CN111659323B - Composite aerogel functional material and preparation method and application thereof - Google Patents
Composite aerogel functional material and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 50
- 239000004964 aerogel Substances 0.000 title claims abstract description 36
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000012855 volatile organic compound Substances 0.000 claims abstract description 10
- 229910003082 TiO2-SiO2 Inorganic materials 0.000 claims abstract description 9
- 230000032683 aging Effects 0.000 claims abstract description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 5
- 239000010703 silicon Substances 0.000 claims abstract description 5
- 239000010936 titanium Substances 0.000 claims abstract description 5
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 48
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 44
- 238000003756 stirring Methods 0.000 claims description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 37
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 22
- 229960000583 acetic acid Drugs 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 22
- 229910021641 deionized water Inorganic materials 0.000 claims description 22
- 239000012362 glacial acetic acid Substances 0.000 claims description 22
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 18
- 239000011259 mixed solution Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007864 aqueous solution Substances 0.000 claims description 11
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 11
- 229940071125 manganese acetate Drugs 0.000 claims description 11
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 11
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052681 coesite Inorganic materials 0.000 claims description 10
- 229910052906 cristobalite Inorganic materials 0.000 claims description 10
- 239000000377 silicon dioxide Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 229910052682 stishovite Inorganic materials 0.000 claims description 10
- 229910052905 tridymite Inorganic materials 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 5
- 238000013329 compounding Methods 0.000 claims description 4
- 229910020442 SiO2—TiO2 Inorganic materials 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- 239000003153 chemical reaction reagent Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 abstract description 26
- 239000003054 catalyst Substances 0.000 abstract description 13
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 6
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 238000006731 degradation reaction Methods 0.000 abstract description 5
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- 238000006303 photolysis reaction Methods 0.000 abstract description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000005284 excitation Effects 0.000 abstract 1
- 239000002243 precursor Substances 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 19
- 238000005303 weighing Methods 0.000 description 14
- 238000001879 gelation Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000003301 hydrolyzing effect Effects 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000008878 coupling Effects 0.000 description 4
- 238000010168 coupling process Methods 0.000 description 4
- 238000005859 coupling reaction Methods 0.000 description 4
- 239000010815 organic waste Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910016978 MnOx Inorganic materials 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000013543 active substance Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- UGACIEPFGXRWCH-UHFFFAOYSA-N [Si].[Ti] Chemical compound [Si].[Ti] UGACIEPFGXRWCH-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007886 mutagenicity Effects 0.000 description 1
- 231100000299 mutagenicity Toxicity 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
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- B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
- B01J13/0091—Preparation of aerogels, e.g. xerogels
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- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
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- 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
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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Abstract
A composite aerogel functional material, a preparation method and application thereof. The method comprises the following steps: firstly, preparing silicon and titanium mixed sol, and adding MnO with a certain proportion2The precursor solution is doped in a cogel mode, and subsequent process adjustment such as aging, replacement, normal-temperature and normal-pressure drying, roasting and the like is carried out on the alcogel to obtain MnOx‑TiO2‑SiO2A composite aerogel catalyst. MnO is improved by the three-dimensional reticular aerogel material prepared by the invention in a cogel modexThe particles are agglomerated, which is beneficial to catalytic oxidation by ozone contact. Through the introduction of 254nm ultraviolet light, under the action of light excitation, the generation and transfer of electrons are promoted, the synergistic effect of ozone photolysis, ozone oxidation and photocatalysis is realized, the utilization rate of ozone and ultraviolet light and the degradation efficiency of VOCs are greatly improved, and the service life of the catalyst is prolonged.
Description
Technical Field
The invention relates to the field of catalytic degradation of VOCs, and particularly relates to a composite aerogel functional material and a preparation method and application thereof.
Background
The industrial level drives the social and economic level to be continuously improved, the life quality of people is also improved, but the people continuously pursue the too high GDP, and the accelerated deterioration of the environment is caused, wherein the environment comprises atmospheric pollution, water body pollution, soil pollution and the like. Volatile Organic Compounds (VOCs) are main components in industrial waste gas, have the properties of hydrophobicity, volatility and the like, cause great threat to human survival by teratogenicity, carcinogenicity and mutagenicity, and become important work in the aspect of air pollution control along with the emergence of various policies in China. The ultraviolet coupling ozone oxidation method is an advanced oxidation technology, and organic waste gas is gradually decomposed into micromolecular substances through the interaction of the organic waste gas, ozone and ultraviolet light, and finally is decomposed into CO2And H2And O. Compared with other treatment methods, the normal-temperature catalysis method has the advantages of low energy consumption, high catalysis efficiency and the like, but has the defects of low utilization efficiency of light and ozone and the like. With the continuous and deep research on the ultraviolet coupling ozone oxidation method, the non-noble metal catalysts such as manganese, cobalt and the like show excellent performance in the reaction system, not only show certain adsorbability, but also greatly improve the utilization efficiency of light and ozone, so the research on the catalysts becomes a main hotspot for degrading organic waste gas by ultraviolet coupling ozone.
The currently researched catalyst aims at treating organic waste gas with large air quantity and low concentration, and still has the problems of poor adsorptivity, low light and ozone utilization efficiency, short service life of the catalyst and the like.
Disclosure of Invention
The technical problem to be solved is as follows: the invention aims to improve the utilization efficiency of a catalytic system to ozone, enhance the photoresponse and catalytic activity of a catalyst, and solve the problems of adsorption of VOCs and the like. Lifting deviceA254 nm ultraviolet lamp is selected as a light source, and the capability of the composite aerogel functional material for photolyzing ozone is fully utilized. At the same time, TiO is selected2-SiO2The composite aerogel is used as a support body, the advantages of high porosity, large specific surface area, strong conductivity, good surface acidity and the like of the composite aerogel are fully exerted, and the adsorption performance and the photocatalytic performance to substrates and ozone are enhanced. Doping MnO in a cogel mannerxThe active components can be better dispersed on the surface of the support body, the good utilization rate of ozone is kept, the photoresponse performance is enhanced, and the effect of fully degrading organic matters is achieved by generating more active substances.
The technical scheme is as follows: a preparation method of a composite aerogel functional material comprises the following preparation steps: (1) preparing a mixed solution of tetraethyl orthosilicate, absolute ethyl alcohol, deionized water and HCl, wherein the molar ratio n (TEOs) to n (EtOH) to n (H)2O): n(HCl)=1:（4～6）:（4～6）:2.4×10-3And putting the mixture into a mixer at 55 ℃ to be stirred and hydrolyzed for 2 to 4 hours to obtain SiO2Sol, marked as sol A; (2) dissolving tetrabutyl titanate in absolute ethyl alcohol, dropwise adding glacial acetic acid into the solution, and quickly stirring to obtain a solution B, wherein the molar ratio of tetrabutyl titanate to absolute ethyl alcohol to glacial acetic acid in the solution B is (1) (10-15) to (1-1.5); preparing a mixed solution C of absolute ethyl alcohol, glacial acetic acid and deionized water, wherein the molar ratio of the absolute ethyl alcohol to the glacial acetic acid to the deionized water is (1-3): 0-0.3): 1; dripping the solution C into the solution B to prepare TiO2The sol is marked as sol D, wherein the mass ratio of the solution C to the solution B is 1 (1-2); (3) adding the sol A into the sol D according to the molar ratio of silicon to titanium of 1 (1-5), and stirring to obtain SiO2-TiO2Compounding the sol followed by MnO of 1 wt.% to 15 wt.%xDropwise adding a pre-prepared 10 wt.% manganese acetate aqueous solution into the composite sol, adding a formamide reagent with a volume ratio of 1 (80-120) to the composite sol under a stirring state, and then placing the mixture in a 35 ℃ water bath kettle to obtain alcogel; (4) adding a mixed solution of tetraethyl orthosilicate and absolute ethyl alcohol in a volume ratio of 1 (3-5) into the obtained alcohol gel to completely immerse the gel, placing the gel in a water bath kettle at 50 ℃, and aging the gel for 12 minutesh, pouring out the supernatant, and performing at least 3 times of replacement on the supernatant by using n-hexane at 40 ℃; (5) placing the gel without the supernatant in a forced air drying box, and performing gradient drying; finally, roasting the mixture in a muffle furnace to obtain MnOx-TiO2-SiO2And (3) compounding the aerogel.
Preferably, TEOs, EtOH, H are contained in the sol A in the step (1)2The molar ratio of O to HCl is 1:4.95:4.95: 2.4X 10-3And the hydrolysis time under stirring is 3 hours.
Preferably, the molar ratio of tetrabutyl titanate, anhydrous ethanol and glacial acetic acid in the solution B in the step (2) is 1:13.6:1.1, the molar ratio of anhydrous ethanol, glacial acetic acid and deionized water in the solution C is 1.7:0.1:1, and the mass ratio of the solution C to the solution B is 1: 1.72.
Preferably, in the step (3), the molar ratio of silicon to titanium is 1:3, and MnO is addedxThe loading amount of the composite sol is 5 wt.%, and the volume ratio of the composite sol to formamide is 1: 110.
Preferably, the volume ratio of the tetraethyl orthosilicate and the absolute ethyl alcohol mixed solution in the step (4) is 1:4, the n-hexane replacement frequency is not less than 3 times, and the replacement time is not less than 3 hours.
Preferably, the gradient drying temperature in the step (5) is 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 150 ℃, and the temperature of each temperature point is kept for 2 hours, and the roasting temperature is 550 ℃ and 5 hours.
The composite aerogel functional material prepared by the preparation method.
The composite aerogel functional material is applied to VOCs treatment.
Has the advantages that: 1. the invention takes the 254nm ultraviolet lamp as the light source, which is beneficial to applying more light energy to the photolysis of ozone, increases the utilization efficiency of ozone, and simultaneously, the ultraviolet light wave can act on the substrate and the catalyst to cause the photocatalysis effect. 2. In the invention, TiO is used2-SiO2The composite aerogel is used as a support body, the common performances of high adsorption, strong electric conduction and the like of the aerogel can be fully exerted, and the surface acidity of the composite aerogel is favorable for adsorbing and decomposing VOCs and ozone. In the same way as thatOf TiO 22-SiO2The composite aerogel is used as a photocatalytic material to promote the synergistic generation of ozone photolysis and photocatalytic effect. 3. The invention reduces MnO by doping active components in a cogel modexThe agglomeration phenomenon of the particles increases the contact range of the ozone and improves the utilization rate of the ozone. 4. The preparation process of the invention is easy to control, and the shape of the catalyst can be changed through the gel condition, thus the compatibility of the catalytic material is increased while the good degradation effect on VOCs is kept.
Drawings
FIG. 1 is a schematic diagram of the removal rate of the composite aerogel functional material prepared in examples 1, 2 and 3 in an ultraviolet coupled ozone oxidation system for toluene;
FIG. 2 is a schematic diagram of the removal rate of the composite aerogel functional material prepared in examples 2, 4 and 5 in an ultraviolet coupled ozone oxidation system for toluene;
FIG. 3 shows two reaction systems O3Catalytic, ultraviolet coupled O3A schematic of the removal efficiency of oxidized p-toluene, wherein the catalyst was prepared as in example 2.
Detailed Description
The present invention will be described in more detail with reference to specific examples, but the present invention is not limited thereto.
Example 1
(1) Respectively weighing 6.62 g of absolute ethyl alcohol, 6.03 g of tetraethyl orthosilicate and 2.58 g of deionized water, sequentially adding the absolute ethyl alcohol, the tetraethyl orthosilicate and the deionized water into a beaker, stirring the mixture, adding 0.7 mL of HCl solution (0.1 mol/L) after uniformly stirring the mixture, placing the beaker at 55 ℃, stirring and hydrolyzing the mixture for 3 hours to obtain SiO2Marking the sol as sol A;
(2) dissolving 9.86 g of tetrabutyl titanate in 18.15 g of absolute ethyl alcohol, dropwise adding 2 g of glacial acetic acid into the mixed solution, stirring to obtain a solution B, weighing 13.41 g of absolute ethyl alcohol, 1 g of glacial acetic acid and 3.06 g of deionized water to prepare a solution C, and dropwise adding the solution C into the solution B to prepare TiO2Sol, marked as sol D;
(3) adding the sol A into the sol D, and stirring to obtain SiO2-TiO2Composite sol of 5 wt.% MnOxWeighing 4.3 g of 10 wt.% manganese acetate aqueous solution, adding the solution to the composite sol, finally adding 670 microliter formamide, uniformly stirring, and placing the beaker in a 35 ℃ water bath kettle for gelation;
(4) after gelation, adding a mixed solution of 5 mL tetraethyl orthosilicate and 20 mL absolute ethyl alcohol, placing a beaker in a water bath at 50 ℃ for 12 h, and after aging, replacing the gel with n-hexane at 40 ℃ for 3 times, each time for 3 h;
(5) and (3) performing gradient drying on the gel after the replacement is finished at 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 150 ℃, preserving heat for 2 h at each temperature point, roasting the dried sample at 550 ℃ for 5 h to obtain the composite functional aerogel: MnOx-TiO2-SiO2。
Example 2
(1) Respectively weighing 6.62 g of absolute ethyl alcohol, 6.03 g of tetraethyl orthosilicate and 2.58 g of deionized water, sequentially adding the absolute ethyl alcohol, the tetraethyl orthosilicate and the deionized water into a beaker, stirring the mixture, adding 0.7 mL of HCl solution (0.1 mol/L) after uniformly stirring the mixture, placing the beaker at 55 ℃, stirring and hydrolyzing the mixture for 3 hours to obtain SiO2Marking the sol as sol A;
(2) dissolving 9.86 g of tetrabutyl titanate in 18.15 g of absolute ethyl alcohol, dropwise adding 2 g of glacial acetic acid into the mixed solution, stirring to obtain a solution B, weighing 13.41 g of absolute ethyl alcohol, 1 g of glacial acetic acid and 3.06 g of deionized water to prepare a solution C, and dropwise adding the solution C into the solution B to prepare TiO2Sol, marked as sol D;
(3) 1/3 sol A is added into the sol D, and SiO is obtained under stirring2-TiO2Composite sol of MnO 5 wt.%xWeighing 3.1 g of 10 wt.% aqueous solution of manganese acetate, adding the aqueous solution of manganese acetate to the composite sol, finally adding 560 μ L of formamide, uniformly stirring, and placing the beaker in a 35 ℃ water bath kettle for gelation;
(4) after gelation, adding a mixed solution of 5 mL tetraethyl orthosilicate and 20 mL absolute ethyl alcohol, placing a beaker in a water bath at 50 ℃ for 12 h, and after aging, replacing the gel with n-hexane at 40 ℃ for 3 times, each time for 3 h;
(5) and (3) performing gradient drying on the gel after the replacement is finished at 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 150 ℃, preserving heat for 2 h at each temperature point, roasting the dried sample at 550 ℃ for 5 h to obtain the composite functional aerogel: MnOx-TiO2-SiO2。
Example 3
(1) Respectively weighing 6.62 g of absolute ethyl alcohol, 6.03 g of tetraethyl orthosilicate and 2.58 g of deionized water, sequentially adding the absolute ethyl alcohol, the tetraethyl orthosilicate and the deionized water into a beaker, stirring the mixture, adding 0.7 mL of HCl solution (0.1 mol/L) after uniformly stirring the mixture, placing the beaker at 55 ℃, stirring and hydrolyzing the mixture for 3 hours to obtain SiO2Marking the sol as sol A;
(2) dissolving 9.86 g of tetrabutyl titanate in 18.15 g of absolute ethyl alcohol, dropwise adding 2 g of glacial acetic acid into the mixed solution, stirring to obtain a solution B, weighing 13.41 g of absolute ethyl alcohol, 1 g of glacial acetic acid and 3.06 g of deionized water to prepare a solution C, and dropwise adding the solution C into the solution B to prepare TiO2Sol, marked as sol D;
(3) 1/5 sol A is added into the sol D, and SiO is obtained under stirring2-TiO2Composite sol of MnO 5 wt.%xWeighing 2.8 g of 10 wt.% aqueous solution of manganese acetate, adding the aqueous solution of manganese acetate to the composite sol, finally adding 560 μ L of formamide, uniformly stirring, and placing the beaker in a 35 ℃ water bath kettle for gelation;
(4) after gelation, adding a mixed solution of 5 mL tetraethyl orthosilicate and 20 mL absolute ethyl alcohol, placing a beaker in a water bath at 50 ℃ for 12 h, and after aging, replacing the gel with n-hexane at 40 ℃ for 3 times, each time for 3 h;
(5) and (3) performing gradient drying on the gel after the replacement is finished at 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 150 ℃, preserving heat for 2 h at each temperature point, roasting the dried sample at 550 ℃ for 5 h to obtain the composite functional aerogel: MnOx-TiO2-SiO2。
Example 4
(1) 6.62 g of absolute ethyl alcohol, 6.03 g of tetraethyl orthosilicate and 2.58 g of deionized water are weighed in sequenceSequentially adding into a beaker, stirring, adding 0.7 mL of HCl solution (0.1 mol/L) after uniformly stirring, placing the beaker at 55 ℃, stirring and hydrolyzing for 3 h to obtain SiO2Marking the sol as sol A;
(2) dissolving 9.86 g of tetrabutyl titanate in 18.15 g of absolute ethyl alcohol, dropwise adding 2 g of glacial acetic acid into the mixed solution, stirring to obtain a solution B, weighing 13.41 g of absolute ethyl alcohol, 1 g of glacial acetic acid and 3.06 g of deionized water to prepare a solution C, and dropwise adding the solution C into the solution B to prepare TiO2Sol, marked as sol D;
(3) 1/3 sol A is added into the sol D, and SiO is obtained under stirring2-TiO2Composite sol of 1 wt.% MnOxWeighing 0.6 g of 10 wt.% aqueous solution of manganese acetate, adding the aqueous solution of manganese acetate to the composite sol, finally adding 560 μ L of formamide, uniformly stirring, and placing the beaker in a 35 ℃ water bath kettle for gelation;
(4) after gelation, adding a mixed solution of 5 mL tetraethyl orthosilicate and 20 mL absolute ethyl alcohol, placing a beaker in a water bath at 50 ℃ for 12 h, and after aging, replacing the gel with n-hexane at 40 ℃ for 3 times, each time for 3 h;
(5) and (3) performing gradient drying on the gel after the replacement is finished at 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 150 ℃, preserving heat for 2 h at each temperature point, roasting the dried sample at 550 ℃ for 5 h to obtain the composite functional aerogel: MnOx-TiO2-SiO2。
Example 5
(1) Respectively weighing 6.62 g of absolute ethyl alcohol, 6.03 g of tetraethyl orthosilicate and 2.58 g of deionized water, sequentially adding the absolute ethyl alcohol, the tetraethyl orthosilicate and the deionized water into a beaker, stirring the mixture, adding 0.7 mL of HCl solution (0.1 mol/L) after uniformly stirring the mixture, placing the beaker at 55 ℃, stirring and hydrolyzing the mixture for 3 hours to obtain SiO2Marking the sol as sol A;
(2) dissolving 9.86 g of tetrabutyl titanate in 18.15 g of absolute ethyl alcohol, dropwise adding 2 g of glacial acetic acid into the mixed solution, stirring to obtain a solution B, weighing 13.41 g of absolute ethyl alcohol, 1 g of glacial acetic acid and 3.06 g of deionized water to prepare a solution C, and then dropwise adding the solution C into the solution BIn (1), preparing TiO2Sol, marked as sol D;
(3) 1/3 sol A is added into the sol D, and SiO is obtained under stirring2-TiO2Composite sol, according to 10 wt.% MnOxWeighing 6.2 g of 10 wt.% aqueous solution of manganese acetate, adding the aqueous solution of manganese acetate to the composite sol, finally adding 560 microliter of formamide, uniformly stirring, and placing the beaker in a 35 ℃ water bath kettle for gelation;
(4) after gelation, adding a mixed solution of 5 mL tetraethyl orthosilicate and 20 mL absolute ethyl alcohol, placing a beaker in a water bath at 50 ℃ for 12 h, and after aging, replacing the gel with n-hexane at 40 ℃ for 3 times, each time for 3 h;
(5) and (3) performing gradient drying on the gel after the replacement is finished at 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 150 ℃, preserving heat for 2 h at each temperature point, roasting the dried sample at 550 ℃ for 5 h to obtain the composite functional aerogel: MnOx-TiO2-SiO2。
And (3) performance testing: composite aerogels prepared in all the above examples were used as test objects
Composite aerogel MnO prepared in all examplesx-TiO2-SiO2Carrying out catalytic degradation on toluene in an ultraviolet-assisted ozone catalytic system, and constructing an ultraviolet coupling ozone oxidation VOCs test system by using a fixed bed reactor, wherein an internal ultraviolet lamp is 25W (the wavelength is 254 nm); toluene was used as an object of investigation, 120 ppm of toluene gas at a flow rate of 1500 mL/min was introduced into the reactor, 2 g of a catalyst was added to the reaction system, and detection and analysis were performed by gas chromatography (FID detector) to calculate the removal rate of toluene. It can be seen from fig. 1 and 2 that too much or too little active component to titanium silicon has a significant effect on the overall catalyst activity. As can be seen from the attached figure 3, the introduction of the 254nm ultraviolet light can effectively improve the utilization efficiency of ozone, generate more active substances to be applied to substrate degradation, and prolong the service life of the catalyst.
By O3Catalytic, ultraviolet coupled O3Oxidation of two reaction systems the composite aerogel prepared in example 2 was subjected toThe test results show in FIG. 3.
The above examples are only for the purpose of analyzing and understanding the preparation method and the application range of the present invention, but the present invention is not limited to the above examples. Those skilled in the art should also appreciate that they can directly make changes, substitutions, modifications and the like to the present invention without departing from the scope of the present patent.
Claims (8)
1. A preparation method of a composite aerogel functional material is characterized by comprising the following preparation steps: (1) preparing a mixed solution of tetraethyl orthosilicate, absolute ethyl alcohol, deionized water and HCl, wherein the molar ratio of n (TEOS) to n (EtOH) to n (H)2O): n(HCl)=1:（4～6）:（4～6）:2.4×10-3And putting the mixture into a mixer at 55 ℃ to be stirred and hydrolyzed for 2 to 4 hours to obtain SiO2Sol, marked as sol A; (2) dissolving tetrabutyl titanate in absolute ethyl alcohol, dropwise adding glacial acetic acid into the solution, and quickly stirring to obtain a solution B, wherein the molar ratio of tetrabutyl titanate to absolute ethyl alcohol to glacial acetic acid in the solution B is (1) (10-15) to (1-1.5); preparing a mixed solution C of absolute ethyl alcohol, glacial acetic acid and deionized water, wherein the molar ratio of the absolute ethyl alcohol to the glacial acetic acid to the deionized water is (1-3): 0-0.3): 1; dripping the solution C into the solution B to prepare TiO2The sol is marked as sol D, wherein the mass ratio of the solution C to the solution B is 1 (1-2); (3) adding the sol A into the sol D according to the molar ratio of silicon to titanium of 1 (1-5), and stirring to obtain SiO2-TiO2Compounding the sol followed by MnO of 1 wt.% to 15 wt.%xDropwise adding a pre-prepared 10 wt.% manganese acetate aqueous solution into the composite sol, adding a formamide reagent with a volume ratio of 1 (80-120) to the composite sol under a stirring state, and then placing the mixture in a 35 ℃ water bath kettle to obtain alcogel; (4) adding a mixed solution of tetraethyl orthosilicate and absolute ethyl alcohol in a volume ratio of 1 (3-5) into the obtained alcohol gel to completely immerse the gel, placing the gel in a water bath kettle at 50 ℃, aging for 12 hours, pouring out supernatant, and performing at least 3 times of replacement by using normal hexane at 40 ℃; (5) placing the gel without the supernatant in a forced air drying box, and performing gradient drying; finally, roasting the mixture in a muffle furnace to obtain MnOx-TiO2-SiO2And (3) compounding the aerogel.
2. The preparation method of the composite aerogel functional material according to claim 1, characterized in that: TEOS, EtOH and H in the sol A in the step (1)2The molar ratio of O to HCl is 1:4.95:4.95: 2.4X 10-3And the stirring hydrolysis time is 3 h.
3. The preparation method of the composite aerogel functional material according to claim 1, characterized in that: the molar ratio of tetrabutyl titanate, anhydrous ethanol and glacial acetic acid in the solution B in the step (2) is 1:13.6:1.1, the molar ratio of anhydrous ethanol, glacial acetic acid and deionized water in the solution C is 1.7:0.1:1, and the mass ratio of the solution C to the solution B is 1: 1.72.
4. The preparation method of the composite aerogel functional material according to claim 1, characterized in that: the molar ratio of silicon to titanium in the step (3) is 1:3, and MnO is adoptedxThe loading amount of the composite sol is 5 wt.%, and the volume ratio of the composite sol to formamide is 1: 110.
5. The preparation method of the composite aerogel functional material according to claim 1, characterized in that: and (4) the volume ratio of the tetraethyl orthosilicate and absolute ethyl alcohol mixed solution in the step (4) is 1:4, the n-hexane replacement frequency is not less than 3 times, and the replacement time is not less than 3 hours.
6. The preparation method of the composite aerogel functional material according to claim 1, characterized in that: and (5) performing gradient drying at 60 ℃, 80 ℃, 100 ℃, 120 ℃ and 150 ℃ respectively, and keeping the temperature of each temperature point for 2 hours, wherein the roasting temperature is 550 ℃ and the roasting time is 5 hours.
7. The composite aerogel functional material prepared by the preparation method of any one of claims 1 to 6.
8. Use of the composite aerogel functional material of claim 7 in the treatment of VOCs.
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