CN116332227B - TiO (titanium dioxide)2Preparation method of star-shaped nano material - Google Patents
TiO (titanium dioxide)2Preparation method of star-shaped nano material Download PDFInfo
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 17
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title 2
- 239000004408 titanium dioxide Substances 0.000 title 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 title 1
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 64
- 238000006243 chemical reaction Methods 0.000 claims abstract description 49
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000012071 phase Substances 0.000 claims abstract description 27
- 239000012074 organic phase Substances 0.000 claims abstract description 24
- QGLWBTPVKHMVHM-KTKRTIGZSA-N (z)-octadec-9-en-1-amine Chemical compound CCCCCCCC\C=C/CCCCCCCCN QGLWBTPVKHMVHM-KTKRTIGZSA-N 0.000 claims abstract description 22
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011541 reaction mixture Substances 0.000 claims abstract description 20
- 239000002244 precipitate Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 16
- 239000012153 distilled water Substances 0.000 claims abstract description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 14
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 claims abstract description 11
- 229940012189 methyl orange Drugs 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 9
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 239000006228 supernatant Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 239000002073 nanorod Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 5
- 239000011941 photocatalyst Substances 0.000 claims description 4
- 230000000593 degrading effect Effects 0.000 claims 1
- 238000001354 calcination Methods 0.000 abstract description 3
- 230000001699 photocatalysis Effects 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000012530 fluid Substances 0.000 abstract 1
- 239000007788 liquid Substances 0.000 description 11
- 238000012546 transfer Methods 0.000 description 10
- 238000007789 sealing Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 5
- 238000003917 TEM image Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 239000012429 reaction media Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000006750 UV protection Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000003630 growth substance Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000002834 transmittance Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
- C01G23/0536—Producing by wet processes, e.g. hydrolysing titanium salts by hydrolysing chloride-containing salts
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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
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Abstract
The invention relates to a preparation method of a TiO 2 star-shaped nano material, which comprises the steps of adding a certain amount of chloroform and oleylamine into a reaction kettle with a polytetrafluoroethylene liner to form an organic phase, rapidly adding a certain amount of TiCl 4 and distilled water into the organic phase to form a two-phase reaction system, heating the reaction kettle to 120-160 ℃, carrying out two-phase thermal reaction for 6-10 hours, cooling the obtained reaction mixture to room temperature, adding absolute ethyl alcohol to dissolve the reaction mixture into a phase, carrying out centrifugal separation, pouring out supernatant fluid, obtaining a lower-layer precipitate, and centrifugally washing the precipitate by using the absolute ethyl alcohol to obtain the TiO 2 star-shaped nano material. The preparation method does not need complex process steps such as calcination, is mild in preparation condition and easy to control, and can be used for preparing the TiO 2 nano material with the star-shaped structure, which has the advantages of uniform appearance, stable structure, excellent performance and clean surface, and the TiO 2 nano material with the star-shaped structure has excellent photocatalytic performance, so that methyl orange can be completely catalyzed and degraded within 2 hours.
Description
Technical Field
The invention belongs to the technical field of inorganic nano material preparation, and particularly relates to a method for preparing a TiO 2 star-shaped nano material by adopting two immiscible solutions through solvothermal reaction.
Background
The nano TiO 2 material is an inorganic nonmetallic material with excellent properties, such as good corrosion resistance, ultraviolet resistance, heat resistance, photocatalysis, thermal stability and the like, and is widely applied to industries of pigment, rubber, plastic, papermaking and the like. Therefore, the nano TiO 2 material with excellent preparation performance is attractive. At present, the preparation of TiO 2 mainly comprises the following modes: high temperature gas phase synthesis, liquid phase sol-gel, hydrolysis, solid material thermal decomposition, coprecipitation, etc. The high temperature vapor phase synthesis method is to utilize the steam of metal compound to produce TiO 2 through chemical reaction. The TiO 2 prepared by the method has good dispersibility, good visible light transmittance and strong ultraviolet shielding capability, but the temperature is generally above 1000 ℃, the one-time investment is huge, the subsequent treatment of powder needs to be solved, and the overall price is relatively high. The sol-gel method for preparing TiO 2 needs to make the solution undergo the sol-gel process, and the obtained product powder is uniform and has good dispersibility, but few crystal nuclei are formed at the initial stage, the reaction time is long, and the cost of raw materials is high. The hydrolysis method utilizes titanium liquid to hydrolyze and generate TiO 2, is heated unevenly in the traditional kettle type structure, has harsh process control conditions, is difficult to control the forming and production of particles, and is unfavorable for production.
For this reason, researchers have developed many new processes to solve the above problems, for example, the chinese invention patent with publication number CN105036186a uses nano TiO 2 to impregnate and react with ethyl alcohol solvent of ethyl orthosilicate, then evaporating to dryness, drying, and then roasting at high temperature to convert ethyl orthosilicate into SiO 2, the method greatly reduces the surface energy of nano TiO 2 particles, thus improving the dispersibility and stability of nano TiO 2, and the materials are cheap, but the method needs higher temperature and needs to be performed under oxygen-enriched condition, and the energy consumption is large. Therefore, it is very necessary to develop a simple and easy method for synthesizing nano TiO 2.
The properties of nanomaterials are not only related to the nature of the metal, but also have a close and inseparable relationship with the morphology and structure of the nanomaterial. The star-shaped nano material has the characteristics of large surface area, self-supporting structure, difficult agglomeration and the like, and is a nano material with great potential. However, the star-structured nano TiO 2 material is rarely involved, and most of the current TiO 2 nano materials are in a spherical or rod-shaped structure. For example, the Chinese patent publication No. CN115304098A uses TiCl 4 as reactant and water as reaction medium, and adopts coprecipitation method to prepare bar-shaped TiO 2 nano particles at 80-90 deg.C by adding proper amount of precipitant and growth regulator. Compared with a rod shape, the star-shaped nano particle structure is more stable, is not easy to aggregate and is convenient to recycle.
Disclosure of Invention
The invention aims to provide a preparation method of a TiO 2 star-shaped nano material, which is characterized in that two immiscible solutions are used as reaction media, and complex process steps such as calcination and the like are not needed, so that the TiO 2 nano material with a star-shaped structure, which has uniform morphology, stable structure, excellent catalytic performance and clean surface, is prepared by a one-step method.
The invention is realized by the following technical scheme, and the preparation method of the TiO 2 star-shaped nano material provided by the invention comprises the following steps:
(1) Respectively adding a certain amount of chloroform and oleylamine into a polytetrafluoroethylene liner of a reaction kettle to form an organic phase for later use;
(2) Respectively taking a certain amount of TiCl 4 and distilled water for later use;
(3) Rapidly adding distilled water and TiCl 4 in the step (2) into the organic phase in the step (1) to form a two-phase reaction system, sealing, heating the reaction kettle to 120-160 ℃, performing two-phase thermal reaction for 6-10 h, and cooling the obtained reaction mixture to room temperature;
(4) Pouring the reaction mixture obtained in the step (3) into a beaker, adding absolute ethyl alcohol to dissolve into a phase, centrifuging, pouring out supernatant to obtain lower-layer sediment, centrifuging and washing the obtained sediment for 3-5 times by using the absolute ethyl alcohol, and drying in vacuum at 40 ℃ to obtain the TiO 2 star-shaped nano material.
In the preparation method of the TiO 2 star-shaped nano material, the volume ratio of the oleylamine to the chloroform in the step (1) is 1:3-1:5.
In the preparation method of the TiO 2 star-shaped nano material, the volume ratio of TiCl 4 to distilled water in the step (2) is 1:3-1:6.
According to the preparation method of the TiO 2 star-shaped nano material, the rotating speed of the centrifugal machine is 1000-1500r/min in the step (4) of centrifugal separation, and the time is 3-5 min.
According to the preparation method of the TiO 2 star-shaped nano material, the prepared TiO 2 star-shaped nano material has star-shaped morphology, the particle size is about 3.0-5.0 mu m, the nano material is formed by assembling dozens of straight nano rods by emitting from the star center to the periphery, the diameter of the nano rods is about 20nm, and the length is 1.5-2.5 mu m.
Furthermore, the prepared TiO 2 star-shaped nano material can be used as a photocatalyst, and has excellent catalytic performance in a photocatalytic degradation test of methyl orange, and the methyl orange can be completely catalytically degraded within 2 hours.
Compared with the prior art, the invention has obvious advantages and beneficial effects. By means of the technical scheme, the invention can achieve quite technical progress and practicability, has wide utilization value, and has at least the following advantages:
(1) The invention takes two immiscible solutions as reaction medium, and the reactants grow and assemble at the interface of the two immiscible phases, wherein the organic phase is chloroform solution dissolved with oleylamine. The oleylamine has amphiphilic property, a longer alkyl chain of the oleylamine is dissolved in a chloroform phase, and an amino functional group can go deep into a water phase, so that the oleylamine can exist at a two-phase interface, and the morphology and structure of a product can be effectively regulated and controlled. The preparation method is simple and convenient, does not need complex processes such as oxygen enrichment, calcination and the like, has low reactant price and mild and easily controlled reaction conditions, and can synthesize the star-shaped TiO 2 nano structure with uniform morphology, stable structure, excellent performance and clean surface in one step.
(2) The invention successfully synthesizes the star-shaped TiO 2 nano structure with self-supporting characteristic by adopting oleylamine at the two-phase interface, the size of TiO 2 nano particles is about 3.0-5.0 mu m, the nano structure is formed by assembling dozens of straight nano rods by emitting from the star center to the periphery, the diameter of the nano rods is about 20nm, the length is 1.5-2.5 mu m, and the nano structure has a typical 3D multi-stage structure. The TiO 2 star-shaped nano material has a more stable structure, is not easy to gather, and is convenient to recycle. The catalyst has excellent catalytic performance in experiments of photocatalytic degradation of methyl orange, and can completely degrade the methyl orange in 2 hours.
Drawings
FIG. 1 is an SEM image at 20000 magnification of a TiO 2 star-shaped nanomaterial prepared in example 3;
FIG. 2 is an SEM image at 100000 magnification of the TiO 2 star-shaped nanomaterial prepared in example 3;
FIG. 3 is a TEM image of the TiO 2 star-shaped nanomaterial prepared in example 3 at 12000 x magnification;
FIG. 4 is a TEM image of the TiO 2 star-shaped nanomaterial prepared in example 3 at 300000 x magnification;
FIG. 5 is an XRD pattern of the TiO 2 star-shaped nanomaterial prepared in example 3;
Fig. 6 is a graph showing the time course of the catalytic photodegradation of methyl orange by using the TiO 2 star-shaped nanomaterial prepared in example 3.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below in conjunction with specific embodiments, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to fall within the scope of the invention.
The invention provides a preparation method of a TiO 2 star-shaped nano material, which specifically comprises the following steps:
(1) Respectively adding a certain amount of chloroform and oleylamine into a polytetrafluoroethylene liner of a reaction kettle to form an organic phase for later use; the volume ratio of the oleylamine to the chloroform is 1:3-1:5;
(2) Respectively taking a certain amount of TiCl 4 and distilled water for later use; the volume ratio of TiCl 4 to distilled water is 1:3-1:6;
(3) Rapidly adding distilled water and TiCl 4 which are measured in the step (2) into the organic phase in the step (1) to form a reaction solution, sealing the reaction solution, heating the reaction kettle to 120-160 ℃, performing two-phase thermal reaction for 6-10 h, and cooling the obtained reaction mixture to room temperature;
(4) Pouring the reaction mixture obtained in the step (3) into a beaker, adding absolute ethyl alcohol, dissolving into a phase, then placing the reaction mixture into a centrifugal machine with the rotating speed of 1000-1500r/min, centrifuging for 3-5min, pouring out supernatant to obtain a lower-layer precipitate, centrifuging and washing the obtained precipitate for 3-5 times by using the absolute ethyl alcohol, and vacuum-drying at 40 ℃ for 24h to obtain the TiO 2 star-shaped nano material.
The following detailed description is given by way of specific examples, which are not meant to limit the invention, but the invention is applicable to extended applications based on the following examples.
Example 1
1) Transferring 7mL of chloroform solution into a polytetrafluoroethylene liner of a 25mL reaction kettle by using a liquid transfer gun, transferring 2mL of oleylamine by using the liquid transfer gun, adding the oleylamine into the chloroform solution of the polytetrafluoroethylene liner, and uniformly mixing to form an organic phase;
2) 1mL TiCl 4 and 5mL distilled water are rapidly added into the organic phase prepared in the step 1), and the organic phase is covered;
3) Placing the reaction solution prepared in the step 2) into a reaction kettle, sealing, heating the reaction kettle to 150 ℃, performing two-phase thermal reaction for 8 hours, stopping the reaction, and cooling the obtained reaction mixture to room temperature for later use;
4) Pouring the reaction mixture prepared in the step 3) into a beaker, adding absolute ethyl alcohol, dissolving into a phase, centrifuging in a centrifuge, pouring out supernatant to obtain a lower-layer precipitate, centrifuging and washing the lower-layer precipitate for 3 times by using the absolute ethyl alcohol, and then drying in vacuum at 40 ℃ for 24 hours to obtain the TiO 2 star-shaped nano material.
Example 2
1) Transferring 7mL of chloroform solution into a polytetrafluoroethylene liner of a 25mL reaction kettle by using a liquid transfer gun, transferring 2mL of oleylamine by using the liquid transfer gun, adding the oleylamine into the chloroform solution of the polytetrafluoroethylene liner, and uniformly mixing to form an organic phase;
2) 1mL TiCl 4 and 6mL distilled water are rapidly added into the organic phase prepared in the step 1), and the organic phase is covered;
3) Placing the reaction solution prepared in the step 2) into a reaction kettle, sealing, heating the reaction kettle to 150 ℃, performing two-phase thermal reaction for 10 hours, stopping the reaction, and cooling the obtained reaction mixture to room temperature for later use;
4) Pouring the reaction mixture prepared in the step 3) into a beaker, adding absolute ethyl alcohol, dissolving into a phase, centrifuging in a centrifuge, pouring out supernatant to obtain a lower-layer precipitate, centrifuging and washing the lower-layer precipitate for 3 times by using the absolute ethyl alcohol, and then drying in vacuum at 40 ℃ for 24 hours to obtain the TiO 2 star-shaped nano material.
Example 3
1) Transferring 8mL of chloroform solution into a polytetrafluoroethylene inner container of a 25mL reaction kettle by using a liquid transfer gun, transferring 2.5mL of oleylamine by using the liquid transfer gun, adding the oleylamine into the chloroform solution of the polytetrafluoroethylene inner container, and uniformly mixing to form an organic phase;
2) 1.2mL TiCl 4 and 5mL distilled water are rapidly added into the organic phase prepared in the step 1), and the organic phase is covered;
3) Placing the reaction solution prepared in the step 2) into a reaction kettle, sealing, heating the reaction kettle to 120 ℃, performing two-phase thermal reaction for 10 hours, stopping the reaction, and cooling the obtained reaction mixture to room temperature for later use;
4) Pouring the reaction mixture prepared in the step 3) into a beaker, adding absolute ethyl alcohol, dissolving into a phase, centrifuging in a centrifuge, pouring out supernatant to obtain a lower-layer precipitate, centrifuging and washing the lower-layer precipitate for 3 times by using the absolute ethyl alcohol, and then drying in vacuum at 40 ℃ for 24 hours to obtain the TiO 2 star-shaped nano material.
Fig. 1-2 are SEM images of the star-shaped TiO 2 nanostructure prepared in this example at different magnifications, and fig. 3-4 are TEM images of the star-shaped TiO 2 nanostructure at different magnifications, and it can be seen that the prepared TiO 2 nanostructure has a star-shaped morphology with a particle size of about 3.0 to 5.0 μm, and is assembled by several tens of straight nanorods emitted from the center of the star to the periphery, the diameter of the nanorods is about 20nm, and the length is 1.5 to 2.5 μm, and has a typical 3D multilevel structure.
Fig. 5 is an XRD pattern of the TiO 2 star nanomaterial prepared in this example, indicating higher purity of the synthesized product.
The photocatalytic performance test was performed on the TiO 2 star-shaped nanomaterial prepared in this example: taking TiO 2 star-shaped nano material prepared by a certain mass as a photocatalyst, taking 10mmol/L of methyl orange as a target degradation product, wherein the volume of the methyl orange is 50mL, the concentration of the TiO 2 star-shaped nano material in a methyl orange solution is 0.8g/L, a 150-watt high-pressure mercury lamp is selected as a light source, the distance between a sample and the lamp tube is 10cm, and carrying out a photocatalytic degradation experiment, wherein FIG. 6 is a photocatalytic degradation effect diagram, and the result shows that the prepared TiO 2 star-shaped nano material shows excellent catalytic performance in the experiment of photocatalytic degradation of methyl orange, and can completely catalyze and degrade the methyl orange within 2h.
Example 4
1) Transferring 8mL of chloroform solution into a polytetrafluoroethylene inner container of a 25mL reaction kettle by using a liquid transfer gun, transferring 1.6mL of oleylamine by using the liquid transfer gun, adding the oleylamine into the chloroform solution of the polytetrafluoroethylene inner container, and uniformly mixing to form an organic phase;
2) 1.5mL TiCl 4 and 5mL distilled water are rapidly added into the organic phase prepared in the step 1), and the organic phase is covered;
3) Placing the reaction solution prepared in the step 2) into a reaction kettle, sealing, heating the reaction kettle to 160 ℃, performing two-phase thermal reaction for 6 hours, stopping the reaction, and cooling the obtained reaction mixture to room temperature for later use;
4) Pouring the reaction mixture prepared in the step 3) into a beaker, adding absolute ethyl alcohol, dissolving into a phase, centrifuging in a centrifuge, pouring out supernatant to obtain a lower-layer precipitate, centrifuging and washing the lower-layer precipitate for 3 times by using the absolute ethyl alcohol, and then drying in vacuum at 40 ℃ for 24 hours to obtain the TiO 2 star-shaped nano material.
Example 5
1) Transferring 9mL of chloroform solution into a polytetrafluoroethylene inner container of a 25mL reaction kettle by using a liquid transfer gun, transferring 2.4mL of oleylamine by using the liquid transfer gun, adding the oleylamine into the chloroform solution of the polytetrafluoroethylene inner container, and uniformly mixing to form an organic phase;
2) 1mL TiCl 4 and 5mL distilled water are rapidly added into the organic phase prepared in the step 1), and the organic phase is covered;
3) Placing the reaction solution prepared in the step 2) into a reaction kettle, sealing, heating the reaction kettle to 120 ℃, performing two-phase thermal reaction for 8 hours, stopping the reaction, and cooling the obtained reaction mixture to room temperature for later use;
4) Pouring the reaction mixture prepared in the step 3) into a beaker, adding absolute ethyl alcohol, dissolving into a phase, centrifuging in a centrifuge, pouring out supernatant to obtain a lower-layer precipitate, centrifuging and washing the lower-layer precipitate for 3 times by using the absolute ethyl alcohol, and then drying in vacuum at 40 ℃ for 24 hours to obtain the TiO 2 star-shaped nano material.
The foregoing is merely an embodiment of the present invention, and the present invention is not limited in any way, and may have other embodiments according to the above structures and functions, which are not listed. Any simple modification, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, without departing from the scope of the technical solution of the present invention, will still fall within the scope of the technical solution of the present invention.
Claims (5)
1. The preparation method of the TiO 2 star-shaped nano material is characterized by comprising the following steps of:
(1) Respectively adding a certain amount of chloroform and oleylamine into a polytetrafluoroethylene liner of a reaction kettle to form an organic phase for later use; the volume ratio of the oleylamine to the chloroform is 1:3-1:5;
(2) Respectively taking a certain amount of TiCl 4 and distilled water for later use; the volume ratio of TiCl 4 to distilled water is 1:3-1:6;
(3) Rapidly adding distilled water and TiCl 4 in the step (2) into the organic phase in the step (1) to form a two-phase reaction system, heating the reaction kettle to 120-160 ℃, performing two-phase thermal reaction for 6-10 h, and cooling the obtained reaction mixture to room temperature;
(4) Pouring the reaction mixture obtained in the step (3) into a beaker, adding absolute ethyl alcohol to dissolve the reaction mixture into a phase, centrifuging, pouring out supernatant to obtain a lower-layer precipitate, centrifuging and washing the precipitate for 3-5 times by using the absolute ethyl alcohol, and drying the precipitate in vacuum at 40 ℃ to obtain the TiO 2 star-shaped nano material.
2. The method for preparing the TiO 2 star-shaped nanomaterial according to claim 1, wherein the rotational speed of a centrifugal machine in the step (4) is 1000-1500 r/min and the time is 3-5 min.
3. The method for preparing the TiO 2 star-shaped nanomaterial as claimed in claim 1, wherein the prepared TiO 2 star-shaped nanomaterial has a star-shaped morphology, the particle size is 3.0-5.0 μm, the nanomaterial is formed by assembling dozens of straight nanorods by emitting from the star center to the periphery, the diameter of the nanorods is 20nm, and the length of the nanorods is 1.5-2.5 μm.
4. The method for preparing a TiO 2 star nanomaterial according to claim 1, wherein the prepared TiO 2 star nanomaterial is used as a photocatalyst.
5. The method for preparing the TiO 2 star-shaped nanomaterial according to claim 4, wherein the TiO 2 star-shaped nanomaterial is used as a photocatalyst for degrading methyl orange.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5536448A (en) * | 1993-10-22 | 1996-07-16 | Ishihara Sangyo Kaisha, Ltd. | Dendrite or asteroidal titanium dioxide micro-particles |
| CN102089246A (en) * | 2008-07-07 | 2011-06-08 | 萨克特本颜料合股公司 | Method for producing microcrystalline titanium oxide |
| CN102962042A (en) * | 2012-11-28 | 2013-03-13 | 上海大学 | Preparation method of porous TiO2 nano optical catalysis material |
| CN104192895A (en) * | 2014-08-12 | 2014-12-10 | 渤海大学 | Method for preparing nanometer TiO2 microspheres |
| CN105126713A (en) * | 2015-07-24 | 2015-12-09 | 北京理工大学 | TiO2-coated nano-crystal material and preparation method thereof |
| CN105439197A (en) * | 2015-12-02 | 2016-03-30 | 中国人民解放军第二军医大学 | Preparation method of urchin-like rutile type nano titanium oxide |
| CN105506736A (en) * | 2015-12-22 | 2016-04-20 | 国家纳米科学中心 | Nano TiO2 single-crystal material, preparation method and application of material |
| CN105543961A (en) * | 2015-12-22 | 2016-05-04 | 国家纳米科学中心 | Nano TiO2 monocrystalline material, preparation method therefor and use of nano TiO2 monocrystalline material |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101279231B (en) * | 2007-04-06 | 2010-05-26 | 清华大学 | Method for assembling three-dimensional aqueous dispersion colloid ball from nanocrystalline |
-
2023
- 2023-03-23 CN CN202310290998.2A patent/CN116332227B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5536448A (en) * | 1993-10-22 | 1996-07-16 | Ishihara Sangyo Kaisha, Ltd. | Dendrite or asteroidal titanium dioxide micro-particles |
| CN102089246A (en) * | 2008-07-07 | 2011-06-08 | 萨克特本颜料合股公司 | Method for producing microcrystalline titanium oxide |
| CN102962042A (en) * | 2012-11-28 | 2013-03-13 | 上海大学 | Preparation method of porous TiO2 nano optical catalysis material |
| CN104192895A (en) * | 2014-08-12 | 2014-12-10 | 渤海大学 | Method for preparing nanometer TiO2 microspheres |
| CN105126713A (en) * | 2015-07-24 | 2015-12-09 | 北京理工大学 | TiO2-coated nano-crystal material and preparation method thereof |
| CN105439197A (en) * | 2015-12-02 | 2016-03-30 | 中国人民解放军第二军医大学 | Preparation method of urchin-like rutile type nano titanium oxide |
| CN105506736A (en) * | 2015-12-22 | 2016-04-20 | 国家纳米科学中心 | Nano TiO2 single-crystal material, preparation method and application of material |
| CN105543961A (en) * | 2015-12-22 | 2016-05-04 | 国家纳米科学中心 | Nano TiO2 monocrystalline material, preparation method therefor and use of nano TiO2 monocrystalline material |
Non-Patent Citations (1)
| Title |
|---|
| 磁性核壳介孔氧化硅微球的制备与应用;付庆涛;何婷婷;于濂清;刘勇军;柴永明;刘晨光;;化学进展;20100630;第22卷(第06期);第1116-1124页 * |
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