a pore diameter of about 220 nm.
(TiO) obtained by the invention2-ZrO2-SiO2) @ inverse opal structure SiO2The catalyst can be used as a composite photocatalyst for degrading pollutants, for example, rhodamine B is taken as an example, and the degradation process and the principle are as follows: first of all with large specific surface area and adsorption active sites (TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2The catalyst can quickly adsorb pollutant molecules; when the photocatalyst is irradiated by sunlight, due to the existence of the inverse opal structure, the absorption and utilization of the photocatalyst to light can be greatly improved by the photon local effect and the slow photon effect of the photocatalyst. Moreover, the inverse opal structure has a pore channel structure, and photo-generated carriers are easy to migrate to the surface to participate in an oxidation-reduction reaction in the photocatalytic reaction process, so that the degradation efficiency of photocatalysis on rhodamine B is effectively improved.
As can be seen from the graph 2, the adsorption equilibrium is achieved after the dark reaction is carried out for 30min, and the adsorption rate reaches 99%, at the moment, the photocatalyst powder is red, and rhodamine B is adsorbed on the surface of the photocatalyst. After the illumination is continued for 30min, the powder color is restored to the original white color, which indicates that the rhodamine B is completely degraded at the moment.
That is, the TiO prepared by the present invention is due to the synergistic effect between the porous ordered inverse opal structure and the different oxides2-ZrO2-SiO2@ inverse opal structure SiO2The composite photocatalyst has good adsorption and photocatalysis performances, and the pollutant degradation efficiency is greatly improved.
Example 2
(TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2The procedure for preparing a composite photocatalyst was the same as in example 1 except that the impregnation time was varied.
In this embodiment: the immersion time was 1 h.
Example 3
(TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2The procedure for preparing a composite photocatalyst was the same as in example 1 except that the heat treatment temperature was changed.
In this embodiment: the heat treatment temperature was 700 ℃.
Claims (9)
1. (TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2The preparation method of the catalyst is characterized by comprising the following steps:
the method comprises the following steps: preparing SiO by using tetraethoxysilane as a starting material, absolute ethyl alcohol and deionized water as solvents and ammonia water to regulate and control hydrolysis rate2Sol;
step two: taking the obtained SiO2Mixing sol and polystyrene emulsion, ultrasonic treating, pouring into crystallizing dish, depositing in oven, and removing polystyrene template to obtain SiO with inverse opal structure2；
Step three: under the condition of continuous magnetic stirring, adding ammonia water into deionized water, and adding zirconium oxychloride and citric acid to prepare a zirconium precursor solution; dissolving ethyl orthosilicate in absolute ethyl alcohol to prepare ethyl orthosilicate solution; dissolving titanium sulfate in deionized water to prepare a titanium solution;
step four: under the condition of continuous magnetic stirring, adding an ethyl orthosilicate solution and a titanium solution into a zirconium precursor solution in sequence to prepare titanium-silicon-zirconium sol;
step five: rapidly filling the obtained titanium-silicon-zirconium sol into SiO with inverse opal structure by a suction filtration method2Drying, placing in a crucible, and performing heat treatment to obtain (TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2A catalyst.
2. The (TiO) according to claim 12-ZrO2-SiO2) @ inverse opal structure SiO2The preparation method of the catalyst is characterized in that in the first step, the volume ratio of ethyl orthosilicate, absolute ethyl alcohol, deionized water to ammonia water is 2 (5-10): (0.5-5.5): (0.1-1), continuously stirring the mixture until the mixed solution is clarified to obtain SiO2And (3) sol.
3. The (TiO) according to claim 12-ZrO2-SiO2) @ inverse opal structure SiO2The preparation method of the catalyst is characterized in that in the step one, SiO is adopted2The volume ratio of the sol to the polystyrene emulsion is (0.5-3): 3.
4. the (TiO) according to claim 12-ZrO2-SiO2) @ inverse opal structure SiO2The preparation method of the catalyst is characterized in that in the second step, ultrasonic treatment is carried out for 30-60 min, then the mixture is poured into a crystallizing dish, and the crystallizing dish is placed into a drying oven with the temperature of 35-60 ℃ for deposition.
5. The (TiO) according to claim 12-ZrO2-SiO2) @ inverse opal structure SiO2The preparation method of the catalyst is characterized in that in the third step, the zirconium ion concentration in the zirconium precursor solution is 0.05 +/-0.1 moL/L, the pH value is adjusted to 7-10 by ammonia water, the mass ratio of zirconium oxychloride to citric acid is 0.5:2, and the raw materials of titanium sulfate, zirconium oxychloride and ethyl orthosilicate are adoptedThe addition amount of (A) is determined by the following formula (I), wherein n (Ti), n (Zr), n (Si) and (3-6): 1: (2-4).
6. The (TiO) according to claim 12-ZrO2-SiO2) @ inverse opal structure SiO2The preparation method of the catalyst is characterized by comprising the step five, and the heat treatment is carried out in a muffle furnace at the temperature of 450-850 ℃ for 1-2 hours.
7. (TiO) prepared according to claim 12-ZrO2-SiO2) @ inverse opal structure SiO2The catalyst is used as a composite photocatalyst for degrading pollutants.
8. Use according to claim 7, wherein the contaminants are organic contaminants.
9. The use according to claim 8, wherein the organic contaminant is rhodamine B.
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