CN108502923B - Preparation method of nano titanium dioxide material with uniform particle size distribution - Google Patents
Preparation method of nano titanium dioxide material with uniform particle size distribution Download PDFInfo
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- CN108502923B CN108502923B CN201810405223.4A CN201810405223A CN108502923B CN 108502923 B CN108502923 B CN 108502923B CN 201810405223 A CN201810405223 A CN 201810405223A CN 108502923 B CN108502923 B CN 108502923B
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- 239000002245 particle Substances 0.000 title claims abstract description 34
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 title claims abstract description 24
- 239000000463 material Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims abstract description 67
- 239000006185 dispersion Substances 0.000 claims abstract description 57
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229920002153 Hydroxypropyl cellulose Polymers 0.000 claims abstract description 45
- 239000001863 hydroxypropyl cellulose Substances 0.000 claims abstract description 45
- 235000010977 hydroxypropyl cellulose Nutrition 0.000 claims abstract description 45
- 238000003756 stirring Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 238000007789 sealing Methods 0.000 claims abstract description 28
- 238000001914 filtration Methods 0.000 claims abstract description 27
- 239000002244 precipitate Substances 0.000 claims abstract description 24
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 21
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 21
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000012153 distilled water Substances 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 15
- 238000001704 evaporation Methods 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 14
- 238000001816 cooling Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 230000008020 evaporation Effects 0.000 claims description 11
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 38
- 239000004408 titanium dioxide Substances 0.000 abstract description 18
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 8
- 230000000694 effects Effects 0.000 description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000011941 photocatalyst Substances 0.000 description 3
- 230000005476 size effect Effects 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000000413 hydrolysate Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/30—Three-dimensional structures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/51—Particles with a specific particle size distribution
- C01P2004/52—Particles with a specific particle size distribution highly monodisperse size distribution
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a preparation method of a nano titanium dioxide material with uniform particle size distribution, which comprises the following steps of 1, adding n-butyl titanate into absolute ethyl alcohol, adding polyvinylpyrrolidone into the absolute ethyl alcohol, sealing and ultrasonically dispersing for 10-30min, and cooling to obtain n-butyl titanate dispersion liquid; step 2, adding the high-substituted hydroxypropyl cellulose into the n-butyl titanate dispersion liquid, slowly stirring until the high-substituted hydroxypropyl cellulose is completely dissolved, and then sealing and ultrasonically treating for 20-50min to obtain a double-dispersion system n-butyl titanate dispersion liquid; step 3, slowly adding distilled water into the n-butyl titanate dispersion liquid of the double dispersion system, uniformly stirring, sealing, heating, ultrasonically reacting for 2-5h, ultrasonically evaporating for 2-4h, and filtering while hot to obtain a precipitate; and 4, adding the precipitate into the methanol reaction solution for micro-electrolysis reaction for 3-5h, filtering, washing and drying to obtain the nano titanium dioxide material with uniform particle size distribution. The invention solves the problem of complex process in the prior art, and the prepared titanium dioxide has good photocatalytic activity, uniform particle size distribution and good structural stability.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a preparation method of a nano titanium dioxide material with uniform particle size distribution.
Background
TiO as one of semiconductor photocatalysts2The photocatalytic material is a novel environment-friendly material which is most researched at present, and the property of the photocatalyst is a key factor in the photocatalytic oxidation process. TiO 22The crystal form, the grain size, the grain diameter, the surface state and other factors have great influence on the photocatalytic performance. The nano-particle with large surface area has good catalytic activity and selectivity due to the surface effect and the volume effect. Nano TiO 22The conduction band energy level and the valence band energy level of the quantum size effect become discrete energy levels due to the quantum size effect, the energy gap is widened, the conduction band potential becomes more negative, and the valence band potential becomes more positive, which means that the quantum size effect has stronger oxidation and reduction capabilities; and because the particle size of the nano particles is small, a photon-generated carrier is easier to migrate to the surface from the inside of the particles than coarse particles, the recombination probability of electrons and holes is obviously reduced, and the photocatalysis performance is also improved. Thus, TiO having a large specific surface area and a small particle diameter is produced2Has been the focus of research in the field of photocatalysis.
With the improvement of living standard of people, environmental materials are paid more attention to by people, and the titanium dioxide photocatalyst has excellent performances of high oxidation activity, strong catalytic performance, stable activity, good moisture resistance, strong sterilization capability and the like, and is widely applied to the aspects of wastewater degradation, harmful gas elimination, sterilization, air purification and the like. However, the existing methods for preparing titanium dioxide powder, such as the traditional solid phase reaction and sintering method, the modern chemical vapor deposition method, the physical vapor deposition method, the chemical vapor infiltration method, the sol-gel method and the like, have the disadvantages of complex process and high cost, and the obtained titanium dioxide powder is often in a mixed crystal form and has uneven granularity, because the photocatalytic degradation activity of rutile titanium dioxide and amorphous titanium dioxide is poor.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a nano titanium dioxide material with uniform particle size distribution, which solves the problem of complex process in the prior art, and the prepared titanium dioxide has good photocatalytic activity, uniform particle size distribution and good structural stability.
In order to achieve the technical purpose, the technical scheme of the invention is as follows:
a preparation method of a nano titanium dioxide material with uniform particle size distribution comprises the following steps:
step 1, adding n-butyl titanate into absolute ethyl alcohol, adding polyvinylpyrrolidone, sealing, ultrasonically dispersing for 10-30min, and cooling to obtain n-butyl titanate dispersion liquid;
step 2, adding the high-substituted hydroxypropyl cellulose into the n-butyl titanate dispersion liquid, slowly stirring until the high-substituted hydroxypropyl cellulose is completely dissolved, and then sealing and ultrasonically treating for 20-50min to obtain a double-dispersion system n-butyl titanate dispersion liquid;
step 3, slowly adding distilled water into the n-butyl titanate dispersion liquid of the double dispersion system, uniformly stirring, sealing, heating, ultrasonically reacting for 2-5h, ultrasonically evaporating for 2-4h, and filtering while hot to obtain a precipitate;
and 4, adding the precipitate into the methanol reaction solution for micro-electrolysis reaction for 3-5h, filtering, washing and drying to obtain the nano titanium dioxide material with uniform particle size distribution.
The mass concentration of the n-butyl titanate in the absolute ethyl alcohol in the step 1 is 30-80g/L, the addition amount of the polyvinylpyrrolidone is 10-20% of the mass of the n-butyl titanate, the ultrasonic frequency of the sealed ultrasonic dispersion is 25-35kHz, the temperature is 50-60 ℃, and the cooling speed is 3-7 ℃/min; step 1, dissolving n-butyl titanate in absolute ethyl alcohol, wherein the n-butyl titanate is preferentially settled at the bottom of the solution in the ethyl alcohol; the polyvinylpyrrolidone has good solubility in the absolute ethyl alcohol, an absolute ethyl alcohol solution with a dispersion effect can be formed, and the polyvinylpyrrolidone is wrapped and dispersed on the surface of the n-butyl titanate along with the dissolution and dispersion of the polyvinylpyrrolidone in the absolute ethyl alcohol; the ultrasonic reaction is adopted to form clutch energy in absolute ethyl alcohol, so that n-butyl titanate is converted into titanium dioxide, a micro-coating structure is formed, and a good dispersion system is formed.
The adding amount of the high-substituted hydroxypropyl cellulose in the step 2 is 50-70% of the mass of the n-butyl titanate, the stirring speed of the slow stirring is 1500r/min, the ultrasonic frequency of the sealing ultrasonic is 35-40kHz, the temperature is 60-75 ℃, and the pressure is 0.3-0.5 MPa; the high-substituted hydroxypropyl cellulose is added into the dispersion liquid, so that a good dissolving effect can be formed, and the high-substituted hydroxypropyl cellulose is completely dissolved in the slow stirring process; the sealing ultrasonic reaction can open a semi-coating structure between the polyvinylpyrrolidone and the titanium dioxide, and then disperse the high-substituted hydroxypropyl cellulose into the system, so that a polyvinylpyrrolidone-high-substituted hydroxypropyl cellulose double-dispersion system can be formed.
The adding amount of the distilled water in the step 3 is 30-40% of the mass of the n-butyl titanate, the slowly adding speed is 1-3g/min, the stirring speed for uniformly stirring is 3000-5000r/min, the ultrasonic frequency of the sealed heating ultrasonic reaction is 20-30kHz, the temperature is 70-80 ℃, the pressure is 2-5MPa, the ultrasonic frequency of the ultrasonic evaporation reaction is 60-80kHz, the temperature is 95-105 ℃, and the hot filtering temperature is not lower than 80 ℃; slowly adding distilled water into the dispersion liquid, forming a hydrolysis system by the n-butyl titanate and the distilled water, hydrolyzing the n-butyl titanate to form titanium dioxide particles, and forming a dispersion effect under the action of polyvinylpyrrolidone and high-substituted hydroxypropyl cellulose to ensure that a suspension is formed; titanium dioxide particles can be dispersed by sealed heating and ultrasonic, a double dispersion system of polyvinylpyrrolidone and high-substituted hydroxypropyl cellulose can be reconstructed by utilizing clutch energy, and meanwhile, the high-substituted hydroxypropyl cellulose forms a balanced system of dissolution and precipitation in water under the conditions of pressure and temperature, so that the titanium dioxide dispersing agent has good dispersibility, and the dispersibility and particle size stability of the titanium dioxide are ensured; and (3) converting ethanol and part of water into gaseous state in the ultrasonic evaporation process, ensuring that the high-substituted hydroxypropyl cellulose wraps the titanium dioxide in a wrapping state under the temperature condition at the time, converting the high-substituted hydroxypropyl cellulose into solid state to form good precipitate, and filtering while the precipitate is hot to obtain the precipitate of the titanium dioxide coated by the high-substituted hydroxypropyl cellulose.
The mass concentration of the precipitate in the step 4 in the methanol reaction solution is 20-40g/L, the voltage of the micro-electrolysis reaction is 15-35V, the current is 200-500mA, the temperature is 30-60 ℃, the filtering and washing adopt absolute ethyl alcohol, and the drying temperature is 150-200 ℃; the precipitate is subjected to micro-electrolysis reaction in a methanol reaction solution, the highly-substituted hydroxypropyl cellulose can be dissolved in methanol to play a good role in dispersion, and only the nano titanium dioxide is dispersed in the methanol due to the dissolution of the highly-substituted hydroxypropyl cellulose serving as a coating material, and a good dispersion system can be formed under the dispersion effect of the highly-substituted hydroxypropyl cellulose; the electrolysis reaction system takes methanol as electrolyte to play a good electrolysis effect through the action of micro-electrolysis reaction, and uniformly dispersed nano titanium dioxide is converted into an anatase structure.
From the above description, it can be seen that the present invention has the following advantages:
1. the invention solves the problem of complex process in the prior art, and the prepared titanium dioxide has good photocatalytic activity, uniform particle size distribution and good structural stability.
2. The invention adopts polyvinylpyrrolidone and highly substituted hydroxypropyl cellulose to form a double-dispersed dispersion system, and can convert the n-butyl titanate into a soluble titanium dioxide type semi-hydrolysate.
3. The invention adopts the water-soluble characteristic of the highly substituted hydroxypropyl cellulose, not only utilizes the good chemical stability of the highly substituted hydroxypropyl cellulose, but also utilizes the self-protection property of the highly substituted hydroxypropyl cellulose in the solution, has good dispersion stability, and ensures the stability of the nano titanium dioxide.
4. According to the invention, the high-substituted hydroxypropyl cellulose is used as the dispersing agent and the wrapping agent, so that a good wrapping effect can be formed, the particle size of the nano titanium dioxide is controlled through the content change of the high-substituted hydroxypropyl cellulose, and the particle size stability is ensured.
Detailed Description
The present invention is described in detail with reference to examples, but the present invention is not limited to the claims.
Example 1
A preparation method of a nano titanium dioxide material with uniform particle size distribution comprises the following steps:
step 1, adding n-butyl titanate into absolute ethyl alcohol, adding polyvinylpyrrolidone, sealing, ultrasonically dispersing for 10min, and cooling to obtain n-butyl titanate dispersion liquid;
step 2, adding the high-substituted hydroxypropyl cellulose into the n-butyl titanate dispersion liquid, slowly stirring until the high-substituted hydroxypropyl cellulose is completely dissolved, and then sealing and ultrasonically treating for 20min to obtain a n-butyl titanate dispersion liquid of a double-dispersion system;
step 3, slowly adding distilled water into the n-butyl titanate dispersion liquid of the double dispersion system, uniformly stirring, sealing, heating, performing ultrasonic reaction for 2 hours, performing ultrasonic evaporation reaction for 2 hours, and filtering while hot to obtain a precipitate;
and 4, adding the precipitate into the methanol reaction solution for micro-electrolysis reaction for 3 hours, filtering, washing and drying to obtain the nano titanium dioxide material with uniform particle size distribution.
The mass concentration of the n-butyl titanate in the absolute ethyl alcohol in the step 1 is 30g/L, the addition amount of the polyvinylpyrrolidone is 10% of the mass of the n-butyl titanate, the ultrasonic frequency of the sealed ultrasonic dispersion is 25kHz, the temperature is 50 ℃, and the cooling speed is 3 ℃/min.
The adding amount of the high-substituted hydroxypropyl cellulose in the step 2 is 50% of the mass of the n-butyl titanate, the stirring speed of the slow stirring is 1000r/min, the ultrasonic frequency of the sealing ultrasonic is 35kHz, the temperature is 60 ℃, and the pressure is 0.3 MPa.
The adding amount of the distilled water in the step 3 is 30% of the mass of the n-butyl titanate, the slowly adding speed is 1g/min, the stirring speed for uniformly stirring is 3000r/min, the ultrasonic frequency of the sealed heating ultrasonic reaction is 20kHz, the temperature is 70 ℃, the pressure is 2MPa, the ultrasonic frequency of the ultrasonic evaporation reaction is 60kHz, the temperature is 95 ℃, and the temperature for hot filtration is 80 ℃.
The mass concentration of the precipitate in the step 4 in the methanol reaction solution is 20g/L, the voltage of the micro-electrolysis reaction is 15V, the current is 200mA, the temperature is 30 ℃, the filtering and washing adopts absolute ethyl alcohol, and the drying temperature is 150 ℃.
Example 2
A preparation method of a nano titanium dioxide material with uniform particle size distribution comprises the following steps:
step 1, adding n-butyl titanate into absolute ethyl alcohol, adding polyvinylpyrrolidone, sealing, ultrasonically dispersing for 30min, and cooling to obtain n-butyl titanate dispersion liquid;
step 2, adding the high-substituted hydroxypropyl cellulose into the n-butyl titanate dispersion liquid, slowly stirring until the high-substituted hydroxypropyl cellulose is completely dissolved, and then sealing and ultrasonically treating for 50min to obtain a n-butyl titanate dispersion liquid of a double-dispersion system;
step 3, slowly adding distilled water into the n-butyl titanate dispersion liquid of the double dispersion system, uniformly stirring, sealing, heating, performing ultrasonic reaction for 5 hours, performing ultrasonic evaporation reaction for 4 hours, and filtering while hot to obtain a precipitate;
and 4, adding the precipitate into the methanol reaction solution for micro-electrolysis reaction for 5 hours, filtering, washing and drying to obtain the nano titanium dioxide material with uniform particle size distribution.
The mass concentration of the n-butyl titanate in the absolute ethyl alcohol in the step 1 is 80g/L, the addition amount of the polyvinylpyrrolidone is 20% of the mass of the n-butyl titanate, the ultrasonic frequency of the sealed ultrasonic dispersion is 35kHz, the temperature is 60 ℃, and the cooling speed is 7 ℃/min.
The adding amount of the high-substituted hydroxypropyl cellulose in the step 2 is 70% of the mass of the n-butyl titanate, the stirring speed of slow stirring is 1500r/min, the ultrasonic frequency of sealing ultrasound is 40kHz, the temperature is 75 ℃, and the pressure is 0.5 MPa.
The adding amount of the distilled water in the step 3 is 40% of the mass of the n-butyl titanate, the slowly adding speed is 3g/min, the stirring speed for uniformly stirring is 5000r/min, the ultrasonic frequency of the sealed heating ultrasonic reaction is 30kHz, the temperature is 80 ℃, the pressure is 5MPa, the ultrasonic frequency of the ultrasonic evaporation reaction is 80kHz, the temperature is 105 ℃, and the temperature for hot filtration is 75 ℃.
The mass concentration of the precipitate in the step 4 in the methanol reaction solution is 40g/L, the voltage of the micro-electrolysis reaction is 35V, the current is 500mA, the temperature is 60 ℃, the filtering and washing adopts absolute ethyl alcohol, and the drying temperature is 200 ℃.
Example 3
A preparation method of a nano titanium dioxide material with uniform particle size distribution comprises the following steps:
step 1, adding n-butyl titanate into absolute ethyl alcohol, adding polyvinylpyrrolidone, sealing, ultrasonically dispersing for 20min, and cooling to obtain n-butyl titanate dispersion liquid;
step 2, adding the high-substituted hydroxypropyl cellulose into the n-butyl titanate dispersion liquid, slowly stirring until the high-substituted hydroxypropyl cellulose is completely dissolved, and then sealing and ultrasonically treating for 30min to obtain a n-butyl titanate dispersion liquid of a double-dispersion system;
step 3, slowly adding distilled water into the n-butyl titanate dispersion liquid of the double dispersion system, uniformly stirring, sealing, heating, performing ultrasonic reaction for 3 hours, performing ultrasonic evaporation reaction for 3 hours, and filtering while hot to obtain a precipitate;
and 4, adding the precipitate into the methanol reaction solution for micro-electrolysis reaction for 4 hours, filtering, washing and drying to obtain the nano titanium dioxide material with uniform particle size distribution.
The mass concentration of the n-butyl titanate in the absolute ethyl alcohol in the step 1 is 50g/L, the addition amount of the polyvinylpyrrolidone is 15% of the mass of the n-butyl titanate, the ultrasonic frequency of the sealed ultrasonic dispersion is 30kHz, the temperature is 55 ℃, and the cooling speed is 5 ℃/min.
The adding amount of the high-substituted hydroxypropyl cellulose in the step 2 is 60% of the mass of the n-butyl titanate, the stirring speed of the slow stirring is 1300r/min, the ultrasonic frequency of the sealing ultrasonic is 35-40kHz, the temperature is 65 ℃, and the pressure is 0.4 MPa.
The adding amount of the distilled water in the step 3 is 35% of the mass of the n-butyl titanate, the slowly adding speed is 2g/min, the stirring speed for uniform stirring is 4000r/min, the ultrasonic frequency of the sealed heating ultrasonic reaction is 25kHz, the temperature is 75 ℃, the pressure is 4MPa, the ultrasonic frequency of the ultrasonic evaporation reaction is 70kHz, the temperature is 100 ℃, and the temperature for hot filtration is 90 ℃.
The mass concentration of the precipitate in the step 4 in the methanol reaction solution is 30g/L, the voltage of the micro-electrolysis reaction is 25V, the current is 400mA, the temperature is 50 ℃, the filtering and washing adopts absolute ethyl alcohol, and the drying temperature is 180 ℃.
Example 4
A preparation method of a nano titanium dioxide material with uniform particle size distribution comprises the following steps:
step 1, adding n-butyl titanate into absolute ethyl alcohol, adding polyvinylpyrrolidone, sealing, ultrasonically dispersing for 5min, and cooling to obtain n-butyl titanate dispersion liquid;
step 2, adding the high-substituted hydroxypropyl cellulose into the n-butyl titanate dispersion liquid, slowly stirring until the high-substituted hydroxypropyl cellulose is completely dissolved, and then sealing and ultrasonically treating for 30min to obtain a n-butyl titanate dispersion liquid of a double-dispersion system;
step 3, slowly adding distilled water into the n-butyl titanate dispersion liquid of the double dispersion system, uniformly stirring, sealing, heating, performing ultrasonic reaction for 3 hours, performing ultrasonic evaporation reaction for 3 hours, and filtering while hot to obtain a precipitate;
and 4, adding the precipitate into the methanol reaction solution for micro-electrolysis reaction for 4 hours, filtering, washing and drying to obtain the nano titanium dioxide material with uniform particle size distribution.
The mass concentration of the n-butyl titanate in the absolute ethyl alcohol in the step 1 is 50g/L, the addition amount of the polyvinylpyrrolidone is 15% of the mass of the n-butyl titanate, the ultrasonic frequency of the sealed ultrasonic dispersion is 30kHz, the temperature is 55 ℃, and the cooling speed is 5 ℃/min.
The adding amount of the high-substituted hydroxypropyl cellulose in the step 2 is 55% of the mass of the n-butyl titanate, the stirring speed of the slow stirring is 1300r/min, the ultrasonic frequency of the sealing ultrasonic is 35-40kHz, the temperature is 70 ℃, and the pressure is 0.4 MPa.
The adding amount of the distilled water in the step 3 is 35% of the mass of the n-butyl titanate, the slowly adding speed is 2g/min, the stirring speed for uniform stirring is 4000r/min, the ultrasonic frequency of the sealed heating ultrasonic reaction is 25kHz, the temperature is 75 ℃, the pressure is 3MPa, the ultrasonic frequency of the ultrasonic evaporation reaction is 70kHz, the temperature is 105 ℃, and the temperature for hot filtration is 95 ℃.
The mass concentration of the precipitate in the step 4 in the methanol reaction solution is 30g/L, the voltage of the micro-electrolysis reaction is 20V, the current is 300mA, the temperature is 40 ℃, the filtering and washing adopts absolute ethyl alcohol, and the drying temperature is 170 ℃.
Performance testing
The comparative example employed commercial P25.
| Example 1 | Example 2 | Example 3 | Example 4 | Comparative example | |
| Particle size | 200nm | 250nm | 289nm | 347nm | 400nm |
| Particle size distribution ratio | 95％ | 94％ | 97％ | 98％ | 84％ |
| Photocatalytic degradation rate | 98％ | 96％ | 99％ | 99％ | 75％ |
| Photocatalytic sterilization rate | 99.98％ | 99.96％ | 99.99％ | 99.99％ | 95.13％ |
In summary, the invention has the following advantages:
1. the invention solves the problem of complex process in the prior art, and the prepared titanium dioxide has good photocatalytic activity, uniform particle size distribution and good structural stability.
2. The invention adopts polyvinylpyrrolidone and highly substituted hydroxypropyl cellulose to form a double-dispersed dispersion system, and can convert the n-butyl titanate into a soluble titanium dioxide type semi-hydrolysate.
3. The invention adopts the water-soluble characteristic of the highly substituted hydroxypropyl cellulose, not only utilizes the good chemical stability of the highly substituted hydroxypropyl cellulose, but also utilizes the self-protection property of the highly substituted hydroxypropyl cellulose in the solution, has good dispersion stability, and ensures the stability of the nano titanium dioxide.
4. According to the invention, the high-substituted hydroxypropyl cellulose is used as the dispersing agent and the wrapping agent, so that a good wrapping effect can be formed, the particle size of the nano titanium dioxide is controlled through the content change of the high-substituted hydroxypropyl cellulose, and the particle size stability is ensured.
It should be understood that the detailed description of the invention is merely illustrative of the invention and is not intended to limit the invention to the specific embodiments described. It will be appreciated by those skilled in the art that the present invention may be modified or substituted equally as well to achieve the same technical result; as long as the use requirements are met, the method is within the protection scope of the invention.
Claims (1)
1. A method for preparing a nano titanium dioxide material with uniform particle size distribution is characterized by comprising the following steps: the preparation method comprises the following steps:
step 1, adding n-butyl titanate into absolute ethyl alcohol, adding polyvinylpyrrolidone, sealing, ultrasonically dispersing for 10-30min, and cooling to obtain n-butyl titanate dispersion liquid;
step 2, adding the high-substituted hydroxypropyl cellulose into the n-butyl titanate dispersion liquid, slowly stirring until the high-substituted hydroxypropyl cellulose is completely dissolved, and then sealing and ultrasonically treating for 20-50min to obtain a double-dispersion system n-butyl titanate dispersion liquid;
step 3, slowly adding distilled water into the n-butyl titanate dispersion liquid of the double dispersion system, uniformly stirring, sealing, heating, ultrasonically reacting for 2-5h, ultrasonically evaporating for 2-4h, and filtering while hot to obtain a precipitate;
step 4, adding the precipitate into a methanol reaction solution for micro-electrolysis reaction for 3-5h, filtering, washing and drying to obtain a nano titanium dioxide material with uniform particle size distribution;
the mass concentration of the n-butyl titanate in the step 1 in the absolute ethyl alcohol is 30-80g/L, and the addition amount of the polyvinylpyrrolidone is 10-20% of the mass of the n-butyl titanate; the ultrasonic frequency of the sealed ultrasonic dispersion is 25-35kHz, the temperature is 50-60 ℃, and the cooling speed is 3-7 ℃/min;
the adding amount of the high-substituted hydroxypropyl cellulose in the step 2 is 50-70% of the mass of the n-butyl titanate, and the stirring speed of the slow stirring is 1000-1500 r/min; the ultrasonic frequency of the sealing ultrasonic is 35-40kHz, the temperature is 60-75 ℃, and the pressure is 0.3-0.5 MPa;
the adding amount of the distilled water in the step 3 is 30-40% of the mass of the n-butyl titanate, the slowly adding speed is 1-3g/min, the stirring speed for uniformly stirring is 3000-5000r/min, the ultrasonic frequency of the sealed heating ultrasonic reaction is 20-30kHz, the temperature is 70-80 ℃, and the pressure is 2-5 MPa; the ultrasonic frequency of the ultrasonic evaporation reaction is 60-80kHz, the temperature is 95-105 ℃, and the hot filtering temperature is not lower than 80 ℃;
the mass concentration of the precipitate in the step 4 in the methanol reaction solution is 20-40g/L, the voltage of the micro-electrolysis reaction is 15-35V, the current is 200-500mA, and the temperature is 30-60 ℃; the filtration washing adopts absolute ethyl alcohol, and the drying temperature is 150-200 ℃.
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