CN113600160A - TiO with photocatalytic function2Preparation of nanowire/graphene aerogel - Google Patents
TiO with photocatalytic function2Preparation of nanowire/graphene aerogel Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 79
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 74
- 239000004964 aerogel Substances 0.000 title claims abstract description 54
- 239000002070 nanowire Substances 0.000 title claims abstract description 50
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 24
- 230000008014 freezing Effects 0.000 claims abstract description 34
- 238000007710 freezing Methods 0.000 claims abstract description 34
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 33
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007787 solid Substances 0.000 claims abstract description 23
- 238000003756 stirring Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 238000000137 annealing Methods 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- -1 alkyl glycoside Chemical class 0.000 claims abstract description 14
- 229930182470 glycoside Natural products 0.000 claims abstract description 13
- 229910021538 borax Inorganic materials 0.000 claims abstract description 12
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 12
- 238000010257 thawing Methods 0.000 claims abstract description 12
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000006185 dispersion Substances 0.000 claims abstract description 9
- 238000005187 foaming Methods 0.000 claims abstract description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000502 dialysis Methods 0.000 claims abstract description 5
- 229910052786 argon Inorganic materials 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 230000035484 reaction time Effects 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 abstract description 45
- 239000000463 material Substances 0.000 abstract description 12
- 238000004887 air purification Methods 0.000 abstract description 3
- 239000012530 fluid Substances 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 230000001476 alcoholic effect Effects 0.000 abstract 1
- 238000000034 method Methods 0.000 description 17
- 239000011259 mixed solution Substances 0.000 description 12
- 239000000243 solution Substances 0.000 description 11
- 238000001179 sorption measurement Methods 0.000 description 11
- 239000002131 composite material Substances 0.000 description 9
- 239000000523 sample Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 8
- 230000006835 compression Effects 0.000 description 6
- 238000007906 compression Methods 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000012300 argon atmosphere Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 239000004088 foaming agent Substances 0.000 description 3
- 239000012520 frozen sample Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 239000000945 filler Substances 0.000 description 2
- 238000001879 gelation Methods 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 210000002345 respiratory system Anatomy 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 239000003381 stabilizer Substances 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 238000010146 3D printing Methods 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 206010014561 Emphysema Diseases 0.000 description 1
- 206010058467 Lung neoplasm malignant Diseases 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- 208000006673 asthma Diseases 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 1
- 229910002113 barium titanate Inorganic materials 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
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- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
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- 206010039083 rhinitis Diseases 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
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- 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
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- 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
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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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Abstract
TiO with photocatalytic function2Preparation of nanowire/graphene aerogel relates to a photocatalytic material in the field of air purification. Adding TiO into the mixture2Mixing the nanowires with the graphene oxide aqueous dispersion to obtain a mixed dispersion; adding sodium hydroxide solid, stirring, adjusting the pH value to 11, adding alkyl glycoside and sodium borate, stirring, foaming, placing in a blast oven for reaction, and adjusting the temperature; freezing the obtained solid, and thawing to completely thawThen, dialysis was performed using a 1% aqueous alcoholic solution; freezing again, drying in a blast oven, and annealing; carrying out heat treatment reaction on the solid obtained by annealing under the protection of argon to obtain TiO2Nanowire/graphene aerogel. The graphene aerogel is used as a carrier, and the GA self high specific surface area can be used for adsorbing the viscous fluid to different degrees. Low cost, can meet different use requirements, can be produced in large batch and has good repeatability. Can be used for photocatalytic formaldehyde degradation.
Description
Technical Field
The invention relates to a photocatalytic material in the field of air purification, in particular to TiO with a photocatalytic function2A preparation method of the nanowire/graphene aerogel.
Background
With the development of socio-economic and the improvement of living standard, people begin to use various furniture and decoration materials in the home, and the problem of indoor air quality is also accompanied. Among them, formaldehyde has been attracting much attention as a known carcinogen and one of the most important VOCs (volatile organic compounds) in indoor places for a long time. Since formaldehyde is highly irritating to the respiratory system and skin mucosa of the human body, for example, 0.08mg of formaldehyde per cubic meter of space will cause discomfort to the eyes and respiratory tract. If the material is used in a high formaldehyde concentration environment for a long time, rhinitis, asthma, emphysema and even lung cancer and other diseases can be caused, so that the preparation of the novel material capable of adsorbing formaldehyde or degrading formaldehyde is not slow.
At present, methods for removing formaldehyde mainly include adsorption methods, plasma methods, photocatalytic methods, and the like. And the adsorption method is one of the most widely used methods. Most of the adsorption materials on the market at present are made of carbon materials, such as graphene aerogel and activated carbon. The Graphene Aerogel (GA) has a strong adsorbability, which is a hotspot of research in recent years, and is generally prepared from Graphene Oxide (GO) by a hydrothermal reaction, a sol-gel method, or 3D printing method. Due to the fact that the graphene aerogel has a rich pore structure and a high specific surface area, the graphene aerogel has more excellent adsorption performance for viscous fluid than other materials, and meanwhile, the GA is endowed with a long service life due to the good elasticity and the good fatigue resistance of the GA. Wu Li Rui et al adopt sponge as skeleton to prepare graphene/carbon nanotube/sponge three-dimensional aerogel structure, modify amino into carbon nanotube in experiment, and improve the adsorption performance of the composite material through chemical adsorption and physical adsorption (Chinese environmental science 2015,35 (11): 3251-3256). Meanwhile, the carbon nanotube enhanced amino functionalized graphene aerogel is prepared, and an amino functional group is introduced into the graphene aerogel by replacing ascorbic acid with ethylenediamine to form a complete three-dimensional network structure, so that a plurality of adsorption sites can be provided, and the chemical reaction with formaldehyde can be promoted. Liangwenjun et al put barium titanate filler in a low temperature plasma reactor, and polarize the filler by applying an alternating current to generate high energy electrons, and the electrons react with formaldehyde molecules (environmental pollution abatement technology and equipment 1008-.
Nanoscale TiO2The N-type semiconductor is composed of a valence band filled with electrons and a conduction band containing holes, and a wider forbidden band exists between the valence band and the conduction band. Nano-sized TiO when in light condition2The electrons in the intermediate valence band are excited to cross the forbidden band and enter the conduction band, and a vacancy is left in the valence band to form a hole-electron pair, so that an electric field is generated, the holes and the electrons migrate to different positions under the action of the electric field, and the electrons can generate superoxide radical (O) with oxygen adsorbed on the surface2 -) The water molecules adsorbed on the surface of the material and the holes form hydroxyl radical (. OH), electron-hole pair, and superoxide radical (. O)2 -) The hydroxyl radical (. OH) is strongly oxidizable and can react with most organic molecules to produce CO2And H2O。
The adsorption rate of the physisorption of the above materials is prolonged with time and gradually reduced as the adsorption sites are reduced, and the use of ethylenediamine for chemisorption may also have irreversible effects on the environment. The method for degrading formaldehyde by using plasma has limited application occasions and relatively high cost. The intrinsic graphene aerogel has the possibility that the framework is not stable enough and the GA three-dimensional structure is possibly damaged in the process of repeated utilization, so that the development of the composite material which can stably adsorb for a long time, is environment-friendly, can be recycled and can degrade formaldehyde in a photocatalysis mode is of great significance.
Disclosure of Invention
The invention aims to provide TiO with a photocatalytic function, which has simple process and low cost and can meet various shape requirements aiming at the problem of preparation of the material2A preparation method of the nanowire/graphene aerogel. Adopts Graphene Oxide (GO), alkyl glycoside, sodium borate and TiO2The nano-wire and the sodium hydroxide are used for preparing the air purification material which can be used for photocatalytic formaldehyde degradation.
The invention comprises the following steps:
1) adding TiO into the mixture2Mixing the nanowires with the graphene oxide aqueous dispersion, and stirring to obtain a mixed dispersion;
2) adding sodium hydroxide solid into the mixed dispersion liquid obtained in the step 1), stirring, adjusting the pH value to 11, adding alkyl glycoside and sodium borate, and stirring to foam;
3) placing the solution foamed in the step 2) in a blast oven for reaction, and adjusting the temperature;
4) freezing the solid obtained in the step 3), then thawing again, and dialyzing by using 1% of water-alcohol solution after completely thawing;
5) freezing the solid dialyzed in the step 4) again, and then drying and annealing the solid in a blast oven;
6) carrying out heat treatment reaction on the solid obtained by annealing in the step 5) under the protection of argon to obtain TiO2Nanowire/graphene aerogel.
In step 1), TiO2The mass ratio of the nanowire to the graphene oxide can be 1 (1-6), the concentration of the graphene oxide is 8-16 mg/mL, and the stirring time is 0.5-1 h.
In the step 2), the mass of the sodium hydroxide solid can be 15-45 g, and the stirring time can be 0.5-1 h; the addition amount of the alkyl glycoside can be 0.5-1.5 mL, and the ratio of the sodium borate to the graphene oxide is 1 (1000-1500); the stirring time is 0.5-1 h, the stirring speed is 900-2000 rpm, and the stirring is carried out until the volume is foamed to be 1.5-3 times of the original volume.
In the step 3), the reaction time can be 6-24 h, and the reaction temperature can be 70-80 ℃.
In the step 4), the freezing temperature is-10 to-20 ℃, and the freezing time is 4 to 18 hours; the dialysis time is 3-24 h.
In the step 5), the freezing temperature is-10 to-20 ℃, and the freezing time is 4 to 18 hours. The drying temperature is 50-65 ℃, and the drying time is 12-48 h; the annealing conditions may be: the heating rate is 1-5 ℃/min, the annealing temperature is 180-220 ℃, and the reaction time is 2-4 h.
In the step 6), the time of the heat treatment reaction is 1-4 h, and the temperature of the heat treatment reaction is 450-550 ℃.
The invention adopts graphene oxide solution and TiO2Mixing the nanowires, preparing the graphene aerogel through a graphene oxide gelation process, and innovatively providing the TiO2The nanowire is loaded on the graphene aerogel, so that the three-dimensional structure of the graphene aerogel can be more stable, and the formaldehyde can be degraded by photocatalysis; in the process of preparing the graphene aerogel, the large-area graphene aerogel can be prepared by foaming the alkyl glycoside serving as the environment-friendly foaming agent. The shape that can change graphite alkene aerogel in the container that holds of difference is placed through mixing liquid to satisfy different user demands. By adding sodium borate, the crosslinking of graphene oxide and adjacent sheets can be promoted, and meanwhile, the self-assembly process of the graphene oxide can be promoted, so that the three-dimensional structure of the graphene oxide is more stable. The processes of freezing, thawing and refreezing can also make the three-dimensional structure of the food more stable. Then, redundant sodium hydroxide and sodium borate in the solution can be washed away through a dialysis process of 1 percent hydroalcoholic solution. The annealing treatment at 200 ℃ can decompose the residual alkyl glycoside therein. The TiO can be prepared by a heat treatment process under the final argon atmosphere2Nanowire-loaded graphene aerogel composites. By taking the graphene aerogel as a carrier, the viscous fluid can be subjected to different degrees by utilizing the high specific surface area of GAAnd (4) adsorbing. In addition, the invention has the advantages of low cost, capability of meeting different use requirements, mass production, good repeatability and the like, and has higher economic value.
Drawings
FIG. 1 shows TiO prepared in example 12A stress-strain diagram of nanowire/graphene aerogel composite compression.
FIG. 2 shows TiO prepared in example 22A stress-strain diagram of nanowire/graphene aerogel composite compression.
FIG. 3 shows TiO prepared in example 42A stress-strain diagram of nanowire/graphene aerogel composite compression.
Detailed Description
In the invention, TiO is mixed with2The nanowires are mixed with a graphene oxide solution, and a bubble-ice template method is used, and a foaming agent alkyl glycoside, a stabilizer borate and sodium hydroxide are added, so that GO undergoes gelation through self-assembly under an alkaline condition, and further GA is prepared. The following examples will further illustrate the present invention with reference to the accompanying drawings.
Example 1:
in this example, a bubble-ice template was used to prepare TiO2The preparation method of the nanowire/graphene aerogel comprises the following steps:
(1) taking 50mL of graphene oxide and TiO of 8mg/mL20.4g of nanowires.
(2) And (2) adding 20g of sodium hydroxide into the mixed + -mixed solution obtained in the step (1), placing the mixed + -mixed solution on a magnetic stirrer, stirring for 0.5h, and adjusting the pH value to be about 11.
(3) Adding 800 μ L of alkyl glycoside to the mixed solution obtained in step (2), adding 0.4mg of sodium borate, stirring the mixed solution, and foaming until the volume becomes 1.5 times of the original volume.
(4) And (4) placing the solution foamed in the step (3) in a forced air oven for reaction at the reaction temperature of 75 ℃ for 12 h.
(5) And (4) freezing the sample obtained in the step (4), wherein the freezing temperature is about-18 ℃ and the freezing time is 6 h.
(6) Thawing the frozen sample obtained in the step (5), and dialyzing by using 1% of water-alcohol solution after completely thawing, wherein the dialysis time is 6 h.
(7) And (4) putting the sample washed in the step (6) into a refrigerator for freezing again, wherein the freezing temperature is about-18 ℃, and the freezing time is 12 hours.
(8) And (3) drying the solid obtained in the step (7) for 12 hours at the temperature of 60 ℃.
(9) And (4) annealing the sample in the step (8), wherein the heating rate is 2 ℃/min, the annealing temperature is 200 ℃, the annealing time is 4h, and the atmosphere condition is air.
(10) And (4) carrying out heat treatment on the solid obtained in the step (9) in an argon atmosphere, wherein the reaction temperature is 500 ℃, and the reaction time is 2 hours.
Example 1 preparation of TiO2The stress-strain diagram for nanowire/graphene aerogel composite compression is shown in figure 1.
Example 2:
in this example, a bubble-ice template was used to prepare TiO2The preparation method of the nanowire/graphene aerogel comprises the following steps:
(1) taking 50mL of 10mg/mL graphene oxide and TiO2Nanowires 1 g.
(2) And (2) adding 30g of sodium hydroxide into the mixed solution obtained in the step (1), placing the mixed solution on a magnetic stirrer, stirring for 0.5h, and adjusting the pH value to be about 11.
(3) Adding 830. mu.L of alkyl glycoside to the mixed solution obtained in step (2), adding 0.5mg of sodium borate, stirring the mixed solution, and foaming until the volume becomes 2 times of the original volume.
(4) And (4) placing the solution foamed in the step (3) in a forced air oven for reaction at the reaction temperature of 80 ℃ for 12 h.
(5) And (4) freezing the sample obtained in the step (4), wherein the freezing temperature is about-18 ℃ and the freezing time is 6 h.
(6) And (4) thawing the frozen sample obtained in the step (5), and dialyzing the obtained solid for 12h after complete thawing.
(7) And (4) putting the sample washed in the step (6) into a refrigerator for freezing again, wherein the freezing temperature is about-18 ℃, and the freezing time is 12 hours.
(8) And (3) drying the solid obtained in the step (7) for 12 hours at the temperature of 60 ℃.
(9) And (4) annealing the sample in the step (8), wherein the heating rate is 2 ℃/min, the annealing temperature is 200 ℃, the annealing time is 4h, and the atmosphere condition is air.
(10) And (4) carrying out heat treatment on the solid obtained in the step (9) in an argon atmosphere, wherein the reaction temperature is 500 ℃, and the reaction time is 2 hours.
Example 2 preparation of TiO2The stress-strain diagram for the nanowire/graphene aerogel composite compression is shown in figure 2.
Example 3:
in this example, a bubble-ice template was used to prepare TiO2The preparation method of the nanowire/graphene aerogel comprises the following steps:
(1) taking 100mL of 16mg/mL graphene oxide and TiO2Nanowires 8 g.
(2) And (2) adding 40g of sodium hydroxide into the mixed solution obtained in the step (1), placing the mixed solution on a magnetic stirrer, stirring for 1 hour, and adjusting the pH value to be about 11.
(3) 2.656mL of alkyl glycoside was added to the mixed solution obtained in step (2), 1.6mg of sodium borate was added, and the mixed solution was stirred and foamed until the volume became 2.5 times the original volume.
(4) And (4) placing the solution foamed in the step (3) in a forced air oven for reaction at the reaction temperature of 75 ℃ for 12 h.
(5) And (4) freezing the sample obtained in the step (4), wherein the freezing temperature is about-18 ℃, and the freezing time is 12 h.
(6) And (4) thawing the frozen sample obtained in the step (5), and dialyzing the obtained solid for 12h after complete thawing.
(7) And (4) putting the sample washed in the step (6) into a refrigerator for freezing again, wherein the freezing temperature is about-18 ℃, and the freezing time is 12 hours.
(8) And (3) drying the solid obtained in the step (7) for 12 hours at the temperature of 60 ℃.
(9) And (4) annealing the sample in the step (8), wherein the heating rate is 2 ℃/min, the annealing temperature is 200 ℃, the annealing time is 4h, and the atmosphere condition is air.
(10) And (4) carrying out heat treatment on the solid obtained in the step (9) in an argon atmosphere, wherein the reaction temperature is 500 ℃, and the reaction time is 2 h.
A stress strain diagram of the TiO2 nanowire/graphene aerogel composite prepared in example 3 under compression is shown in fig. 3.
Table 1 shows TiO prepared in examples 1 to 32Elastic modulus of nanowire/graphene aerogel.
TABLE 1
Examples | 1 | 2 | 3 |
Modulus of elasticity (MPa) | 0.07942 | 0.01084 | 0.00315 |
As can be seen from Table 1 and FIGS. 1 to 3, TiO compounds obtained in examples 1 to 32The nanowire/graphene aerogel has lower elastic modulus, and when the concentration is increased, the foaming volume is increased, so that the loading line and the unloading line of the nanowire/graphene aerogel are almost overlapped, the elastic hysteresis loop is small, and the elastic modulus of the graph 3 is lower than that of the graphs 1 and 2 by one order of magnitude, which shows that the TiO is2The doping of the nano-wire plays a certain supporting role on the three-dimensional structure of the graphene aerogel, so that the surfaceShowing better elasticity.
The invention adopts a sol-gel method, takes bubbles and ice as templates and takes TiO as2Mixing the nanowire with a graphene oxide solution, and adding a foaming agent alkyl glycoside and a stabilizer sodium borate to prepare TiO2Nanowire/graphene aerogel. The innovative proposal of the TiO2Doping of nanowires into graphene aerogel, TiO on the one hand2The addition of the nano wire can enable the three-dimensional structure of the graphene aerogel to be more stable, and lower elastic modulus can be generated, and on the other hand, TiO2The addition of (2) enables the graphene aerogel to realize the performance of degrading formaldehyde through photocatalysis. TiO22The nanowire/graphene aerogel has the advantages of good elasticity, adjustable shape, photocatalytic performance, strong experimental repeatability and the like, so that the nanowire/graphene aerogel has great competitiveness in the existing adsorption and purification materials and has high commercial value.
Claims (10)
1. TiO with photocatalytic function2The preparation method of the nanowire/graphene aerogel is characterized by comprising the following steps:
1) adding TiO into the mixture2Mixing the nanowires with the graphene oxide aqueous dispersion, and stirring to obtain a mixed dispersion;
2) adding sodium hydroxide solid into the mixed dispersion liquid obtained in the step 1), stirring, adjusting the pH value to 11, adding alkyl glycoside and sodium borate, stirring and foaming;
3) placing the solution foamed in the step 2) in a blast oven for reaction, and adjusting the temperature;
4) freezing the solid obtained in the step 3), then thawing again, and dialyzing by using 1% of water-alcohol solution after completely thawing;
5) freezing the solid dialyzed in the step 4) again, and then drying and annealing the solid in a blast oven;
6) carrying out heat treatment reaction on the solid obtained by annealing in the step 5) under the protection of argon to obtain TiO2Nanowire/graphene aerogel.
2. As claimed inClaim 1 of the TiO having a photocatalytic function2Preparation of nanowire/graphene aerogel, characterized in that in step 1), the TiO is2The mass ratio of the nanowires to the graphene oxide is 1 (1-6).
3. TiO with photocatalytic function according to claim 12The preparation method of the nanowire/graphene aerogel is characterized in that in the step 1), the concentration of the graphene oxide aqueous dispersion is 8-16 mg/mL, and the stirring time is 0.5-1 h.
4. TiO with photocatalytic function according to claim 12The preparation method of the nanowire/graphene aerogel is characterized in that in the step 2), the addition amount of the sodium hydroxide solid is 15-45 g, and the stirring time is 0.5-1 h.
5. TiO with photocatalytic function according to claim 12The preparation method of the nanowire/graphene aerogel is characterized in that in the step 2), the addition amount of the alkyl glycoside is 0.5-1.5 mL, and the ratio of the sodium borate to the graphene oxide is 1 (1000-1500).
6. TiO with photocatalytic function according to claim 12The preparation method of the nanowire/graphene aerogel is characterized in that in the step 2), the stirring foaming time is 0.5-1 h, the stirring foaming speed is 900-2000 rpm, and the stirring is carried out until the volume is foamed to be 1.5-3 times of the original volume.
7. TiO with photocatalytic function according to claim 12The preparation method of the nanowire/graphene aerogel is characterized in that in the step 3), the reaction time can be 6-24 hours, and the reaction temperature can be 70-80 ℃.
8. TiO with photocatalytic function according to claim 12The preparation method of the nanowire/graphene aerogel is characterized in that in the step 4), the freezing temperature is-10 to-20 ℃, and the freezing temperature is cooledThe freezing time is 4-18 h; the dialysis time is 3-24 h.
9. TiO with photocatalytic function according to claim 12The preparation method of the nanowire/graphene aerogel is characterized in that in the step 5), the freezing temperature is-10 to-20 ℃, and the freezing time is 4 to 18 hours; the drying temperature is 50-65 ℃, and the drying time is 12-48 h; the annealing conditions may be: the heating rate is 1-5 ℃/min, the annealing temperature is 180-220 ℃, and the reaction time is 2-4 h.
10. TiO with photocatalytic function according to claim 12The preparation method of the nanowire/graphene aerogel is characterized in that in the step 6), the time of the heat treatment reaction is 1-4 hours, and the temperature of the heat treatment reaction is 450-550 ℃.
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