CN112934211B - Preparation method of silica aerogel with photocatalytic activity - Google Patents
Preparation method of silica aerogel with photocatalytic activity Download PDFInfo
- Publication number
- CN112934211B CN112934211B CN202110126872.2A CN202110126872A CN112934211B CN 112934211 B CN112934211 B CN 112934211B CN 202110126872 A CN202110126872 A CN 202110126872A CN 112934211 B CN112934211 B CN 112934211B
- Authority
- CN
- China
- Prior art keywords
- graphene
- aerogel
- silicon oxide
- solution
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 143
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 39
- 239000004965 Silica aerogel Substances 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 121
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 121
- 229910052814 silicon oxide Inorganic materials 0.000 claims abstract description 86
- 239000000243 solution Substances 0.000 claims abstract description 68
- 239000004964 aerogel Substances 0.000 claims abstract description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 39
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000000463 material Substances 0.000 claims abstract description 33
- 230000005855 radiation Effects 0.000 claims abstract description 32
- 239000000843 powder Substances 0.000 claims abstract description 28
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 26
- 229910001868 water Inorganic materials 0.000 claims abstract description 25
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 21
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 19
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 19
- 239000010703 silicon Substances 0.000 claims abstract description 19
- 239000007864 aqueous solution Substances 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 14
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 14
- 230000032683 aging Effects 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 20
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 12
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 12
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 11
- 239000004246 zinc acetate Substances 0.000 claims description 11
- 229960000583 acetic acid Drugs 0.000 claims description 10
- 239000012362 glacial acetic acid Substances 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 4
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 3
- 230000003197 catalytic effect Effects 0.000 abstract description 27
- 229910052681 coesite Inorganic materials 0.000 abstract description 11
- 229910052906 cristobalite Inorganic materials 0.000 abstract description 11
- 229910052682 stishovite Inorganic materials 0.000 abstract description 11
- 229910052905 tridymite Inorganic materials 0.000 abstract description 11
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000006185 dispersion Substances 0.000 abstract description 6
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 description 25
- 239000013078 crystal Substances 0.000 description 14
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 11
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 10
- 239000011787 zinc oxide Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 238000001132 ultrasonic dispersion Methods 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 239000002245 particle Substances 0.000 description 7
- 239000002131 composite material Substances 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 4
- 239000011943 nanocatalyst Substances 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 4
- 229940007718 zinc hydroxide Drugs 0.000 description 4
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 4
- 229910007156 Si(OH)4 Inorganic materials 0.000 description 3
- 229910002808 Si–O–Si Inorganic materials 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000006068 polycondensation reaction Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910008051 Si-OH Inorganic materials 0.000 description 2
- 229910006358 Si—OH Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000009413 insulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Images
Classifications
-
- 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
- B01J21/18—Carbon
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- B01J35/23—
-
- B01J35/39—
Abstract
The invention belongs to the technical field of photocatalytic materials, and particularly relates to a preparation method of silica aerogel with photocatalytic activity, which comprises the following steps: (1) mixing a graphene aqueous solution, an organic silicon source solution and ammonia water, and then sequentially carrying out water bath and aging to obtain graphene/silicon oxide sol; (2) carrying out microwave radiation treatment on the graphene/silicon oxide sol to obtain silicon oxide/graphene aerogel powder; (3) mixing the silicon oxide/graphene aerogel powder, water and an inorganic salt absolute ethyl alcohol solution to obtain a silicon oxide/graphene aerogel-hydroxide colloidal solution, and then performing microwave radiation on the colloidal solution to obtain the silicon oxide/graphene aerogel photocatalytic material. The method is not only beneficial to improving SiO2The strength, mechanical property and electric conductivity of the aerogel can also improve the dispersion and photocatalytic performance of the catalyst, and the silicon oxide/oxide aerogel catalytic material with high catalytic activity and good stability can be obtained.
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to a preparation method of silica aerogel with photocatalytic activity.
Background
SiO2The aerogel is a disordered mesoporous material, has small density, low thermal conductivity coefficient, good optical property and large high specific surface area, contains rich Si-OH groups on the surface, shows good adsorption property, and is an ideal carrier of the nano catalyst. In SiO2Adding nanometer catalyst (TiO) with photocatalytic activity into aerogel2ZnO) can be prepared into a complex having both properties of aerogel and photocatalyst, namely SiO2The composite catalyst has thermal stability, mechanical stability and photocatalytic activity, and has wide application prospect in various fields of heat preservation and insulation, building glass, adsorption, catalysis and the like. However, SiO2The aerogel does not have photocatalytic oxidation performance, is fragile, has poor mechanical performance, poor conductivity and the like, and limits the application of the aerogel in the field of photocatalysis.
Disclosure of Invention
The technical problem to be solved by the invention is that SiO2The aerogel has the problems of frangibility, poor mechanical property, poor conductivity and the like, and the SiO modified by the graphene and oxide catalyst composite is developed2The research of the aerogel obtains the aerogel catalytic material with good mechanical property and high catalytic activity. The invention aims to provide a preparation method of a silicon oxide/oxide aerogel catalytic material with high catalytic activity and good stability.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of silica aerogel with photocatalytic activity, which comprises the following steps:
(1) mixing a graphene aqueous solution, an organic silicon source solution and ammonia water, and then sequentially carrying out water bath and aging to obtain graphene/silicon oxide sol;
(2) carrying out microwave radiation treatment on the graphene/silicon oxide sol obtained in the step (1) to obtain silicon oxide/graphene aerogel powder;
(3) mixing the silicon oxide/graphene aerogel powder, water and an inorganic salt absolute ethyl alcohol solution to obtain a silicon oxide/graphene aerogel-hydroxide colloidal solution;
(4) and (4) subjecting the silica/graphene aerogel-hydroxide colloidal solution obtained in the step (3) to microwave radiation to obtain the silica/oxide aerogel photocatalytic material.
Further, in the step (1), the organic silicon source is one or more of ethyl orthosilicate, butyl orthosilicate and n-methylsilane.
Further, the organic silicon source solution is obtained by mixing an organic silicon source, absolute ethyl alcohol and glacial acetic acid, wherein the volume ratio of the organic silicon source to the absolute ethyl alcohol to the glacial acetic acid is 5-6 mL: 20-30 mL: 0.1-0.5 mL.
Further, in the step (1), the concentration of the graphene aqueous solution is 0.8-1.2 g/L, and the graphene is graphene oxide or reduced graphene oxide.
Further, in the step (1), the volume ratio of the graphene aqueous solution, the organic silicon source solution and the ammonia water is 35-40: 25-38: 5 to 15, and the concentration of ammonia water is 0.5 to 1.0 mol/L.
Further, in the step (1), the temperature of the water bath treatment is 80-90 ℃, and the time of the water bath treatment is 2-4 hours; the aging time is 12-24 h.
Further, in the step (2), the power of microwave radiation is 150-300W, and the time of microwave radiation is 20-40 min.
Further, in the step (3), the volume ratio of the water to the inorganic salt absolute ethyl alcohol solution is 100-150 mL: 10-20 mL; the inorganic salt absolute ethyl alcohol solution is prepared from inorganic salt and absolute ethyl alcohol according to a mass-volume ratio of 5-10 g: 10-20 mL of mixed solution; the inorganic salt is one or more of butyl titanate, zinc acetate, tetraisopropyl titanate, zinc nitrate and zinc acetate.
Further, in the step (4), the power of microwave radiation is 400-800W, and the time of microwave radiation is 20-40 min.
The invention has the beneficial effects that:
1. the technical conception is as follows: firstly, modifying silicon oxide aerogel by using graphene and an oxide catalyst, embedding graphene in the silicon oxide aerogel to obtain graphene/silicon oxide aerogel powder with good mechanical property and conductivity, then uniformly loading nano oxide on the silicon oxide/graphene aerogel powder by using a microwave radiation method, and finally preparing the silicon oxide/oxide aerogel catalytic material with high catalytic activity and stable structure. The graphene has large specific surface area, super strong mechanical property and good conductivity, and modification by the graphene is beneficial to improving the mechanical strength and conductivity of the silica aerogel; the silica aerogel has the advantages of large specific surface area, good optical performance and strong corrosion resistance, the dispersion and catalytic stability of the nano catalyst can be improved by using the silica aerogel for loading, and the aerogel with good conductivity can capture and conduct photoexcited electrons, accelerate the separation of photo-generated electron-hole pairs and improve the photocatalytic efficiency of the nano catalyst. In addition, microwave heating has the characteristics of selective heating, uniform heating, short reaction time, good product uniformity and the like, so that the method can shorten the reaction practice, has low energy consumption of the preparation process, and can synthesize the nano material with small granularity, high purity and better crystallization at low temperature. Therefore, the silicon oxide/oxide aerogel catalytic material prepared by the microwave method has the advantages of simple preparation process and low price, and the prepared catalytic material with uniform particle size and good crystallinity has wide application prospect in the fields of sewage treatment, environmental protection, building materials, solar cells and the like.
2. The invention principle is as follows: formation of Si (OH) by hydrolysis of organosilicon4Then by Si (OH) in a sol-gel process4Obtaining a silica gel having a three-dimensional network structure; meanwhile, in the process of forming the silicon oxide gel, the graphene is uniformly embedded in the silicon oxide gel to form an organic whole; silicon oxide/graphene is used as a carrier, and aerogel is endowed to the silicon oxide/graphene through oxide catalyst loadingThe glue has good photocatalysis performance, thereby obtaining the silicon oxide/oxide catalytic material with good catalysis performance. The main chemical reaction process is as follows:
(1) hydrolysis of silicones
Si(OR)4+4H2O→Si(OH)4+4ROH, wherein R represents an organofunctional group;
(2)Si(OH)4polycondensation of (2): Si-OH in silicic acid molecules forms Si-O-Si through further dehydration condensation, and the specific reaction is as follows: 2Si (OH)4→(OH)3Si-O-Si(OH)3+H2O
(3)Si(OH)4Dehydration: the transformation process from sol to gel, further polycondensation between Si-O-Si, dehydration to produce SiO2And SiO is irradiated with microwave2Has an increasing molecular mass, and these SiO2Are connected together to form a three-dimensional network structure, forming a pore structure. After gelation, SiO2The colloidal particles keep the network structure in the solvent, the solvent is filled in the gaps of the colloidal particles, and finally SiO is formed2An aerogel.
Graphene uniformly dispersed in Si (OH)4In solution, in Si (OH)4Polycondensation and dehydration to form SiO2The three-dimensional network structure process is easy to wrap the graphene in the structure to construct a silicon oxide/graphene colloidal particle, and finally silicon oxide/graphene aerogel powder is formed. Graphene is an ideal nano catalyst carrier, has high specific surface area, super strong mechanical property and excellent conductivity, is easy to capture electrons and effectively conduct electrons, and can prevent the recombination of photogenerated carriers in the catalyst. So that graphene is embedded in SiO2Adding SiO into aerogel2Conductivity and mechanical properties of the aerogel.
(4) The silicon oxide/graphene aerogel powder is uniformly dispersed in water, the inorganic salt absolute ethyl alcohol solution is added and then hydrolyzed to form hydroxide small crystal nuclei, the hydroxide small crystal nuclei are coated on the surface of the silicon oxide/graphene aerogel powder, and large crystal nuclei are formed on the surface of the hydroxide small crystal nuclei silicon oxide/graphene aerogel powder along with the lapse of time. Then under the action of microwave radiation, the small crystal nuclei are decomposed to form oxide crystals attached to the silicon oxide/graphene aerogel powder, and finally the silicon oxide aerogel catalytic material is formed.
The method is mainly characterized in that the silicon oxide/graphene aerogel powder with good conductivity is prepared by a microwave heating method, then the silicon oxide/graphene aerogel is uniformly loaded with the catalyst nano material by the microwave heating method, and finally the silicon oxide/oxide aerogel catalytic material with stable performance and strong catalytic activity is obtained. According to the method, the silicon oxide/graphene aerogel powder and the silicon oxide/oxide aerogel catalytic material are quickly synthesized without heating.
3. Compared with the prior art, the invention has the advantages that: (1) preparing silicon oxide/graphene aerogel particles by using a microwave heating method to obtain graphene/silicon oxide aerogel composite powder with light weight and large specific surface area; (2) the method is characterized in that silicon oxide/graphene aerogel powder is used as a carrier, and the uniform loading of catalyst nanoparticles is realized by a microwave heating method. The invention can effectively control the particle size of the catalyst nano particles, and the prepared silicon oxide/graphene aerogel nano particles are firmly combined with the oxide particles, are uniformly coated and have good photocatalytic performance and stability; (3) by utilizing the superiority of microwave heating, the silicon oxide/oxide aerogel photocatalytic material with catalytic activity can be directly obtained without subsequent heat treatment, the preparation process is relatively simple, the production cost is low, and the industrialization is easy to realize.
Drawings
Fig. 1 is an XRD pattern of the silicon oxide/graphene-titanium oxide catalytic material obtained in example 1.
Fig. 2 and 3 are SEM images at 2 ten thousand times and 16 ten thousand times respectively of the silicon oxide/graphene-zinc oxide catalytic material obtained in example 2.
Fig. 4 shows the photocatalytic performance of the silicon oxide/graphene-titanium oxide catalytic material obtained in example 3 under the irradiation of ultraviolet light. Before 0 minute, the adsorption state in the dark state was observed, and after 0 minute, the degradation of the organic dye was observed after the irradiation with ultraviolet light.
Fig. 5 shows the stability of the silicon oxide/graphene-zinc oxide catalytic material obtained in example 4 in degrading organic substances under ultraviolet irradiation.
Detailed Description
The invention provides a preparation method of silica aerogel with photocatalytic activity, which comprises the following steps:
(1) mixing a graphene aqueous solution, an organic silicon source solution and ammonia water, and then sequentially carrying out water bath and aging to obtain graphene/silicon oxide sol;
(2) carrying out microwave radiation treatment on the graphene/silicon oxide sol obtained in the step (1) to obtain silicon oxide/graphene aerogel powder;
(3) mixing the silicon oxide/graphene aerogel powder, water and an inorganic salt absolute ethyl alcohol solution to obtain a silicon oxide/graphene aerogel-hydroxide colloidal solution;
(4) and (4) subjecting the silica/graphene aerogel-hydroxide colloidal solution obtained in the step (3) to microwave radiation to obtain the silica/oxide aerogel photocatalytic material.
In the invention, 5-15 mL of graphene solution with the concentration of 0.8-1.2 g/L is added into 20-30 mL of deionized water for ultrasonic dispersion for 5-15 min, and the ultrasonic dispersion frequency is 30-40 kHZ, so as to obtain the uniformly dispersed graphene solution. The graphene is preferably graphene oxide or reduced graphene oxide.
In the invention, 10mL of graphene aqueous solution with the concentration of 1.0g/L is added into 15mL of deionized water for ultrasonic dispersion for 10min, and the ultrasonic dispersion frequency is 35kHZ, so that the uniformly dispersed graphene aqueous solution is obtained.
In the invention, in the step (1), the organic silicon source is one or more of ethyl orthosilicate, butyl orthosilicate and n-methylsilane, and preferably n-methylsilane.
In the invention, the organic silicon source solution is obtained by mixing an organic silicon source, absolute ethyl alcohol and glacial acetic acid, wherein the volume ratio of the organic silicon source to the absolute ethyl alcohol to the glacial acetic acid is 5-6 mL: 20-30 mL: 0.1-0.5 mL, preferably 5.5 mL: 25mL of: 0.3 mL.
In the invention, in the step (1), the volume ratio of the graphene aqueous solution, the organic silicon source solution and the ammonia water is 35-40: 25-38: 5-15, and the volume ratio is preferably 37-39: 28-35: 8 to 12, and the concentration of the ammonia water is 0.5 to 1.0mol/L, preferably 0.8 mol/L.
In the invention, in the step (1), the temperature of the water bath is 80-90 ℃, preferably 85 ℃, and the time of the water bath is 2-4 hours, preferably 3 hours. In the present invention, the water bath functions to form small crystal nuclei of the graphene oxide silica sol.
In the invention, the aging time is 12-24 h, preferably 18 h. In the invention, the aging is used for growing the small crystal nucleus of the silica sol into the large crystal nucleus of graphene silica, so as to form a more stable crystal nucleus.
In the invention, in the step (2), the power of microwave radiation is 150-300W, preferably 200W, and the time of microwave radiation is 20-40 min, preferably 30 min. In the invention, the microwave radiation in the step (2) is used for controlling the shape of the crystal nucleus, so that the graphene silicon oxide large crystal nucleus grows further, and the crystallinity of the graphene silicon oxide large crystal nucleus is improved.
In the invention, the step (3) is to disperse all the silicon oxide/graphene aerogel powder obtained in the step (2) in 100-150 mL of water, stir for 20-40 min at the ultrasonic frequency of 30-40 kHZ, then add 10-20 mL of inorganic salt absolute ethyl alcohol solution, and continue to perform ultrasonic treatment for 30-45 min.
In the invention, in the step (3), the volume ratio of water to the inorganic salt absolute ethyl alcohol solution is 100-150 mL: 10-20 mL, preferably 120 mL: 15 mL; the inorganic salt absolute ethyl alcohol solution is prepared from inorganic salt and absolute ethyl alcohol according to a mass-volume ratio of 5-10 g: 10-20 mL of mixed solution, preferably 6-9 g: 8-15 mL; the inorganic salt is one or more of butyl titanate, zinc acetate, tetraisopropyl titanate, zinc nitrate and zinc acetate, and preferably butyl titanate and zinc acetate.
In the invention, in the step (4), the power of microwave radiation is 400-800W, preferably 600W, and the time of microwave radiation is 20-40 min, preferably 30 min. In the present invention, in step (4), the microwave radiation is used to form oxide nuclei from the hydroxide, and simultaneously grow the oxide nuclei to form more crystalline oxide.
In the present invention, the oxide in the obtained silica/oxide aerogel photocatalytic material is preferably titanium oxide or zinc oxide.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
(1) Adding 5mL of reduced graphene oxide solution with the concentration of 1.2g/L into 30mL of deionized water, and performing ultrasonic dispersion to obtain uniformly dispersed reduced graphene oxide aqueous solution;
(2) adding 5mL of tetraethoxysilane into 30mL of absolute ethyl alcohol, violently stirring for 30min, adding 0.5mL of glacial acetic acid, and then carrying out ultrasonic treatment and stirring for 30min to obtain a uniformly dispersed tetraethoxysilane solution;
(3) slowly adding the reduced graphene oxide dispersion solution obtained in the step (1) into the ethyl orthosilicate solution obtained in the step (2) under ultrasonic stirring, adding 15mL of ammonia water solution with the concentration of 1.0mol/L after ultrasonic stirring for 15min, carrying out water bath for 4h at the temperature of 90 ℃, and then aging for 24h at room temperature;
(4) pouring the silicon oxide/reduced graphene oxide sol obtained in the step (3) into a round-bottom flask, then performing microwave radiation for 40min under the power of 400W, cooling to room temperature, filtering and washing to obtain silicon oxide/reduced graphene oxide aerogel powder;
(5) dispersing the silicon oxide/reduced graphene oxide aerogel powder obtained in the step (4) in 100mL of deionized water, pouring the deionized water into a round-bottom flask, ultrasonically stirring for 40min, slowly adding 20mL of butyl titanate absolute ethanol solution (the mass-volume ratio of butyl titanate to absolute ethanol is 10g:20mL), and ultrasonically stirring for 45min to obtain silicon oxide/reduced graphene oxide aerogel-titanium hydroxide colloidal solution;
(6) and (3) putting the round-bottom flask filled with the silicon oxide/reduced graphene oxide aerogel-titanium hydroxide colloidal solution in the step (5) into a microwave oven, then performing microwave radiation for 40min at the power of 400W, cooling to room temperature, filtering and washing to obtain the silicon oxide/reduced graphene oxide-titanium oxide aerogel photocatalytic material. The phases of the obtained products are shown in figure 1.
Example 2
(1) Adding 15mL of 0.8g/L graphene solution into 20mL of deionized water, and performing ultrasonic dispersion to obtain a uniformly dispersed graphene aqueous solution;
(2) adding 6mL of n-butyl silicate into 20mL of absolute ethyl alcohol, stirring vigorously for 15min, adding 0.1mL of glacial acetic acid, and then carrying out ultrasonic treatment and stirring for 15min to obtain a uniformly dispersed n-butyl silicate solution;
(3) slowly adding the graphene dispersion solution obtained in the step (1) into the n-butyl silicate solution obtained in the step (2) under ultrasonic stirring, adding 5mL of 0.5mol/L ammonia water solution after ultrasonic stirring for 30min, carrying out water bath at the temperature of 80 ℃ for 2h, and then aging at room temperature for 12 h;
(4) pouring the silicon oxide/graphene sol obtained in the step (3) into a round-bottom flask, then performing microwave radiation for 20min under the power of 800W, cooling to room temperature, filtering and washing to obtain silicon oxide/graphene aerogel powder;
(5) dispersing the silicon oxide/graphene aerogel powder obtained in the step (4) in 150mL of deionized water, pouring the deionized water into a round-bottom flask, ultrasonically stirring for 20min, slowly adding 10mL of zinc acetate absolute ethyl alcohol solution (the mass-volume ratio of zinc acetate to absolute ethyl alcohol is 8g:15mL), and ultrasonically stirring for 30min to obtain a silicon oxide/graphene aerogel-zinc hydroxide colloidal solution;
(6) and (3) putting the round-bottom flask filled with the silica/graphene aerogel-zinc hydroxide colloidal solution in the step (5) into a microwave oven, then performing microwave radiation for 20min at the power of 800W, cooling to room temperature, filtering and washing to obtain the silica/zinc oxide aerogel photocatalytic material.
Example 3
(1) Adding 10mL of graphene solution with the concentration of 1.0g/L into 25mL of deionized water, and performing ultrasonic dispersion to obtain uniformly dispersed graphene aqueous solution;
(2) adding 6mL of n-methylsilane into 25mL of absolute ethanol, stirring vigorously for 20min, adding 0.3mL of glacial acetic acid, and performing ultrasonic treatment and stirring for 20min to obtain a uniformly dispersed n-methylsilane solution;
(3) slowly adding the graphene dispersion solution obtained in the step (1) into the n-methylsilane solution obtained in the step (2) under ultrasonic stirring, adding 10mL of 1.0mol/L ammonia water solution after ultrasonic stirring for 25min, carrying out water bath for 3h at the temperature of 85 ℃, and then aging for 20h at room temperature;
(4) pouring the silicon oxide/graphene sol obtained in the step (3) into a round-bottom flask, then performing microwave radiation for 20-40 min under the power of 400-800W, cooling to room temperature, filtering and washing to obtain silicon oxide/graphene aerogel powder;
(5) dispersing the silicon oxide/graphene aerogel powder obtained in the step (4) in 140mL of deionized water, pouring the deionized water into a round-bottom flask, ultrasonically stirring for 30min, slowly adding 15mL of tetraisopropyl titanate absolute ethanol solution (the mass-volume ratio of tetraisopropyl titanate to absolute ethanol is 7g:15mL), and ultrasonically stirring for 35min to obtain a silicon oxide/graphene aerogel-titanium hydroxide colloidal solution;
(6) and (3) putting the round-bottom flask filled with the silica/graphene aerogel-titanium hydroxide colloidal solution in the step (5) into a microwave oven, then performing microwave radiation for 30min at the power of 600W, cooling to room temperature, filtering and washing to obtain the silica/graphene-titanium oxide aerogel photocatalytic material.
Example 4
(1) Adding 10mL of graphene oxide solution with the concentration of 0.9g/L into 30mL of deionized water, and performing ultrasonic dispersion to obtain uniformly dispersed graphene oxide aqueous solution;
(2) adding 6mL of tetraethoxysilane into 25mL of absolute ethyl alcohol, violently stirring for 25min, adding 0.4mL of glacial acetic acid, and then carrying out ultrasonic treatment and stirring for 25min to obtain a uniformly dispersed tetraethoxysilane solution;
(3) slowly adding the graphene oxide dispersion solution obtained in the step (1) into the ethyl orthosilicate solution obtained in the step (2) under ultrasonic stirring, adding 10mL of 0.8mol/L ammonia water solution after ultrasonic stirring for 30min, carrying out water bath at the temperature of 85 ℃ for 3h, and then aging at room temperature for 20 h;
(4) pouring the silicon oxide/graphene oxide sol obtained in the step (3) into a round-bottom flask, then performing microwave radiation for 20min under the power of 700W, cooling to room temperature, filtering and washing to obtain silicon oxide/graphene oxide aerogel powder;
(5) dispersing the graphene oxide/silicon oxide aerogel powder obtained in the step (4) in 120mL of deionized water, pouring the deionized water into a round-bottom flask, ultrasonically stirring for 30min, slowly adding 20mL of zinc nitrate absolute ethyl alcohol solution (the mass-volume ratio of zinc nitrate to absolute ethyl alcohol is 5g:15mL), and ultrasonically stirring for 35min to obtain a silicon oxide/graphene oxide aerogel-zinc hydroxide colloidal solution;
(6) and (3) putting the round-bottom flask filled with the silica/graphene oxide aerogel-zinc hydroxide colloidal solution in the step (5) into a microwave oven, then performing microwave radiation for 20min at the power of 600W, cooling to room temperature, filtering and washing to obtain the silica/graphene oxide-zinc oxide aerogel photocatalytic material.
Fig. 1 is an XRD pattern of the silicon oxide/reduced graphene oxide-titanium oxide catalytic material obtained in example 1. It can be seen from the figure that the composite material obtained is mainly composed of anatase titanium oxide crystals.
Fig. 2 and 3 are SEM images of samples obtained in example 2. As can be seen from the figure, the obtained sample is a bulk material consisting of nanoparticles.
Fig. 4 shows that the silicon oxide/graphene-titanium oxide catalytic material obtained in example 3 degrades organic substances by photocatalysis under the irradiation of ultraviolet light. As can be seen from the figure, the addition of silicon oxide and graphene can improve the photocatalytic performance of titanium oxide, but the enhancement effect of graphene is better than that of silicon oxide. In addition, the silicon oxide/graphene-titanium oxide catalytic material with more excellent performance can be obtained by the composite modification of the graphene and the silicon oxide. The result shows that the modification of graphene and silicon oxide has good photocatalytic enhancement effect.
Fig. 5 shows the stability of the silicon oxide/graphene oxide-zinc oxide catalytic material obtained in example 4 in degrading organic substances under ultraviolet irradiation. As can be seen from the figure, the obtained silicon oxide/graphene oxide-zinc oxide catalytic material sample still has good photocatalytic degradation capability after 5 times of recycling. The results show that the obtained silicon oxide/graphene oxide-zinc oxide catalytic material has good photocatalytic stability.
From the above examples, the present invention provides a silica/graphene oxide-oxide photocatalytic material having high photocatalytic stability.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A preparation method of silica aerogel with photocatalytic activity is characterized by comprising the following steps:
(1) mixing a graphene aqueous solution, an organic silicon source solution and ammonia water, and then sequentially carrying out water bath and aging to obtain graphene/silicon oxide sol;
(2) carrying out microwave radiation treatment on the graphene/silicon oxide sol obtained in the step (1) to obtain silicon oxide/graphene aerogel powder;
(3) mixing the silicon oxide/graphene aerogel powder obtained in the step (2), water and an inorganic salt absolute ethyl alcohol solution to obtain a silicon oxide/graphene aerogel-hydroxide colloidal solution;
(4) subjecting the silica/graphene aerogel-hydroxide colloidal solution obtained in the step (3) to microwave radiation to obtain a silica/oxide aerogel photocatalytic material;
in the step (2), the power of microwave radiation is 150-300W, and the time of microwave radiation is 20-40 min;
in the step (4), the power of microwave radiation is 400-800W, and the time of microwave radiation is 20-40 min;
in the step (3), the inorganic salt absolute ethyl alcohol solution is prepared by mixing inorganic salt and absolute ethyl alcohol according to a mass-volume ratio of 5-10 g: 10-20 mL of mixed solution; the inorganic salt is one or more of butyl titanate, zinc acetate, tetraisopropyl titanate, zinc nitrate and zinc acetate.
2. The method for preparing silica aerogel having photocatalytic activity according to claim 1, wherein in step (1), the organic silicon source is one or more of ethyl orthosilicate, butyl orthosilicate and n-methylsilane.
3. The method for preparing silica aerogel with photocatalytic activity according to claim 2, wherein the organic silicon source solution is prepared by mixing an organic silicon source, absolute ethyl alcohol and glacial acetic acid, wherein the volume ratio of the organic silicon source to the absolute ethyl alcohol to the glacial acetic acid is 5-6 mL: 20-30 mL: 0.1-0.5 mL.
4. The method according to claim 3, wherein in the step (1), the concentration of the graphene aqueous solution is 0.8-1.2 g/L, and the graphene is graphene oxide or reduced graphene oxide.
5. The method for preparing silica aerogel having photocatalytic activity according to claim 4, wherein in the step (1), the volume ratio of the graphene aqueous solution, the organic silicon source solution and the ammonia water is 35-40: 25-38: 5 to 15, and the concentration of ammonia water is 0.5 to 1.0 mol/L.
6. The preparation method of the silica aerogel with photocatalytic activity according to claim 5, wherein in the step (1), the temperature of the water bath is 80-90 ℃, and the time of the water bath is 2-4 h; the aging time is 12-24 h.
7. The method for preparing silica aerogel having photocatalytic activity according to claim 6, wherein in step (3), the volume ratio of the water to the inorganic salt absolute ethyl alcohol solution is 100 to 150 mL: 10-20 mL; the inorganic salt absolute ethyl alcohol solution is prepared from inorganic salt and absolute ethyl alcohol according to a mass-volume ratio of 5-10 g: 10-20 mL of mixed solution; the inorganic salt is one or more of butyl titanate, zinc acetate, tetraisopropyl titanate, zinc nitrate and zinc acetate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110126872.2A CN112934211B (en) | 2021-01-29 | 2021-01-29 | Preparation method of silica aerogel with photocatalytic activity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110126872.2A CN112934211B (en) | 2021-01-29 | 2021-01-29 | Preparation method of silica aerogel with photocatalytic activity |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112934211A CN112934211A (en) | 2021-06-11 |
| CN112934211B true CN112934211B (en) | 2022-01-25 |
Family
ID=76239791
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110126872.2A Active CN112934211B (en) | 2021-01-29 | 2021-01-29 | Preparation method of silica aerogel with photocatalytic activity |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112934211B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113578212B (en) * | 2021-07-09 | 2022-08-02 | 西安理工大学 | Zinc oxide/graphene oxide/carbon nanotube aerogel and method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104826582B (en) * | 2015-04-04 | 2017-09-29 | 绥化学院 | A kind of preparation method of graphene meso-porous titanium dioxide silica aerogel |
| CN107325328B (en) * | 2017-06-15 | 2019-06-07 | 北京化工大学 | A kind of preparation method of graphene/silicon dioxide compound particle |
| CN108715444B (en) * | 2018-06-15 | 2020-02-04 | 中国科学院苏州纳米技术与纳米仿生研究所 | Super-hydrophobic silicon oxide hybrid graphene aerogel micro powder, preparation method and application thereof |
| CN110833799B (en) * | 2019-11-04 | 2021-11-19 | 江苏一夫新材料产业技术研究院有限公司 | Graphene-elemental silicon composite aerogel and preparation method thereof |
-
2021
- 2021-01-29 CN CN202110126872.2A patent/CN112934211B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN112934211A (en) | 2021-06-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103599800B (en) | The preparation method of glass fiber loaded silver-silver bromide-titanium oxide composite material | |
| CN101791547B (en) | Method for preparing TiO2 nanocryatal/nanotube composite photocatalyst | |
| CN103657623B (en) | Microballoon-type titanium dioxide photocatalyst and preparation method thereof | |
| CN105964250B (en) | It is a kind of with visible light-responded Ag10Si4O13Photochemical catalyst and its preparation method and application | |
| CN107362799B (en) | Preparation method of titanium dioxide/cuprous oxide composite photocatalyst | |
| CN110975894B (en) | Visible light response type efficient and stable nano CsPbBr 3 /TiO 2 Composite photocatalyst and preparation method thereof | |
| CN105217676B (en) | Titania aerogel with nanometer sheet and nano-porous structure and preparation method thereof | |
| CN103730259B (en) | A kind of nanocrystalline titanium dioxide film of two-specification pore structure and manufacturing method of nanocrystalline titanium dioxide film and preparation method thereof | |
| CN102423702A (en) | Graphene oxide/titanium dioxide composite photocatalysis material and preparation method thereof | |
| CN104310469A (en) | Method for preparing titanium dioxide porous material | |
| CN103908979A (en) | Supported nano TiO2 catalyst and preparation method thereof | |
| CN114196241A (en) | Photocatalytic self-cleaning coating and preparation method and application thereof | |
| CN101518730A (en) | Composite nanometer titanium dioxide photocatalysis material and preparation method thereof | |
| CN112934211B (en) | Preparation method of silica aerogel with photocatalytic activity | |
| CN104689784A (en) | SiO2 composite aerogel material loaded with photocatalyst and preparation method of SiO2 composite aerogel material | |
| CN102909045B (en) | Preparation method of micron-order load type TiO2 catalyst | |
| CN105645459A (en) | Surface modified urchin-shaped ZnO/TiO2 composite material and preparation method thereof | |
| CN107522169A (en) | A kind of normal temperature prepares pure organic homogeneous precipitation method of nano-oxide | |
| CN105056927A (en) | TiO2 nanotube composite SiO2 aerogel-based photocatalytic material and preparation method thereof | |
| CN112138612A (en) | Preparation method of graphene-organic silicon composite aerogel | |
| CN108654663B (en) | Boron-nitrogen co-doped single crystal mesoporous TiO prepared by mixed nitrate molten salt method2Method for catalyzing materials | |
| CN109482191B (en) | Foamed nickel loaded zinc titanate/tourmaline photocatalytic material and preparation method thereof | |
| CN101456561B (en) | Method for preparing nano mullite powder | |
| CN107008337B (en) | Non-stoichiometric copper bismuthate nano material and preparation method and application thereof | |
| CN111229194A (en) | (TiO)2-ZrO2-SiO2) @ inverse opal structure SiO2Preparation and use of catalysts |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |