WO2022007756A1 - 二氧化钛材料及其制备方法、分散性提升方法、应用 - Google Patents

二氧化钛材料及其制备方法、分散性提升方法、应用 Download PDF

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WO2022007756A1
WO2022007756A1 PCT/CN2021/104577 CN2021104577W WO2022007756A1 WO 2022007756 A1 WO2022007756 A1 WO 2022007756A1 CN 2021104577 W CN2021104577 W CN 2021104577W WO 2022007756 A1 WO2022007756 A1 WO 2022007756A1
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titanium dioxide
titanium
nano
water
dispersion
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French (fr)
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梁先华
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宁波极微纳新材料科技有限公司
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • 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

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  • the invention particularly relates to a titanium dioxide material and its preparation method, dispersibility improvement method and application.
  • Nano-titanium dioxide refers to titanium dioxide with a particle size of less than 100 nanometers. It has special effects such as small particle size, high specific surface area, excellent photocatalytic activity, stable chemical and thermal properties, and super affinity. Self-cleaning materials, sunscreen skin care products and other fields have irreplaceable application advantages. For example, nano-titanium dioxide can be used to decompose formaldehyde, benzene, TVOC, SOx, NOx, etc.
  • nano-titanium dioxide is used in glass, shutters, Mirrors, street lamps and other surfaces can achieve self-cleaning effect; nano-titanium dioxide is also widely used in medical equipment, catheters, operating rooms, sunscreen cosmetics, sunscreen clothing, whitening products, anti-aging coatings and other fields; in addition, nano-titanium dioxide can also be used in lithium Energy conversion and storage fields such as anode materials for ion batteries, photocatalysis or photoelectric catalytic production of hydrogen energy.
  • nano-TiO2 particles are small in size, have a large number of defects on the surface, large surface activity, and are in a thermodynamically unstable state.
  • the nanoparticles dispersed in the liquid medium are easy to coagulate, agglomerate, and coagulate, and cannot form a stable dispersion.
  • the unique properties of nanoparticles cause great defects in practical applications.
  • the key to the preparation of nano-dispersion is to overcome the force of particle agglomeration, improve the stability of nanoparticles in liquid medium and prolong the dispersion stability time.
  • the physical dispersion method mainly uses external forces to disperse the nanoparticles, including mechanical stirring dispersion, ultrasonic dispersion and high-energy treatment dispersion.
  • the disadvantage of the physical dispersion method is that if the external force stops, the particles will re-aggregate.
  • the chemical dispersion method is to use surface chemical methods to add surface treatment agents for dispersion.
  • the preparation of water-phase dispersed nanoparticles is usually achieved by the induction and restraint of water-soluble surfactants or polymers, but the surface of the particles is covered with modified molecules such as organics.
  • modified molecules such as organics.
  • the contribution of dispersion control to improving material properties is reduced; at the same time, different application systems may also have adverse adverse effects with surface-modified molecules, reducing the application performance of the final product.
  • the titanium dioxide dispersion products obtained by the above methods are all liquid suspensions, the particles cannot be completely monodispersed and the particle size is uneven, and a stable colloidal dispersion cannot be formed, resulting in high transportation costs and practical application.
  • nano-TiO2 powders on the market are large particles formed by agglomeration of nano-scale particles, not nano-TiO2 materials in the true sense. These materials have poor dispersibility in water, are opaque, It is easy to settle, resulting in a great defect in practical application. Therefore, in order to further improve the application field and use effect of TiO2 nanomaterials, it is urgent to develop a nano-TiO2 powder with monodispersion and high activity, which can effectively solve the technical problem of how to quickly and efficiently disperse in the application of nano-TiO2.
  • the main properties that this powder should have are: (1) The powder must be stably dispersed in the liquid medium to form a highly transparent nanoparticle dispersion, and the dispersed nanoparticles need to be stable for a long time and not agglomerate to produce precipitation; (2) The powder has no surface organic modification molecules in the process of preparation or processing, which can make the application field of the nano-titanium dioxide powder universal; (4) In the field of photocatalytic application, the nano titanium dioxide powder dispersion liquid has high photocatalytic activity.
  • Nanoparticles with ultra-small particle size can exhibit more excellent properties in energy, environment, and catalysis.
  • titanium dioxide materials with a particle size of less than 100 nanometers have special effects such as small particle size, high specific surface area, excellent photocatalytic activity, stable chemical and thermal properties, and super affinity, which are used in air treatment, sterilization and self-cleaning. Materials, sunscreen skin care products and other fields have irreplaceable application advantages.
  • nano-titania particle dispersion have important effects on the reaction process and the final product.
  • product performance largely depends on the dispersion degree of titanium dioxide powder in liquid medium.
  • the application effect is also better.
  • nano-TiO2 particles are small in size, have a large number of defects on the surface, large surface activity, and are in a thermodynamically unstable state.
  • the nanoparticles dispersed in the liquid medium are easy to coagulate, agglomerate, and coagulate, and cannot form a stable dispersion.
  • Preventing the agglomeration of nano-titanium dioxide particles and obtaining monodisperse titanium dioxide nanoparticles can greatly improve the performance of titanium dioxide nanomaterials in the fields of optics, electricity, and catalysis.
  • the physical dispersion method mainly uses external forces to disperse the nanoparticles, including mechanical stirring dispersion, ultrasonic dispersion and high-energy treatment dispersion.
  • the disadvantage of the physical dispersion method is that if the external force stops, the particles will re-aggregate.
  • the chemical dispersion method is to use surface chemical methods to add surface treatment agents for dispersion.
  • the preparation of water-phase dispersed nanoparticles is usually achieved by the induction and restraint of water-soluble surfactants or polymers, but the surface of the particles is covered with modified molecules such as organics.
  • modified molecules such as organics.
  • the contribution of dispersibility control to improving material properties is reduced, such as the preparation of water-soluble titanium dioxide nanoparticles by the reaction of titanium alkoxides and alkylamines, but the presence of such alkaline reagents passivates the surface activity of the product to make it photocatalytic
  • different application systems may also have adverse adverse effects with the surface-modified molecules, reducing the application performance of the final product.
  • the use of polyethylene glycol as a stabilizer makes the dispersibility of titanium dioxide nanoparticles somewhat improved.
  • Another object of the present invention is to provide a technical method for greatly improving the dispersibility of nano-titanium dioxide, so as to promote the application field and use effect of nano-titanium dioxide materials.
  • the present invention adopts the following technical solutions:
  • a preparation method of titanium dioxide material comprising the following steps:
  • the titanium alkoxide is reacted with water to form a hydrated titanium hydroxide precipitate
  • the mixture of the titanium hydroxide and the acid solution is heated and reacted under sealing conditions to obtain a solid titanium dioxide material with crystalline nano titanium dioxide particles.
  • the solid titanium dioxide material can be spontaneously dispersed in water to form an aqueous dispersion in which the nano titanium dioxide particles are stably suspended .
  • it also includes: treating the separated and dried titanium hydroxide to obtain titanium hydroxide containing nano-crystal seeds; the treatment method is selected from hydrothermal treatment, annealing treatment, mixed crystal One of the methods or a combination of several methods.
  • the titanium alkoxide is selected from titanium methoxide, titanium ethoxide, titanium isopropoxide, titanium n-propoxide, tetrabutyl titanate, titanium isobutoxide, titanium pentoxide, titanium isoamyloxide , one or more of titanium hexoxide, titanium ethylene glycol and titanium glycerol.
  • the conditions for the reaction of titanium alkoxide and water are direct contact reaction of titanium alkoxide and water; the direct contact reaction includes titanium alkoxide directly added to water, water directly added to titanium alkoxide, water vapor One or a combination of one or several ways of directly feeding the titanium alkoxide into the titanium alkoxide, directly feeding the titanium alkoxide gas into the water, and directly contacting the water vapor with the titanium alkoxide gas.
  • the mass percentage of the small amount of acid solution and titanium hydroxide is 2% to 100%; the preferred mass percentage is 5% to 50%.
  • the acid solution is selected from a hydrochloric acid solution, a perchloric acid solution, a hypochlorous acid solution, a nitric acid solution, a hydrofluoric acid solution, a titanium tetrachloride solution, and a titanium trichloride solution. Or a combination of several; the mass fraction of acid in the acid solution is 1% to 50%.
  • the sealing is to put a mixture of titanium hydroxide and an acid solution into a container with a fixed volume and seal; the container with a fixed volume does not change in volume under the condition of heating.
  • the temperature of the heating reaction is 100 degrees Celsius to 200 degrees Celsius; the time of the heating reaction is 2 hours to 24 hours.
  • a titanium dioxide material prepared by the preparation method described in any one of the above embodiments the titanium dioxide material is solid; the titanium dioxide material contains crystalline nano-titanium dioxide particles; the titanium dioxide material is mixed with water and can spontaneously disperse to form nano-titanium dioxide Aqueous dispersions in which particles are stably suspended.
  • the surface of the titanium dioxide material is acidic.
  • the titanium dioxide material is composed of agglomerates of nano-scale titanium dioxide particles; the particle size of the nano-scale titanium dioxide particles is 3 nanometers to 20 nanometers.
  • the titanium dioxide material does not contain organic matter.
  • the solid titanium dioxide material is particles above the micron scale, and the tap density is higher than 0.8 grams per milliliter; the form of the solid titanium dioxide material is powdered solid, granular solid or a mixture of powder and particles solid.
  • the crystal phase of the crystalline nano-titania particles includes one or a combination of anatase phase, rutile phase, and brookite phase.
  • condition of the spontaneous dispersion is to directly put into water without stirring to form a dispersion.
  • condition of the spontaneous dispersion is that the water does not contain one or a combination of additives or dispersants.
  • condition of the spontaneous dispersion is that there is no surface modification of the titanium dioxide material.
  • the aqueous dispersion in which the nano-titanium dioxide particles are stably suspended is a colloidal dispersion; and the time of stable suspension of the nano-titanium dioxide particles is more than 6 months.
  • a method and product for improving the dispersibility of titanium dioxide comprising the following steps:
  • Titanium dioxide nanoparticles are small in size and uniform in particle size, which expands the application of the material in glass and other light-transmitting and beautiful materials.
  • the particle size of the product is about 5 nanometers, and the distribution is uniform, which is conducive to forming a uniform and transparent film layer on the surface of the material. Compared with the imported nano-photocatalyst, the transparency is increased by 75 times.
  • the method for improving the dispersibility of titanium dioxide does not use any surface organic additive, which makes the application field of the nano titanium dioxide dispersion universal, and increases the application field and effect of the dispersion.
  • Figure 10 is a scanning electron microscope image of the product obtained in Comparative Example 1, and the product is a petal-shaped large particle agglomerate;
  • Fig. 13 is the optical picture that massfraction is that the precursor titanium hydroxide suspension of 5/1000 is left standstill for 2 hours, has obvious layering phenomenon, and the suspension is unstable;
  • Fig. 14 is the SEM image obtained by drip-coating the product obtained in Example 1 on a silicon wafer after being dispersed in water and observed after drying;
  • Fig. 15 is the scanning electron microscope image obtained after the precursor titanium hydroxide is dispersed in water and then drop-coated on a silicon wafer and observed after drying;
  • FIG. 16 is a scanning electron microscope image obtained by dispersing the product obtained in Comparative Example 1 on a silicon wafer after being drop-coated with water and observing after drying.
  • the micron-scale particles are composed of nanoscale titanium dioxide particle agglomerates, and the particle size of the nanoscale titanium dioxide particles is mainly distributed around 5 nanometers, indicating that the nanoscale titanium dioxide obtained in this example has a small particle size , the monodispersity is better.
  • Figure 3 is the X-ray diffraction pattern of the titanium dioxide product prepared in Example 1.
  • the product titanium dioxide photocatalyst obtained in Example 1 has excellent photocatalytic activity, and the catalytic efficiency is 11 times that of the P25 material.
  • the nano-titanium dioxide material obtained in Example 1 also has excellent formaldehyde removal effect.
  • the specific test method is: spray 50 ml of the titanium dioxide obtained in Example 1 with a concentration of 1% on a paper base of 1 square meter.
  • the dispersion liquid was dried naturally; then, the above-mentioned paper base was put into a test chamber with a volume of 1 cubic meter, a certain concentration and volume of formaldehyde was introduced, the fan was turned on, and the air in the chamber was evenly mixed; Sampling at regular intervals to detect the formaldehyde concentration in the air in the cabin.
  • This test uses P25 material as a control test. As can be seen in Figure 9, after 12 hours, the formaldehyde removal rate of the product of Example 1 is 99 percent, while the formaldehyde removal rate of P25 is only 25 percent, it can be seen that the obtained The product titanium dioxide photocatalyst has excellent formaldehyde removal effect.
  • the chemical mechanism process of "dissolution-limited growth" obtained by this technology has significant differences and technological innovation effects from the “dissolution-growth” process of the hydrothermal method.
  • Solvent it is usually necessary to completely soak and disperse the reactants in water for the reaction.
  • the reactant in this technology is only mixed with a small amount of acid solution, and there is only a thin water layer on the surface, which limits the ion diffusion migration path and distance during the transformation and recrystallization process of the reactant powder, which limits the transformation reaction.
  • the nanomaterial products with uniform size and ultra-fine size can be obtained; at the same time, the catalyst in this technology promotes the dissolution of the precursor, increases the concentration and nucleation number of solute titanium ions in the thin water layer, and further promotes the particle size The formation of nano-titanium dioxide products with uniform size, and finally the formation of monodisperse nano-titanium dioxide materials.
  • the surface of the titanium dioxide material does not contain organic modification additives, and when mixed with water, it can spontaneously disperse to form an aqueous dispersion in which the nano-titanium dioxide particles are stably suspended.
  • the nanoparticles in the dispersion are uniform in size, stable in dispersion and suspension, and no delamination is found after 6 months of storage; the appearance of the dispersion is blue, and there is an obvious Tyndall phenomenon under light; no bubbles are found in the dispersion during the shaking process, indicating that there is no Organic Additives.
  • Titanium dioxide nanoparticles are small in size and uniform in particle size, which expands the application of the material in glass and other light-transmitting and beautiful materials.
  • the particle size of the product is about 5 nanometers, and the distribution is uniform, which is conducive to forming a uniform and transparent film layer on the surface of the material. Compared with the imported nano-photocatalyst, the transparency is increased by 75 times.
  • Titanium dioxide photocatalyst has excellent photocatalytic activity and high removal efficiency of pollutants such as dyes and formaldehyde.
  • the photocatalytic efficiency is more than 10 times that of imported P25 products, which improves the application effect of nano-photocatalysts in the fields of photocatalytic decomposition of air pollutants such as formaldehyde, sterilization and self-cleaning materials.
  • the product is cheap, safe, environmentally friendly and non-toxic.
  • raw materials can be recycled and reused, the synthesis process is safe, environmentally friendly and non-toxic; the product yield is high and the price is low.
  • the titanium dioxide material product obtained in this Example 2 is a powdery solid, the appearance color is white, and the tap density is about 0.87 grams per milliliter.
  • the morphology of the sample was observed by low magnification scanning electron microscope to be irregular micro-particles; further magnification of the scanning electron microscope showed that these micro-particles were mainly composed of agglomeration of nano-scale titanium dioxide particles with good dispersibility from 5 nm to 15 nm.
  • X-ray diffraction confirmed that the main crystal phase of the nano-titania obtained in Example 2 was anatase phase with good crystallinity, and also contained a small amount of rutile phase. The separation effect is correct, and the photocatalytic efficiency of the titanium dioxide material is improved.
  • Example 2 Put a small amount of the titanium dioxide material product obtained in Example 2 into pure water, it can be seen that the titanium dioxide material product spontaneously "dissolves" and is dispersed in the pure water to form a colloidal water dispersion in which nano-scale titanium dioxide particles are stably suspended.
  • the particles have stable suspension and no agglomeration, with obvious Tyndall phenomenon, and the dispersion liquid will not appear obvious layering phenomenon after being placed for 8 months.
  • the nano-titanium dioxide obtained in Example 2 is dispersed in pure water to form an aqueous dispersion whose mass fraction of nano-titanium dioxide is five ten thousandths.
  • Ultraviolet light strong ultraviolet absorption; at the same time, it has extremely high light transmittance in the visible light region greater than 400 nanometers, and the transmittance is greater than 90%.
  • the transparency of the product obtained in Example 2 is increased by 53 times, which greatly expands the application of the titanium dioxide material in the fields of ultraviolet absorption and aesthetics.
  • the nano-titania material obtained in Example 2 has good photocatalytic activity.
  • the experimental operation is the same as in Example 1.
  • the efficiency of decomposing methylene blue dye obtained by nano-titanium dioxide material in Example 2 is about 9.6 times that of commercial P25 material, and the formaldehyde removal rate in 12 hours is 90%, which has excellent formaldehyde removal effect.
  • the titanium dioxide material product obtained in Example 3 is a powdery solid after natural drying at normal temperature and pressure, the appearance color is light gray-white, and the tap density is about 0.91 grams per milliliter.
  • the morphology of the sample was observed by low magnification SEM to be irregular micro-particles; further magnification of SEM shows that these micro-particles are mainly composed of 10-20 nanometers, which are well-dispersed nano-scale titanium dioxide particles agglomerated.
  • X-ray diffraction confirmed that the main crystal phase of the nano-titania obtained in Example 2 was anatase phase with good crystallinity, and also contained a small amount of rutile phase. The separation effect is correct, and the photocatalytic efficiency of the titanium dioxide material is improved.
  • Example 3 Put a small amount of the titanium dioxide material product obtained in Example 3 into deionized water, and it can be seen that the titanium dioxide material product is spontaneously "dissolved” and dispersed in the deionized water to form a colloidal water dispersion in which the nano-titanium dioxide particles are stably suspended.
  • the medium nanoparticles have stable suspension and no agglomeration, with obvious Tyndall phenomenon, and the dispersion will not appear obvious delamination after 6 months.
  • the nano-titanium dioxide obtained in Example 3 is dispersed in deionized water to form an aqueous dispersion with a mass fraction of nano-titanium dioxide that is 5/10,000.
  • the aqueous dispersion can completely absorb less than 370 nanometers in a 1-centimeter-thick quartz cuvette.
  • Ultraviolet light strong ultraviolet absorption; at the same time, it has extremely high light transmittance in the visible light region greater than 400 nanometers, and the transmittance is greater than 80%.
  • the transparency of the product obtained in Example 3 is increased by 45 times, which greatly expands the application of the titanium dioxide material in the fields of ultraviolet absorption and aesthetics.
  • the nano-titania material obtained in Example 3 has good photocatalytic activity.
  • the experimental operation is the same as that of Example 1.
  • the efficiency of decomposing methylene blue dye obtained by nano-titanium dioxide material in Example 3 is about 7.2 times that of commercial P25 material, and the 12-hour formaldehyde removal rate is 85%, which has excellent formaldehyde removal effect.
  • Example 4 Put a small amount of the titanium dioxide material product obtained in Example 4 into pure water, it can be seen that the titanium dioxide material product spontaneously "dissolves" and is dispersed in the pure water to form a colloidal water dispersion in which nano titanium dioxide particles are stably suspended.
  • the particles have stable suspension and no agglomeration, with obvious Tyndall phenomenon, and the dispersion liquid will not appear obvious stratification after being placed for 6 months.
  • the nano-titanium dioxide obtained in Example 4 is dispersed in pure water to form an aqueous dispersion whose mass fraction of nano-titanium dioxide is five ten thousandths.
  • Ultraviolet light strong ultraviolet absorption; at the same time, it has extremely high light transmittance in the visible light region greater than 400 nanometers, and the transmittance is greater than 90%.
  • the transparency of the product obtained in Example 4 is increased by 61 times, which greatly expands the application of the titanium dioxide material in the fields of ultraviolet absorption and aesthetics.
  • the nano-titania material obtained in Example 4 has good photocatalytic activity.
  • the experimental operation is the same as that of Example 1.
  • the efficiency of decomposing methylene blue dye obtained by nano-titanium dioxide material in Example 4 is about 10 times that of commercial P25 material, and the 12-hour formaldehyde removal rate is 93%, which has excellent formaldehyde removal effect.
  • water vapor and titanium ethoxide gas are mixed to form a hydrated titanium hydroxide precipitate; the above-mentioned hydrated titanium hydroxide precipitate is separated and washed to remove organic matter, and then separated and dried to obtain hydroxide Titanium powder. Then, take 2 grams of the titanium hydroxide powder obtained above, add 1.8 grams of nitric acid solution with a mass fraction of 5% under stirring, and continue stirring to form a slightly wet titanium hydroxide mixture. Subsequently, the above-mentioned slightly wet titanium hydroxide mixture was put into the reactor and sealed. Finally, the above reaction kettle was placed in a microwave oven, and heated in a microwave at 140 degrees Celsius for 3 hours to obtain a nano-titanium dioxide product.
  • the titanium dioxide material product obtained in Example 5 is a powdery solid after natural drying at normal temperature and normal pressure, the appearance color is white, and the tap density is about 0.95 grams per milliliter.
  • the morphology of the sample was observed by low magnification SEM to be irregular micro-particles; further magnification of SEM shows that these micro-particles are mainly composed of 10-20 nanometers, which are well-dispersed nano-scale titanium dioxide particles agglomerated.
  • X-ray diffraction confirmed that the main crystal phase of the nano-titania obtained in Example 5 was anatase phase with good crystallinity.
  • Example 5 Put a small amount of the titanium dioxide material product obtained in Example 5 into pure water, it can be seen that the titanium dioxide material product spontaneously "dissolves" and is dispersed in the pure water to form a colloidal water dispersion in which the nanometer titanium dioxide particles are stably suspended.
  • the particles have stable suspension and no agglomeration, with obvious Tyndall phenomenon, and the dispersion liquid will not appear obvious stratification after being placed for 6 months.
  • the nano-titanium dioxide obtained in Example 5 is dispersed in pure water to form an aqueous dispersion whose mass fraction of nano-titanium dioxide is five ten thousandths.
  • Ultraviolet light strong ultraviolet absorption; at the same time, it has extremely high light transmittance in the visible light region greater than 400 nanometers, and the transmittance is greater than 50%.
  • the transparency of the product obtained in Example 5 is increased by 30 times, which expands the application of the titanium dioxide material in the fields of ultraviolet absorption and aesthetics.
  • the nano-titania material obtained in Example 5 has good photocatalytic activity.
  • the experimental operation is the same as that of Example 1.
  • the efficiency of decomposing methylene blue dye obtained by nano-titanium dioxide material in Example 5 is about 8 times that of commercial P25 material, and the 12-hour formaldehyde removal rate is 95%, which has excellent formaldehyde removal effect.
  • the titanium dioxide material product obtained in Example 6 is a powdery solid after natural drying at normal temperature and normal pressure, the appearance color is white, and the tap density is about 1.0 grams per milliliter.
  • the morphology of the sample was observed by low magnification scanning electron microscope to be irregular micro-particles; further magnification of the scanning electron microscope showed that these micro-particles were mainly composed of agglomeration of nano-scale titanium dioxide particles with good dispersibility from 5 nm to 15 nm.
  • X-ray diffraction confirmed that the main crystal phase of the nano-titania obtained in Example 6 was anatase phase with good crystallinity.
  • Example 6 Put a small amount of the titanium dioxide material product obtained in Example 6 into pure water, it can be seen that the titanium dioxide material product is spontaneously "dissolved” and dispersed in the pure water, forming a colloidal water dispersion in which nano titanium dioxide particles are stably suspended.
  • the particles have stable suspension and no agglomeration, with obvious Tyndall phenomenon, and the dispersion liquid will not appear obvious stratification after being placed for 6 months.
  • the nano-titania material obtained in Example 6 has good photocatalytic activity.
  • the experimental operation is the same as that of Example 1.
  • the efficiency of decomposing methylene blue dye obtained by nano-titanium dioxide material in Example 6 is about 7.4 times that of commercial P25 material, and the 12-hour formaldehyde removal rate is 96%, which has excellent formaldehyde removal effect.
  • the dispersion liquid composite material is transparent and can be sprayed on the surface of transparent and beautiful materials, without spots after drying, and does not affect the color of the material surface; the dispersion liquid composite material is used to form a dense coating on the surface of the material, which is not easy to fall off, and has excellent Its photocatalytic properties can remove formaldehyde, and it has antibacterial and self-cleaning functions.
  • nano-titanium dioxide product obtained in any one of Examples 1 to 6, and add it to 100 grams of 50% ethanol aqueous solution to form a dispersion; then take 50 grams of the above dispersion, and slowly add 0.5 Milliliter of ethyl orthosilicate to form a mixed solution; finally, the mixed solution was reacted at 80 degrees Celsius for 5 hours under stirring conditions to obtain a nano-titanium oxide/silicon oxide transparent composite material.
  • the composite material is transparent and can be sprayed on the surface of transparent and beautiful materials. It does not produce spots after drying, and does not affect the color of the material surface.
  • the composite material is used to form a dense coating on the surface of the material, which is not easy to fall off and has excellent photocatalytic performance. , can remove formaldehyde, has antibacterial and self-cleaning functions.
  • the reactants cannot be completely converted into crystalline nano-titanium dioxide products; the product obtained in this comparative example contains a large number of large particles, which cannot be dispersed in water to form a stable and transparent dispersion, and the obtained product is a suspension liquid. Precipitation and stratification will appear within hours; in addition, the photocatalytic performance of this comparative product is lower than that of the P25 commercial product, the degradation efficiency of methylene blue is only 0.9 times that of P25, and the photocatalytic performance is poor.
  • the invention effect of the product of the embodiment cannot be obtained in terms of product morphology, dispersibility, chemical efficiency and other structures and properties.
  • titanium hydroxide (Guangdong Wengjiang Chemical Reagent Co., Ltd., CAS No.: 20338-08-3, purity ⁇ 99%) powder was weighed and placed in a pressure-resistant anti-corrosion tube. Then, heat the pressure-resistant anti-corrosion pipe to 120 degrees Celsius, keep the pressure of the hydrogen chloride injection port in the pipe about 2 atmospheres (fluctuate between 1.5 atmospheres and 2 atmospheres), and the injection pressure of the water vapor port is about 1 atmosphere. Constant temperature at 120 degrees Celsius for 24 hours to obtain nano titanium dioxide powder materials with significantly improved dispersion, stability and transparency.
  • the main crystal phase of the titanium dioxide material obtained in Example 11 is anatase phase.
  • the product is mixed with water, and can also spontaneously disperse to form an aqueous dispersion of stably suspended nano titanium dioxide particles without stirring.
  • Figure 12 is an aqueous dispersion with a mass fraction of 5/1000 obtained after adding water to the nano-titanium dioxide product obtained in this example, the dispersion has good monodispersity and can form a relatively stable colloidal dispersion in the aqueous solution , with obvious Tyndall phenomenon; the nanoparticles are stably suspended, not easy to settle, and the solution is placed for more than 3 days without obvious stratification.
  • Figure 13 is an optical picture of the precursor titanium hydroxide suspension with a mass fraction of 5/1000 standing for 2 hours. It can be seen that there is an obvious layering phenomenon, and the suspension is unstable. It can be seen that this technology The suspension stability of the obtained product was increased by more than 36 times.
  • the light transmittance of the titanium dioxide material aqueous dispersion obtained in Example 11 at a wavelength of 550 nanometers is 85%, compared with 2.5% of the light transmittance of the titanium hydroxide suspension of the same concentration precursor, and the transparency is increased by 34 times.
  • the specific experimental operation is as follows: take a small amount of the titanium dioxide material obtained in Example 11, prepare it into an aqueous dispersion with a mass fraction of 5/10,000, for comparison, and also prepare a precursor hydroxide with a mass fraction of 5/10,000. Titanium suspension; then respectively take the above dispersion in a 1 cm thick quartz cuvette, test the transmittance of the sample at a wavelength of 550 nm, and use pure water as a blank.
  • the precursor is an aggregate of nanoparticles of about 50 nanometers, with poor dispersion, which further shows that the precursor is easy to settle and stratify in water.
  • the dispersion degree of the titanium dioxide product obtained after the treatment by this technology has been significantly improved, and the dispersion degree has been increased by about 50 times.
  • the titanium dioxide product processed by this technology has been significantly improved in terms of dispersibility, dispersion stability, and transparency after dispersion, which will greatly expand the application of titanium dioxide materials in the fields of ultraviolet absorption and aesthetics.
  • the advantages of the present invention are: (1) The technical method does not use any surface organic additive, which makes the application field of the nano titanium dioxide dispersion universal, and increases the application field and effect of the dispersion. (2) The processing temperature of the technical method is low, the operation steps are simple, and the price is low, which is favorable for large-scale industrialization and application.
  • the main crystal phase of the titanium dioxide material obtained in Example 12 is anatase phase, and contains a trace amount of rutile phase.
  • This product is mixed with water, and can spontaneously disperse without stirring to form an aqueous dispersion in which nano-titanium dioxide particles are stably suspended, with obvious Tyndall phenomenon. Significant delamination occurred.
  • the precursor titanium hydroxide suspension was left standing for 2 hours, an obvious layering phenomenon appeared. It can be seen that the suspension stability of the product obtained by this technology has increased by more than 24 times.
  • the light transmittance of the titanium dioxide material aqueous dispersion obtained in Example 12 at a wavelength of 550 nanometers is 67%. Compared with the 2.5% light transmittance of the titanium hydroxide suspension of the same concentration of the precursor, the transparency is increased by 27 times.
  • the specific experimental operation is the same as that in Example 1. Using the same electron microscope observation method in Example 1, the dispersion degree of the titanium dioxide material aqueous dispersion obtained in Example 12 was increased by about 20 times. It can be seen that the titanium dioxide product processed by this technology has been significantly improved in terms of dispersibility, dispersion stability, and transparency after dispersion, which will greatly expand the application of titanium dioxide materials in the fields of ultraviolet absorption and aesthetics.
  • amorphous nano-titanium dioxide particles weigh 10 grams of self-made amorphous nano-titanium dioxide particles and place them in a pressure-resistant anti-corrosion tube.
  • the preparation method of the amorphous nano-titanium dioxide particles is: slowly add an ethanol solution containing titanium isopropoxide dropwise to a pH value of 2 Hydrolyzed in nitric acid-ethanol aqueous solution, washed, separated and dried. Subsequently, the pressure-resistant anti-corrosion pipe was heated to 140 degrees Celsius, the pressure of the hydrogen chloride injection port in the pipe was kept constant at 2 atmospheres, and the temperature was kept at 140 degrees Celsius for 16 hours to obtain a water-phase monodispersion with significantly improved dispersion, stability and transparency. Nano titanium dioxide powder material.
  • the crystal phase of the titanium dioxide material obtained in Example 13 was an anatase phase.
  • This product is mixed with water, and can spontaneously disperse without stirring to form an aqueous dispersion in which nano-titanium dioxide particles are stably suspended, with obvious Tyndall phenomenon. Significant delamination occurred. For comparison, when the precursor suspension was left standing for 5 hours, an obvious stratification phenomenon appeared. It can be seen that the suspension stability of the product obtained by this technology has increased by more than 288 times.
  • the light transmittance of the titanium dioxide material aqueous dispersion obtained in Example 13 at a wavelength of 550 nanometers is 95%, which is 16 times higher than that of the 6% light transmittance of the precursor suspension of the same concentration.
  • the specific experiment Operation is the same as Example 1. Using the same electron microscope observation method in Example 1, the dispersion degree of the titanium dioxide material aqueous dispersion obtained in Example 13 was increased by about 10 times. It can be seen that the titanium dioxide product processed by this technology has been significantly improved in terms of dispersibility, dispersion stability, and transparency after dispersion, which will greatly expand the application of titanium dioxide materials in the fields of ultraviolet absorption and aesthetics.
  • the pressure-resistant anti-corrosion pipe was heated to 200 degrees Celsius, the pressure of the hydrogen chloride injection port in the pipe was kept constant at 5 atmospheres, and the injection pressure of the water vapor port was 5 atmospheres, and the temperature was kept at 200 degrees Celsius for 10 hours to obtain dispersion and stability.
  • Transparent and significantly improved nano titanium dioxide powder material was obtained.
  • any numerical value recited herein includes all values of the lower value and the upper value in one unit increments from the lower value to the upper value, where there is an interval of at least two units between any lower value and any higher value, i.e. Can.
  • the number of components or process variables eg, temperature, pressure, time, etc.
  • the intent is to illustrate that the The specification also explicitly lists values such as 15 to 85, 22 to 68, 43 to 51, 30 to 32, and the like.
  • one unit is appropriately considered to be 0.0001, 0.001, 0.01, 0.1.

Abstract

提供一种二氧化钛材料及其制备方法和用途、提升二氧化钛分散性的方法。该二氧化钛材料的制备方法包括：将钛醇盐与水反应形成水合氢氧化钛沉淀；分离并干燥该水合氢氧化钛沉淀；将干燥后的氢氧化钛与少量酸溶液进行混合；将该氢氧化钛与酸溶液的混合物在密封条件下加热反应，获得含有结晶性纳米二氧化钛粒子的固体二氧化钛材料。该固体二氧化钛材料可在水中自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液，可用于制备复合材料，或用于空气、水质的净化，抗菌消毒，自清洁，防晒护肤等领域。该提升二氧化钛分散性的方法包括：将前驱物固体二氧化钛A放置在容器内，并向其中充注氯化氢气体并进行低温加热处理，获得分散性二氧化钛B产物。

Description

二氧化钛材料及其制备方法、分散性提升方法、应用
交叉参考相关引用
本申请要求2020年7月6日递交的申请号为202010642226.7、发明名称为“一种二氧化钛材料及其制备方法、应用”，以及2020年7月6日递交的申请号为202010642931.7、发明名称为“一种提升二氧化钛分散性的方法”的中国专利申请的优先权，其全部内容通过引用结合在本申请中。
技术领域
本发明特别涉及一种二氧化钛材料及其制备方法、分散性提升方法、应用。
背景技术
纳米二氧化钛是指粒径小于100纳米的二氧化钛，具有小的粒径、高的比表面积、优异的光催化活性、稳定的化学与热性能、超亲性等特殊效应，在空气治理、杀菌消毒、自清洁材料、防晒护肤品等领域具有不可替代的应用优势。如纳米二氧化钛可用于分解甲醛、苯、TVOC、SOx、NOx等，也可以用于冰箱污染异味清除、空调气洁净等，起到室内、车内空气治理的功效；纳米二氧化钛应用于玻璃、百叶窗、镜子、路灯等表面，可以实现自清洁效果；纳米二氧化钛还在医疗设备、导管、手术室、防晒化妆品、防晒服、增白产品、耐老化涂料等领域广泛应用；此外，纳米二氧化钛还可用于锂离子电池的负极材料、氢能源的光催化或光电催化制取等能源转化及存储领域。
随着二氧化钛运用范围的不断扩大，如在空气治理、材料成型、涂料、油墨制备等应用领域，产品性能很大程度上依赖于二氧化钛粉体在液体介质中的分散程度，分散越好，最终产品应用效果也越好。通常，纳米二氧化钛颗粒尺寸小，表面存在大量的缺陷，表面活性大，处于热力学不稳定状态，分散在液体介质中的纳米颗粒易凝结、团聚，发生聚沉，不能形成稳定的分散液，失去了纳米颗粒特有的性能，造成在实际应用中具有很大的缺陷。主要表现在：(1)在光触媒领域，它们配制成光触媒后无法喷涂于门窗、皮具等表面，因为会形成白色斑点，影响美观，团聚后的纳米颗粒光催化活性不高，去除甲醛等污染物效果不明显；(2)在自清洁领域，由于它们的光散射、反射强，造成透光率差，因此无法直接用于玻璃、镜子等透明表面；(3)在美容护肤产品领域，它们无法用来制造透明、自然肤色的护肤、防晒产品，会使肌肤呈现不自然的白色；(4)在膜产品领域，无法在透明薄膜制品、透明耐用面漆、精细陶瓷等方面广泛应用。
通常，纳米分散液的制备关键是克服使颗粒团聚的作用力，提高纳米颗粒在液相介质中的稳定性和延长分散稳定时间。目前，有报道采用物理分散法和化学分散法制备稳 定的纳米颗粒分散液。其中，物理分散法主要是利用外界作用力使纳米粒子分散，包括机械搅拌分散，超声波分散和高能处理法分散，物理分散法存在的缺点是，如果外界作用力停止，粒子会重新聚集。化学分散法则是利用表面化学方法，加入表面处理剂进行分散，如水相分散纳米颗粒的制备通常是通过水溶性表面活性剂或聚合物的诱导和约束实现，但颗粒表面覆盖了有机物等修饰分子，削减了分散性控制对于提升材料性能的贡献；同时，不同的应用体系也可能会和表面修饰的分子起到不良的反作用效果，降低最终产品的应用性能。此外，上述方式获得的二氧化钛分散液产物都为液体悬浊液，颗粒无法完全单分散且粒子颗粒大小不均匀，无法形成稳定的胶体状分散液，造成运输成本高和实际应用受限等困难。
受制备技术与合成工艺等影响，当前市场上所谓的纳米二氧化钛粉体都是由纳米级颗粒团聚而成的大颗粒，并不是真正意义上的纳米二氧化钛材料，这些材料在水中分散性差、不透明、易于沉降，造成在实际应用中具有很大的缺陷。因此，为进一步提升二氧化钛纳米材料的应用领域和使用效果，亟需开发一种具有单分散、高活性的纳米二氧化钛粉体，可以有效解决纳米二氧化钛应用中如何快速高效分散的技术难题。这种粉体应具有的主要性能有：(1)粉体必须能稳定分散在液相介质中形成透明性高的纳米颗粒分散液，分散后的纳米粒子需长时间稳定且不团聚产生沉淀；(2)粉体在制备或处理过程中无表面有机物修饰分子，可使纳米二氧化钛粉体的应用领域具有普适性；(3)粉体在分散应用过程中不能添加有机物等作为纳米粒子的分散剂，分散液配制过程中尽量做到无毒无害；(4)在光催化应用领域，该纳米二氧化钛粉体分散液具有高的光催化活性。
还有，材料的性质与其尺寸有着非常重要的关系，粒径超小的纳米粒子能够在能源、环境、催化等方面展现更加优异的性质。如粒径小于100纳米的二氧化钛材料，具有小的粒径、高的比表面积、优异的光催化活性、稳定的化学与热性能、超亲性等特殊效应，在空气治理、杀菌消毒、自清洁材料、防晒护肤品等领域具有不可替代的应用优势。
纳米二氧化钛粒子分散液的浓度和稳定性对于反应过程和最终产物都有重要的影响。随着二氧化钛运用范围的不断扩大，如在空气治理、材料成型、涂料、油墨制备等应用领域，产品性能很大程度上依赖于二氧化钛粉体在液体介质中的分散程度，分散越好，最终产品应用效果也越好。通常，纳米二氧化钛颗粒尺寸小，表面存在大量的缺陷，表面活性大，处于热力学不稳定状态，分散在液体介质中的纳米颗粒易凝结、团聚，发生聚沉，不能形成稳定的分散液，失去了纳米颗粒特有的性能，造成在实际应用中具有很大的缺陷。主要表现在：(1)在光触媒领域，它们配制成光触媒后无法喷涂于门窗、 皮具等表面，因为会形成白色斑点，影响美观，团聚后的纳米颗粒光催化活性不高，去除甲醛等污染物效果不明显；(2)在自清洁领域，由于它们的光散射、反射强，造成透光率差，因此无法直接用于玻璃、镜子等透明表面；(3)在美容护肤产品领域，它们无法用来制造透明、自然肤色的护肤、防晒产品，会使肌肤呈现不自然的白色；(4)在膜产品领域，无法在透明薄膜制品、透明耐用面漆、精细陶瓷等方面广泛应用。
阻止纳米二氧化钛粒子团聚，获得具有单分散的二氧化钛纳米粒子，可以大幅度提升二氧化钛纳米材料在光学、电学、催化等领域的使用性能。目前，有报道采用物理分散法和化学分散法制备稳定的纳米颗粒分散液。其中，物理分散法主要是利用外界作用力使纳米粒子分散，包括机械搅拌分散，超声波分散和高能处理法分散，物理分散法存在的缺点是，如果外界作用力停止，粒子会重新聚集。化学分散法则是利用表面化学方法，加入表面处理剂进行分散，如水相分散纳米颗粒的制备通常是通过水溶性表面活性剂或聚合物的诱导和约束实现，但颗粒表面覆盖了有机物等修饰分子，削减了分散性控制对于提升材料性能的贡献，如利用钛醇盐和烷基胺反应制备水溶性二氧化钛纳米粒子，但是这种碱性试剂的存在却钝化了产物的表面活性从而使其光催化性能降低；同时，不同的应用体系也可能会和表面修饰的分子起到不良的反作用效果，降低最终产品的应用性能，如使用聚乙二醇作为稳定剂虽然使二氧化钛纳米粒子的分散性有所提高，但是却降低了其催化活性。此外，上述方式获得的二氧化钛分散液产物仍旧为液体悬浊液，颗粒无法完全单分散且粒子颗粒大小不均匀，无法形成稳定的胶体状分散液，造成运输成本高和实际应用受限等困难。
因此，亟需开发一种不使用任何表面有机物添加剂，在低温下处理即可大大提升纳米二氧化钛分散性的技术方法，推动二氧化钛纳米材料的应用领域和使用效果。
发明内容
为提升二氧化钛纳米材料的应用领域和使用效果，本发明的一个目的是提供一种具有单分散、高活性的纳米二氧化钛粉体材料及其制备方法。
本发明的还有一个目的是提供一种大幅提升纳米二氧化钛分散性的技术方法，以促进二氧化钛纳米材料的应用领域和使用效果。
为达到上述目的，本发明采用如下技术方案：
一种二氧化钛材料的制备方法，包括以下步骤：
将钛醇盐与水反应形成水合氢氧化钛沉淀；
将所述水合氢氧化钛沉淀进行分离并干燥；
将所述干燥后的氢氧化钛与少量的酸溶液进行混合；
将所述氢氧化钛与酸溶液的混合物在密封条件下进行加热反应，获得有结晶性纳米二氧化钛粒子的固体二氧化钛材料，该固体二氧化钛材料可在水中自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液。
作为一种优选的实施方式，还包括：对所述分离并干燥后的氢氧化钛进行处理，获得含有纳米晶种的氢氧化钛；所述处理方式选自热液处理、退火处理、混入晶种的方式中的一种或者几种方式的组合。
作为一种优选的实施方式，所述钛醇盐选自甲醇钛、乙醇钛、异丙醇钛、正丙醇钛、钛酸四丁酯、异丁醇钛、戊醇钛、异戊醇钛、己醇钛、乙二醇钛、丙三醇钛中的一种或者几种。
作为一种优选的实施方式，所述钛醇盐与水反应的条件为钛醇盐与水直接接触反应；所述直接接触反应包括钛醇盐直接加入水中、水直接加入钛醇盐中、水汽直接通入钛醇盐中、钛醇盐气体直接通入水中、水汽与钛醇盐气体直接接触中的一种或者几种方式的组合。
作为一种优选的实施方式，所述少量的酸溶液与氢氧化钛的质量百分比为百分之二至百分之百；优选的质量百分比为百分之五至百分之五十。
作为一种优选的实施方式，所述酸溶液选自盐酸溶液、高氯酸溶液、次氯酸溶液、硝酸溶液、氢氟酸溶液、四氯化钛溶液、三氯化钛溶液中的一种或者几种的组合；所述酸溶液中酸的质量分数为百分之一至百分之五十。
作为一种优选的实施方式，所述密封为将氢氧化钛与酸溶液的混合物放入体积固定的容器中密封；所述体积固定的容器在加热的情况下不发生体积变化。
作为一种优选的实施方式，所述加热反应的温度为100摄氏度至200摄氏度；所述加热反应的时间为2小时至24小时。
一种采用上任意一项实施方式所述制备方法所制备的二氧化钛材料，所述二氧化钛材料为固体；所述二氧化钛材料含有结晶性纳米二氧化钛粒子；所述二氧化钛材料与水混合可自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液。
作为一种优选的实施方式，所述二氧化钛材料表面为酸性。
作为一种优选的实施方式，所述二氧化钛材料由纳米级二氧化钛粒子团聚体构成；所述纳米级二氧化钛粒子的粒径为3纳米至20纳米。
作为一种优选的实施方式，所述二氧化钛材料不含有机物。
作为一种优选的实施方式，所述二氧化钛材料固体为微米尺度以上颗粒，振实密度高于0.8克每毫升；所述二氧化钛材料固体的形态为粉末状固体、颗粒状固体或粉末与颗粒的混合状固体。
作为一种优选的实施方式，所述结晶性纳米二氧化钛粒子的晶相包括锐钛矿相、金红石相、板钛矿相中的一种或者几种的组合。
作为一种优选的实施方式，所述自发分散的条件为直接投入水中不经过搅拌即可形成分散液。
作为一种优选的实施方式，所述自发分散的条件为水中不含添加剂或分散剂中的一种或者几种的组合。
作为一种优选的实施方式，所述自发分散的条件为无二氧化钛材料表面修饰。
作为一种优选的实施方式，所述纳米二氧化钛粒子稳定悬浮的水分散液为胶体分散液；所述纳米二氧化钛粒子稳定悬浮的时间超过6个月。
一种二氧化钛材料，所述二氧化钛材料为固体；所述二氧化钛材料含有结晶性纳米二氧化钛粒子；所述二氧化钛材料与水混合可自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液。
一种如上所述的任意一种二氧化钛材料的应用，
将所述二氧化钛材料分散于溶剂中；
将所述分散后的纳米二氧化钛与其它材料结合形成复合材料；所述结合的方式选自物理混合或化学反应的方式形成复合材料。
一种如上所述的任意一种二氧化钛材料的应用，
将所述二氧化钛材料直接加入水中形成纳米二氧化钛粒子稳定悬浮的水分散液；
将所述纳米二氧化钛粒子稳定悬浮的水分散液应用于空气净化、水质净化、抗菌消毒、自清洁、防晒护肤领域中的一种或者多种。
一种提升二氧化钛分散性的方法及产物，包括以下步骤：
将前驱物固体二氧化钛A在氯化氢气氛中热处理，获得分散性二氧化钛B产物。
一种提升二氧化钛分散性的方法及产物，包括以下步骤：
将前驱物固体二氧化钛A放置于容器内；
将所述放置前驱物固体二氧化钛A的容器内充注氯化氢气体并进行低温加热处理，获得分散性二氧化钛B产物。
作为一种优选的实施方式，与前驱物二氧化钛A相比，所述分散性二氧化钛B产物在 水中的分散度提高十倍以上。
作为一种优选的实施方式，与前驱物二氧化钛A相比，所述分散性二氧化钛B产物在水中的分散稳定性提高十倍以上。
作为一种优选的实施方式，与前驱物二氧化钛A相比，所述分散性二氧化钛B产物在水中分散后的透明度提高十倍以上。
作为一种优选的实施方式，所述分散性二氧化钛B产物在不含添加剂或分散剂的纯水中可自发分散形成稳定的分散液；所述分散液主要为胶体状分散。
作为一种优选的实施方式，所述分散性二氧化钛B产物为粒径小于100纳米的纳米级二氧化钛粒子或粒径小于100纳米的纳米级二氧化钛粒子团聚体；所述分散性二氧化钛B产物的表面为酸性。
作为一种优选的实施方式，所述分散性二氧化钛B产物为结晶性纳米二氧化钛；所述结晶性纳米二氧化钛的晶相为锐钛矿相、金红石相、板钛矿相中的一种或者几种的组合。
作为一种优选的实施方式，所述前驱物固体二氧化钛A为粒径小于100纳米的纳米级二氧化钛粒子或粒径小于100纳米的纳米级二氧化钛粒子团聚体。
作为一种优选的实施方式，所述前驱物固体二氧化钛A为粒径小于50纳米的纳米级二氧化钛粒子或粒径小于50纳米的纳米级二氧化钛粒子团聚体。
作为一种优选的实施方式，所述前驱物固体二氧化钛A为结晶性二氧化钛颗粒或无定型二氧化钛颗粒。
作为一种优选的实施方式，所述前驱物固体二氧化钛A还包括氢氧化钛、氢氧化钛水合物、钛酸、钛酸水合物中的一种或者几种的组合。
作为一种优选的实施方式，所述氯化氢气氛中还含有水汽；所述水汽的压力为0.1个大气压至10个大气压。
作为一种优选的实施方式，所述氯化氢气氛中氯化氢气体的压力为0.5个大气压至20个大气压。
作为一种优选的实施方式，所述氯化氢气氛中氯化氢气体的压力为1个大气压至10个大气压。
作为一种优选的实施方式，所述氯化氢气氛中氯化氢气体的压力可以恒定或者发生改变。
作为一种优选的实施方式，所述氯化氢气氛由持续的方式或间歇的方式提供。
作为一种优选的实施方式，所述氯化氢气氛的来源可以由反应体系内部提供或外部输入提供。
作为一种优选的实施方式，所述热处理的温度为80摄氏度至300摄氏度；优选的热处理温度为100摄氏度至200摄氏度。
作为一种优选的实施方式，所述热处理的时间为2小时至48小时。
作为一种优选的实施方式，所述氯化氢气氛中氯化氢气体在预定压力范围内波动；所述氯化氢气氛由持续的方式提供；所述氯化氢气氛由外部输入提供。
相比于现有报道的所有纳米二氧化钛粉体材料，本发明的优点在于：
1.二氧化钛材料具有快速分散，操作简单的特性。本发明为固体纳米二氧化钛粉体，添加到水中10秒内即可形成透明的纳米胶体悬浊液，操作简单、现用现配，解决了现有纳米二氧化钛粉体无法均匀分散的技术难题。
2.二氧化钛材料表面不含有机物修饰添加物，与水混合可自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液。分散液中纳米颗粒尺寸均匀，分散悬浮稳定，放置6个月未发现分层；分散液外观呈现蓝色，在光照下出现明显的丁达尔现象；分散液在摇晃过程中未发现气泡，说明无有机添加物。
3.二氧化钛纳米粒子尺寸小、粒径均一，拓展了材料在玻璃等透光、美观等材料的应用。产品构成粒径为5纳米左右，分布均匀，利于在材料表面形成厚度均一、透明的膜层，与国外进口纳米光触媒对比，透明度提高了75倍。
4.二氧化钛光催化剂具有优异的光催化活性，染料、甲醛等污染物去除效率高。光催化效率是国外进口P25产品的10倍以上，提升了纳米光触媒在光催化分解甲醛等空气污染物、杀菌消毒、自清洁材料领域的应用效果。
5.产品价格低廉、安全环保无毒。本技术合成过程中可以做到原材料的回收再利用，合成过程安全环保无毒；产品产率高，价格低廉。
6.本提升二氧化钛分散性的方法不使用任何表面有机物添加剂，使纳米二氧化钛分散液的应用领域具有普适性，增加了分散液的使用领域和使用效果。
7.本提升二氧化钛分散性的方法的处理温度较低，操作步骤简单、价格低廉，利于大规模工业化推广应用。
参照后文的说明和附图，详细公开了本发明的特定实施方式，指明了本发明的原理可以被采用的方式。应该理解，本发明的实施方式在范围上并不因而受到限制。
针对一种实施方式描述和/或示出的特征可以以相同或类似的方式在一个或更多个其它实施方式中使用，与其它实施方式中的特征相组合，或替代其它实施方式中的特征。
应该强调，术语“包括/包含”在本文使用时指特征、整件、步骤或组件的存在，但并不排除一个或更多个其它特征、整件、步骤或组件的存在或附加。
附图说明
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。
图1为实施例1得到的二氧化钛材料的低倍扫描电镜图，主要为微米尺度以上颗粒组成；
图2为实施例1得到的二氧化钛材料的高倍扫描电镜图，微米尺度的颗粒由纳米级二氧化钛粒子团聚体构成；
图3为实施例1制备得到的二氧化钛产物的X射线衍射图，主要晶相为锐钛矿相，含有少量的金红石相和板钛矿相；
图4为实施例1获得的二氧化钛材料与水混合，立即自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液；
图5为实施例1获得的二氧化钛的水分散液为胶体状分散液，具有明显的丁达尔现象；
图6为实施例1得到的二氧化钛水分散液滴涂在铜网上干燥后观测得到的透射电镜图；
图7为实施例1得到的浓度为万分之五的纳米二氧化钛水分散液与P25水分散液的紫外-可见光吸收曲线；
图8为实施例1得到的纳米二氧化钛产物及P25的光催化降亚甲基蓝的曲线；
图9为实施例1得到的纳米二氧化钛产物及P25的甲醛去除效果的曲线；
图10为对比例1获得的产物的扫描电镜图，产物为花瓣状的大颗粒团聚体；
图11为对比例1得到的产物加水后获得的悬浊液经24小时后沉淀分层的结果图。
图12为实施例1得到的纳米二氧化钛产物加水后获得的质量分数为千分之五的水分散液，具有较为稳定的分散状态；
图13为质量分数为千分之五的前驱物氢氧化钛悬浊液静置2小时的光学图片，具有 明显的分层现象，悬浊液不稳定；
图14为实施例1获得的产物经水分散后滴涂在硅片上，干燥后观察得到的扫描电镜图；
图15为前驱物氢氧化钛经水分散后滴涂在硅片上，干燥后观察得到的扫描电镜图；
图16为对比例1获得的产物经水分散后滴涂在硅片上，干燥后观察得到的扫描电镜图。
具体实施方式
为了使本技术领域的人员更好地理解本发明中的技术方案，下面将结合本发明实施例中的附图，对本发明实施例中的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有做出创造性劳动的前提下所获得的所有其他实施例，都应当属于本发明保护的范围。
除非另有定义，本文所使用的所有的技术和科学术语与属于本发明的技术领域的技术人员通常理解的含义相同。本文中在本发明的说明书中所使用的术语只是为了描述具体的实施方式的目的，不是旨在于限制本发明。本文所使用的术语“和/或”包括一个或多个相关的所列项目的任意的和所有的组合。
实施例1
搅拌下，将10克钛酸四丁酯缓慢滴加到200毫升去离子水中，搅拌形成水合氢氧化钛沉淀；将上述水合氢氧化钛沉淀经分离洗涤操作去除有机物，后经分离干燥获得氢氧化钛粉末。随后，取2克上述获得的氢氧化钛粉末，搅拌下加入0.5克质量分数为百分之二十的盐酸溶液，持续搅拌形成微湿的氢氧化钛混合物。随后，将上述微湿的氢氧化钛混合物放入反应釜中密封。最后，将上述反应釜放入烘箱中，在140摄氏度下加热15小时，获得纳米二氧化钛产物。
本实施例1获得的二氧化钛材料产物为粉末状固体，颜色为浅白色。取少量实施例1获得粉末在导电胶上铺展薄薄一层，用于扫描电镜观察样品的形貌，如图1和图2所示。图1可以看出，实施例1得到的二氧化钛材料主要为微米尺度以上颗粒组成，振实密度约为0.85克每毫升。放大扫描倍率，如图2所示，微米尺度的颗粒由纳米级二氧化钛粒子团聚体构成，纳米级二氧化钛粒子的粒径主要分布在5纳米左右，说明本实施例获得的纳米二氧化钛具有小的粒径，单分散性较好。图3是实施例1制备得到的二氧化钛产物的X射线衍射图，从图3可以看出本实施例1制得的纳米二氧化钛主要晶相为锐 钛矿相，具有较好的结晶性，同时还含有少量的金红石相和板钛矿相；本实施例获得的复合晶相有利于促进光生“电子-空穴”对的分离效果，提升二氧化钛材料的光催化效率。本实施例1获得的二氧化钛材料与水混合，可自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液。如图4所示，取少量实施例1获得的二氧化钛材料放入玻璃瓶中，用移液枪往玻璃瓶中加入去离子水，可以看到，在没有搅拌的条件下，粉体也可立马分散在水中形成分散液。如图5所示，该分散液具有很好的单分散性，在水溶液中可以形成稳定的胶体状分散液，具有明显的丁达尔现象；纳米粒子悬浮稳定、不团聚也不易沉降，放置6个月以上溶液未发生分层现象。如图6所示，将上述分散液滴涂于铜网上，采用透射电镜观察，可以进一步看出本实施例获得的材料加水后纳米二氧化钛粒子完全分散，分散后的纳米颗粒的粒径也和扫描电镜观察得到的一致。将实施例1得到的纳米二氧化钛分散于水中，形成浓度为万分之五的水分散液，后取上述分散液体于1厘米厚的石英比色皿中，测试样品的紫外-可见光吸收曲线。如图7所示，本实施例1得的二氧化钛材料分散液在极低的浓度下，能完全吸收小于370纳米的紫外光，紫外线吸收能力强；同时在大于400纳米的可见光区域具有极高的透光性，透光度大于百分之九十五以上。同P25纳米二氧化钛材料相比，以550纳米波长为例，本实施例获得的产品透明度提高了75倍，大大的拓展了二氧化钛材料在紫外吸收、美观等产品领域的应用。本实施例获得纳米二氧化钛材料具有很好的光催化活性，具体的比较方式为，分别称取本实施例1获得的产物和P25(德固萨)样品1克分散于100毫升浓度为2.0×10-5摩尔每升的亚甲基蓝溶液中，放置在暗处磁搅拌30分钟，使其达到温度平衡和吸附平衡。后开启模拟太阳光灯，搅拌，每隔固定时间取出3毫升样品，离心分离颗粒，用紫外-可见光谱仪在665纳米处测量溶液的吸光度，计算亚甲基蓝的剩余浓度。图8中可以看出，本实施例1获得的产物二氧化钛光催化剂具有优异的光催化活性，催化效率是P25材料的11倍。此外，本实施例获1得的纳米二氧化钛材料还具有优异的除甲醛效果，具体的测试方法为：往1平方米的纸基上喷涂50毫升浓度为百分之一的实施例1获得的二氧化钛分散液，自然干燥；随后，将上述纸基放入容积为1立方米的测试舱中，通入一定浓度和体积的甲醛，开启风扇，使舱内空气混合均匀；后开启模拟太阳光灯，每隔一定时间采样检测舱内空气中的甲醛浓度。本测试采用P25材料作为对照试验。图9中可以看出，经过12小时，实施例1产品的甲醛去除率为百分之九十九，而P25的甲醛去除率仅为百分之二十五，可见，本实施例1获得的产物二氧化钛光催化剂具有优异的除甲醛效果。
同水热法相比，本技术获得的“溶解-限域生长”的化学机理过程与水热法的“溶解 -生长”过程具有显著的差异和技术创新效果，其中，水热法是以水作为溶剂，通常需要将反应物完全浸泡并分散在水中进行反应。本技术中的反应物只和少量酸溶液混合，仅在表面有一层薄薄水层，限制了转化时反应物粉体经溶解和再结晶过程中的离子扩散迁移路径和距离，使转化反应限制在微小体积内，从而获得尺寸大小均一、超细的纳米材料产物；同时，本技术中的催化剂促使前驱物溶解，增加了溶质钛离子在薄薄水层的浓度和成核数量，进一步促进颗粒大小均匀的纳米二氧化钛产物的形成，最终形成单分散纳米二氧化钛材料。
综上，相比于现有报道的所有纳米二氧化钛粉体材料，本发明的优点在于：
(1)二氧化钛材料具有快速分散，操作简单的特性。本发明为固体纳米二氧化钛粉体，添加到水中10秒内即可形成透明的纳米胶体悬浊液，操作简单、现用现配，解决了现有纳米二氧化钛粉体无法均匀分散的技术难题。
(2)二氧化钛材料表面不含有机物修饰添加物，与水混合可自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液。分散液中纳米颗粒尺寸均匀，分散悬浮稳定，放置6个月未发现分层；分散液外观呈现蓝色，在光照下出现明显的丁达尔现象；分散液在摇晃过程中未发现气泡，说明无有机添加物。
(3)二氧化钛纳米粒子尺寸小、粒径均一，拓展了材料在玻璃等透光、美观等材料的应用。产品构成粒径为5纳米左右，分布均匀，利于在材料表面形成厚度均一、透明的膜层，与国外进口纳米光触媒对比，透明度提高了75倍。
(4)二氧化钛光催化剂具有优异的光催化活性，染料、甲醛等污染物去除效率高。光催化效率是国外进口P25产品的10倍以上，提升了纳米光触媒在光催化分解甲醛等空气污染物、杀菌消毒、自清洁材料领域的应用效果。
(5)产品价格低廉、安全环保无毒。本技术合成过程中可以做到原材料的回收再利用，合成过程安全环保无毒；产品产率高，价格低廉。
实施例2
搅拌下，将10克钛酸四丁酯缓慢滴加到200毫升去离子水中，搅拌形成水合氢氧化钛沉淀；将上述水合氢氧化钛沉淀经分离洗涤操作去除有机物，后经分离干燥获得氢氧化钛粉末。随后，取2克上述获得的氢氧化钛粉末，搅拌下加入0.1克质量分数为百分之五十的四氯化钛溶液，持续搅拌形成微湿的氢氧化钛混合物。随后，将上述微湿的氢氧化钛混合物放入反应釜中密封。最后，将上述反应釜放入烘箱中，在180摄氏度下加热10小时，获得纳米二氧化钛产物。
本实施例2获得的二氧化钛材料产物为粉末状固体，外观颜色为白色，振实密度约为0.87克每毫升。低倍扫描电镜观察到样品的形貌为无规则的微米颗粒；进一步放大扫描电镜倍率，可以观察到这些微米颗粒主要由5纳米至15纳米，分散性较好的纳米级二氧化钛粒子团聚构成。X射线衍射证实本实施例2获得的纳米二氧化钛主要晶相为结晶性良好的锐钛矿相，同时还含有微量的金红石相，锐钛/金红石复合晶相有利于促进光生“电子-空穴”对的分离效果，提升二氧化钛材料的光催化效率。
将少量本实施例2获得的二氧化钛材料产物放入纯净水中，可以看到二氧化钛材料产物自发的“溶解”分散在纯净水中，形成纳米二氧化钛粒子稳定悬浮的胶体状水分散液，该分散液中纳米粒子悬浮稳定、不团聚，具有明显的丁达尔现象，分散液放置8个月也不会出现明显分层现象。
将实施例2得到的纳米二氧化钛分散于纯净水中，形成纳米二氧化钛质量分数为万分之五的水分散液，该水分散液在1厘米厚的石英比色皿中，能完全吸收小于370纳米的紫外光，紫外线吸收能力强；同时在大于400纳米的可见光区域具有极高的透光性，透光度大于百分之九十。同P25纳米二氧化钛材料相比，以550纳米波长为例，本实施例2获得的产品透明度提高了53倍，大大的拓展了二氧化钛材料在紫外吸收、美观等产品领域的应用。
本实施例2获得纳米二氧化钛材料具有很好的光催化活性。实验操作同实施例1，本实施例2获得纳米二氧化钛材料分解亚甲基蓝染料的效率大约是商业P25材料的9.6倍，12小时甲醛去除率为百分之九十，具有优异的除甲醛效果。
实施例3
搅拌下，将10克钛酸四丁酯缓慢滴加到200毫升去离子水中，搅拌形成水合氢氧化钛沉淀；将上述水合氢氧化钛沉淀经分离洗涤操作去除有机物，后经分离干燥获得氢氧化钛粉末。随后，取2克上述获得的氢氧化钛粉末，搅拌下加入1.5克质量分数为百分之十的次氯酸溶液，持续搅拌形成微湿的氢氧化钛混合物。随后，将上述微湿的氢氧化钛混合物放入反应釜中密封。最后，将上述反应釜放入烘箱中，在120摄氏度下加热24小时，获得纳米二氧化钛产物。
本实施例3获得的二氧化钛材料产物常温常压自然干燥后为粉末状固体，外观颜色为浅灰白色，振实密度约为0.91克每毫升。低倍扫描电镜观察到样品的形貌为无规则的微米颗粒；进一步放大扫描电镜倍率，可以观察到这些微米颗粒主要由10纳米至20纳米，分散性较好的纳米级二氧化钛粒子团聚构成。X射线衍射证实本实施例2获得的纳 米二氧化钛主要晶相为结晶性良好的锐钛矿相，同时还含有少量的金红石相，锐钛/金红石复合晶相有利于促进光生“电子-空穴”对的分离效果，提升二氧化钛材料的光催化效率。
将少量本实施例3获得的二氧化钛材料产物放入去离子水中，可以看到二氧化钛材料产物自发的“溶解”分散在去离子水中，形成纳米二氧化钛粒子稳定悬浮的胶体状水分散液，该分散液中纳米粒子悬浮稳定、不团聚，具有明显的丁达尔现象，分散液放置6个月也不会出现明显分层现象。
将实施例3得到的纳米二氧化钛分散于去离子水中，形成纳米二氧化钛质量分数为万分之五的水分散液，该水分散液在1厘米厚的石英比色皿中，能完全吸收小于370纳米的紫外光，紫外线吸收能力强；同时在大于400纳米的可见光区域具有极高的透光性，透光度大于百分之八十。同P25纳米二氧化钛材料相比，以550纳米波长为例，本实施例3获得的产品透明度提高了45倍，大大的拓展了二氧化钛材料在紫外吸收、美观等产品领域的应用。
本实施例3获得纳米二氧化钛材料具有很好的光催化活性。实验操作同实施例1，本实施例3获得纳米二氧化钛材料分解亚甲基蓝染料的效率大约是商业P25材料的7.2倍，12小时甲醛去除率为百分之八十五，具有优异的除甲醛效果。
实施例4
搅拌下，往200毫升去离子水中逐渐通入钛酸异丙酯气体，酸异丙酯气体通入的总量为10克，形成水合氢氧化钛沉淀；将上述水合氢氧化钛沉淀经分离洗涤操作去除有机物，后经分离干燥获得氢氧化钛粉末。随后，取2克上述获得的氢氧化钛粉末，搅拌下加入1.0克质量分数为百分之十五的高氯酸溶液，持续搅拌形成微湿的氢氧化钛混合物。随后，将上述微湿的氢氧化钛混合物放入反应釜中密封。最后，将上述反应釜放入微波炉中，在160摄氏度下微波加热2小时，获得纳米二氧化钛产物。
本实施例4获得的二氧化钛材料产物经常温常压自然干燥后为粉末状固体，外观颜色为浅灰白色，振实密度约为0.93克每毫升。低倍扫描电镜观察到样品的形貌为无规则的微米颗粒；进一步放大扫描电镜倍率，可以观察到这些微米颗粒主要由8纳米至18纳米，分散性较好的纳米级二氧化钛粒子团聚构成。X射线衍射证实本实施例4获得的纳米二氧化钛主要晶相为结晶性良好的锐钛矿相，同时还含有微量的金红石相，锐钛/金红石复合晶相有利于促进光生“电子-空穴”对的分离效果，提升二氧化钛材料的光催化效率。
将少量本实施例4获得的二氧化钛材料产物放入纯净水中，可以看到二氧化钛材料产物自发的“溶解”分散在纯净水中，形成纳米二氧化钛粒子稳定悬浮的胶体状水分散液，该分散液中纳米粒子悬浮稳定、不团聚，具有明显的丁达尔现象，分散液放置6个月也不会出现明显分层现象。
将实施例4得到的纳米二氧化钛分散于纯净水中，形成纳米二氧化钛质量分数为万分之五的水分散液，该水分散液在1厘米厚的石英比色皿中，能完全吸收小于370纳米的紫外光，紫外线吸收能力强；同时在大于400纳米的可见光区域具有极高的透光性，透光度大于百分之九十。同P25纳米二氧化钛材料相比，以550纳米波长为例，本实施例4获得的产品透明度提高了61倍，大大拓展了二氧化钛材料在紫外吸收、美观等产品领域的应用。
本实施例4获得纳米二氧化钛材料具有很好的光催化活性。实验操作同实施例1，本实施例4获得纳米二氧化钛材料分解亚甲基蓝染料的效率大约是商业P25材料的10倍，12小时甲醛去除率为百分之九十三，具有优异的除甲醛效果。
实施例5
按水和乙醇钛质量比为10:1的量，将水汽和乙醇钛气体混合，形成水合氢氧化钛沉淀；将上述水合氢氧化钛沉淀经分离洗涤操作去除有机物，后经分离干燥获得氢氧化钛粉末。随后，取2克上述获得的氢氧化钛粉末，搅拌下加入1.8克质量分数为百分之五的硝酸溶液，持续搅拌形成微湿的氢氧化钛混合物。随后，将上述微湿的氢氧化钛混合物放入反应釜中密封。最后，将上述反应釜放入微波炉中，在140摄氏度下微波加热3小时，获得纳米二氧化钛产物。
本实施例5获得的二氧化钛材料产物经常温常压自然干燥后为粉末状固体，外观颜色为白色，振实密度约为0.95克每毫升。低倍扫描电镜观察到样品的形貌为无规则的微米颗粒；进一步放大扫描电镜倍率，可以观察到这些微米颗粒主要由10纳米至20纳米，分散性较好的纳米级二氧化钛粒子团聚构成。X射线衍射证实本实施例5获得的纳米二氧化钛主要晶相为结晶性良好的锐钛矿相。
将少量本实施例5获得的二氧化钛材料产物放入纯净水中，可以看到二氧化钛材料产物自发的“溶解”分散在纯净水中，形成纳米二氧化钛粒子稳定悬浮的胶体状水分散液，该分散液中纳米粒子悬浮稳定、不团聚，具有明显的丁达尔现象，分散液放置6个月也不会出现明显分层现象。
将实施例5得到的纳米二氧化钛分散于纯净水中，形成纳米二氧化钛质量分数为万 分之五的水分散液，该水分散液在1厘米厚的石英比色皿中，能完全吸收小于370纳米的紫外光，紫外线吸收能力强；同时在大于400纳米的可见光区域具有极高的透光性，透光度大于百分之五十。同P25纳米二氧化钛材料相比，以550纳米波长为例，本实施例5获得的产品透明度提高了30倍，拓展了二氧化钛材料在紫外吸收、美观等产品领域的应用。
本实施例5获得纳米二氧化钛材料具有很好的光催化活性。实验操作同实施例1，本实施例5获得纳米二氧化钛材料分解亚甲基蓝染料的效率大约是商业P25材料的8倍，12小时甲醛去除率为百分之九十五，具有优异的除甲醛效果。
实施例6
搅拌下，将10克乙二醇钛缓慢滴加到200毫升去离子水中，搅拌形成水合氢氧化钛沉淀；将上述水合氢氧化钛沉淀经分离洗涤操作去除有机物，后经分离干燥获得氢氧化钛粉末。随后，取2克上述获得的氢氧化钛，搅拌下加入0.8克质量分数为百分之十的氢氟酸溶液，持续搅拌形成微湿的氢氧化钛混合物。随后，将上述微湿的氢氧化钛混合物放入反应釜中密封。最后，将上述反应釜放入油浴中，在180摄氏度下加热10小时，获得纳米二氧化钛产物。
本实施例6获得的二氧化钛材料产物经常温常压自然干燥后为粉末状固体，外观颜色为白色，振实密度约为1.0克每毫升。低倍扫描电镜观察到样品的形貌为无规则的微米颗粒；进一步放大扫描电镜倍率，可以观察到这些微米颗粒主要由5纳米至15纳米，分散性较好的纳米级二氧化钛粒子团聚构成。X射线衍射证实本实施例6获得的纳米二氧化钛主要晶相为结晶性良好的锐钛矿相。
将少量本实施例6获得的二氧化钛材料产物放入纯净水中，可以看到二氧化钛材料产物自发的“溶解”分散在纯净水中，形成纳米二氧化钛粒子稳定悬浮的胶体状水分散液，该分散液中纳米粒子悬浮稳定、不团聚，具有明显的丁达尔现象，分散液放置6个月也不会出现明显分层现象。
将实施例6得到的纳米二氧化钛分散于纯净水中，形成纳米二氧化钛质量分数为万分之五的水分散液，该水分散液在1厘米厚的石英比色皿中，能完全吸收小于370纳米的紫外光，紫外线吸收能力强；同时在大于400纳米的可见光区域具有极高的透光性，透光度大于百分之六十。同P25纳米二氧化钛材料相比，以550纳米波长为例，本实施例6获得的产品透明度提高了40倍，拓展了二氧化钛材料在紫外吸收、美观等产品领域的应用。
本实施例6获得纳米二氧化钛材料具有很好的光催化活性。实验操作同实施例1，本实施例6获得纳米二氧化钛材料分解亚甲基蓝染料的效率大约是商业P25材料的7.4倍，12小时甲醛去除率为百分之九十六，具有优异的除甲醛效果。
实施例7
取实施例1至6任一方式获得的纳米二氧化钛产物1克，加入到50克水中形成水分散液；后取上述分散液20克与20克质量分数为百分之五的聚乙烯醇水溶液中混合，得到纳米二氧化钛/聚乙烯醇透明分散液复合材料。该分散液复合材料为透明状，可以喷涂在透明、美观材料表面，干燥后不产生斑点，不影响材料表面的颜色；该分散液复合材料使用在材料表面形成致密涂层，不易脱落，具有优异的光催化性能，可以去除甲醛，具有抗菌和自清洁功能。
实施例8
取实施例1至6任一方式获得的纳米二氧化钛产物1克，加入到100克质量分数为百分之五十的乙醇水溶液中形成分散液；后取上述分散液50克，往其中缓慢加入0.5毫升的正硅酸乙酯形成混合液；最后，将上述混合液在搅拌条件下，于80摄氏度下反应5小时，获得纳米氧化钛/氧化硅透明复合材料。该复合材料为透明状，可以喷涂在透明、美观材料表面，干燥后不产生斑点，不影响材料表面的颜色；该复合材料使用在材料表面形成致密涂层，不易脱落，具有优异的光催化性能，可以去除甲醛，具有抗菌和自清洁功能。
实施例9
取实施例1至6任一方式获得的纳米二氧化钛产物1克，加入到100克水中形成水分散液，该分散液即为光触媒；将上述光触媒喷涂墙体表面，干燥后不产生斑点，具有优异的光催化分解有机物性能，可用于去除甲醛等室内、车内有机空气污染物，起到空气净化的效果。
实施例10
取实施例1至6任一方式获得的纳米二氧化钛产物1克，加入到50克水中形成水分散液，该分散液即为光触媒；将上述光触媒喷涂基材表面，干燥后不产生斑点，具有优异抗菌消毒功能。
对比例1
搅拌下，将10克钛酸四丁酯缓慢滴加到200毫升去离子水中，搅拌形成水合氢氧化钛沉淀；将上述水合氢氧化钛沉淀经分离洗涤操作去除有机物，后经分离干燥获得氢氧 化钛粉末。随后，取2克上述获得的氢氧化钛粉末，搅拌下加入5克质量分数为百分之二十的盐酸溶液，持续搅拌形成氢氧化钛悬浊液。随后，将上述氢氧化钛悬浊液放入反应釜中密封。最后，将上述反应釜放入烘箱中，在140摄氏度下加热15小时，获得产物。本对比例获得产物中含有大量的花瓣状大颗粒，如扫描电镜图10所示；同时产品无法分散在水中形成稳定、透明的分散液，得到的产物为悬浊液体，几个小时内便会出现沉淀分层，如图11所示；XRD测试表明本对比例获得的二氧化钛产物主要为金红石相二氧化钛，无法获得实施例1得到的高活性锐钛矿相二氧化钛；本对比例产品的亚甲基蓝的光催化降解性能小于P25商业产品，效率只是P25的三分之一，也仅为实施例1产品性能的三十分之一，光催化性能极差；此外，本对比例1得的二氧化钛材料分散液在极低浓度下的可见光透光度小于百分之五，大大限制了该材料在自清洁、美观、膜等产品领域的应用。本对比例在产物形貌、分散性、晶相、催化效率等结构、性能上均无法获得实施例产物的发明效果。
对比例2
搅拌下，将10克钛酸四丁酯缓慢滴加到200毫升去离子水中，搅拌形成水合氢氧化钛沉淀；将上述水合氢氧化钛沉淀经分离洗涤操作去除有机物，后经分离干燥获得氢氧化钛粉末。随后，取2克上述获得的氢氧化钛粉末，搅拌下加入0.5克水，持续搅拌形成微湿的氢氧化钛。随后，将上述微湿的氢氧化钛放入反应釜中密封。最后，将上述反应釜放入烘箱中，在140摄氏度下加热15小时，获得产物。本对比例无法将反应物完全转化为结晶性的纳米二氧化钛产物；本对比例获得产物中含有大量大颗粒，无法分散在水中形成稳定、透明的分散液，得到的产物为悬浊液体，几个小时内便会出现沉淀分层；此外，本对比产物的光催化性能小于P25商业产品，亚甲基蓝的降解效率仅为P25的0.9倍，光催化性能不佳。本对比例在产物形貌、分散性、化效率等结构、性能上均无法获得实施例产物的发明效果。
实施例11
首先，称取10克氢氧化钛(广东翁江化学试剂有限公司，CAS号:20338-08-3，纯度≥99％)粉末放置于耐压防腐管中。随后，将耐压防腐管加热至120摄氏度，保持管内氯化氢注入口的压力约为2个大气压(在1.5个大气压至2个大气压之间波动)，水汽口的注入压力约为1个大气压，于120摄氏度下恒温24小时，获得分散度、稳定性、透明的显著提升的纳米二氧化钛粉体材料。
本实施例11获得的二氧化钛材料的主要晶相为锐钛矿相。本产物与水混合，在没有 搅拌的条件下，也可自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液。图12为本实施例得到的纳米二氧化钛产物加水后获得的质量分数为千分之五的水分散液，该分散液具有较好的单分散性，在水溶液中可以形成较为稳定的胶体状分散液，具有明显的丁达尔现象；纳米粒子悬浮稳定、不易沉降，放置3天以上溶液未发生明显分层现象。用于对比，图13为质量分数为千分之五的前驱物氢氧化钛悬浊液静置2小时的光学图片，可以看出具有明显的分层现象，悬浊液不稳定，可见本技术获得的产物悬浮稳定性增加了36倍以上。
本实施例11获得的二氧化钛材料水分散液在550纳米波长下的透光率为85％，相比于同浓度前驱物氢氧化钛悬浊液透光率的2.5％，透明度提升了34倍。具体的实验操作为：取少量本实施例11获得的二氧化钛材料，配制成质量分数为万分之五的水分散液，用于对比，也配制了质量分数为万分之五的前驱物氢氧化钛悬浊液；后分别取上述分散液于1厘米厚的石英比色皿中，测试样品在550纳米波长下的透光度，采用纯水作为空白。
取少量本实施例11获得的产物分散于去离子水中后取少量滴在硅片上，自然晾干，将晾干后的硅片用导电胶粘附在扫描电镜的样品台上，用于扫描电镜观察样品的形貌，如图3所示。从图14可以看出产物二氧化钛纳米粒子分散度好，可以铺展在硅片上，颗粒的大小约为50纳米，颗粒的均一度较好。作为对比，图15为前驱物氢氧化钛的扫描电镜图，可以看出前驱物为50纳米左右的纳米颗粒堆积成的聚集体，分散度差，也进一步说明前驱物在水中易于沉降分层。通过分别统计扫描电镜图片上相同面积中的颗粒数量，可以估算出本技术处理后得到的二氧化钛产物的分散度得到了显著的提升，分散度大约提升了50倍。可见，本技术处理得到的二氧化钛产物在分散度、分散稳定性、分散后的透明度等方面均得到了显著的提高，将大大拓展二氧化钛材料在紫外吸收、美观等产品领域的应用。
综上，本发明的优点在于：(1)本技术方法不使用任何表面有机物添加剂，使纳米二氧化钛分散液的应用领域具有普适性，增加了分散液的使用领域和使用效果。(2)本技术方法的处理温度较低，操作步骤简单、价格低廉，利于大规模工业化推广应用。
实施例12
首先，称取10克氢氧化钛(广东翁江化学试剂有限公司，CAS号:20338-08-3，纯度≥99％)粉末放置于耐压防腐管中。随后，将耐压防腐管加热至150摄氏度，保持管内氯化氢注入口的压力约为8个大气压，水汽口的注入压力约为8个大气压，于150摄 氏度下恒温12小时，获得分散度、稳定性、透明的显著提升的纳米二氧化钛粉体材料。
本实施例12获得的二氧化钛材料的主要晶相为锐钛矿相，含有微量金红石相。本产物与水混合，在没有搅拌的条件下，可自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液，具有明显的丁达尔现象；分散液中纳米粒子悬浮稳定、不易沉降，放置2天溶液未发生明显分层现象。用于对比，前驱物氢氧化钛悬浊液静置2小时出现明显的分层现象，可见本技术获得的产物悬浮稳定性增加了24倍以上。
本实施例12获得的二氧化钛材料水分散液在550纳米波长下的透光率为67％，相比于同浓度前驱物氢氧化钛悬浊液透光率的2.5％，透明度提升了27倍，具体的实验操同实施例1。采用实施例1相同的电镜观察方法，本实施例12获得的二氧化钛材料水分散液的分散度大约提升了20倍。可见，本技术处理得到的二氧化钛产物在分散度、分散稳定性、分散后的透明度等方面均得到了显著的提高，将大大拓展二氧化钛材料在紫外吸收、美观等产品领域的应用。
实施例13
首先，称取10克自制的无定型纳米二氧化钛颗粒放置于耐压防腐管中，该无定型纳米二氧化钛颗粒的制备方法为：将含有异丙醇钛的乙醇溶液缓慢滴加到pH值为2的硝酸-乙醇水溶液中水解，并经洗涤、分离干燥后获得。随后，将耐压防腐管加热至140摄氏度，保持管内氯化氢注入口的压力为2个大气压不变，于140摄氏度下恒温16小时，获得分散度、稳定性、透明的显著提升的水相单分散纳米二氧化钛粉体材料。
本实施例13获得的二氧化钛材料的晶相为锐钛矿相。本产物与水混合，在没有搅拌的条件下，可自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液，具有明显的丁达尔现象；分散液中纳米粒子悬浮稳定、不易沉降，放置60天溶液未发生明显分层现象。用于对比，前驱物悬浊液静置5小时出现明显的分层现象，可见本技术获得的产物悬浮稳定性增加了288倍以上。
本实施例13获得的二氧化钛材料水分散液在550纳米波长下的透光率为95％，相比于同浓度前驱物悬浊液透光率的6％，透明度提升了16倍，具体的实验操同实施例1。采用实施例1相同的电镜观察方法，本实施例13获得的二氧化钛材料水分散液的分散度大约提升了10倍。可见，本技术处理得到的二氧化钛产物在分散度、分散稳定性、分散后的透明度等方面均得到了显著的提高，将大大拓展二氧化钛材料在紫外吸收、美观等产品领域的应用。
实施例14
首先，称取10克自制的结晶性纳米二氧化钛颗粒放置于耐压防腐管中，该结晶性纳米二氧化钛颗粒的制备方法为：将含有异丙醇钛的乙醇溶液缓慢滴加到pH值为2的硝酸-乙醇水溶液中水解，并经洗涤、分离干燥后，经300摄氏度退火处理3小时获得，该结晶性的晶相为锐钛矿相。随后，将耐压防腐管加热至200摄氏度，保持管内氯化氢注入口的压力为5个大气压不变，水汽口的注入压力为5个大气压，于200摄氏度下恒温10小时，获得分散度、稳定性、透明的显著提升的纳米二氧化钛粉体材料。
本实施例14获得的二氧化钛材料的晶相为锐钛矿相。本产物与水混合，在没有搅拌的条件下，可自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液，具有明显的丁达尔现象；分散液中纳米粒子悬浮稳定、不易沉降，放置10天溶液未发生明显分层现象。用于对比，前驱物悬浊液静置3小时出现明显的分层现象，可见本技术获得的产物悬浮稳定性增加了80倍以上。
本实施例14获得的二氧化钛材料水分散液在550纳米波长下的透光率为83％，相比于同浓度前驱物悬浊液透光率的3.6％，透明度提升了23倍，具体的实验操同实施例1。采用实施例1相同的电镜观察方法，本实施例14获得的二氧化钛材料水分散液的分散度大约提升了20倍。可见，本技术处理得到的二氧化钛产物在分散度、分散稳定性、分散后的透明度等方面均得到了显著的提高，将大大拓展二氧化钛材料在紫外吸收、美观等产品领域的应用。
对比例3
首先，称取10克氢氧化钛(广东翁江化学试剂有限公司，CAS号:20338-08-3，纯度≥99％，粒径为20-30nm)粉末放置于耐压防腐管中。随后，将耐压防腐管加热至120摄氏度，保持管内水汽口的注入压力约为1个大气压，于120摄氏度下恒温24小时，获得产物。本对比例获得产物形貌和前驱物基本一致，如扫描电镜图16所示；同时产品无法分散在水中形成稳定、透明的分散液，得到的产物为悬浊液体，2小时便会出现沉淀分层。因此，本对比例处理无法改变二氧化钛产物在分散度、分散稳定性、分散后的透明度等方面的性能。
本文引用的任何数值都包括从下限值到上限值之间以一个单位递增的下值和上值的所有值，在任何下值和任何更高值之间存在至少两个单位的间隔即可。举例来说，如果阐述了一个部件的数量或过程变量(例如温度、压力、时间等)的值是从1到90，优选从20到80，更优选从30到70，则目的是为了说明该说明书中也明确地列举了诸如15到85、22到68、43到51、30到32等值。对于小于1的值，适当地认为一个单位是0.0001、 0.001、0.01、0.1。这些仅仅是想要明确表达的示例，可以认为在最低值和最高值之间列举的数值的所有可能组合都是以类似方式在该说明书明确地阐述了的。
除非另有说明，所有范围都包括端点以及端点之间的所有数字。与范围一起使用的“大约”或“近似”适合于该范围的两个端点。因而，“大约20到30”旨在覆盖“大约20到大约30”，至少包括指明的端点。
应该理解，以上描述是为了进行图示说明而不是为了进行限制。通过阅读上述描述，在所提供的示例之外的许多实施方式和许多应用对本领域技术人员来说都将是显而易见的。因此，本教导的范围不应该参照上述描述来确定，而是应该参照所附权利要求以及这些权利要求所拥有的等价物的全部范围来确定。出于全面之目的，所有文章和参考包括专利申请和公告的公开都通过参考结合在本文中。在前述权利要求中省略这里公开的主题的任何方面并不是为了放弃该主体内容，也不应该认为发明人没有将该主题考虑为所公开的发明主题的一部分。

Claims (34)

  1. 一种二氧化钛材料的制备方法，其特征在于，包括以下步骤：
    将钛醇盐与水反应形成水合氢氧化钛沉淀；
    将所述水合氢氧化钛沉淀进行分离并干燥；
    将所述干燥后的氢氧化钛与少量的酸溶液进行混合；
    将所述氢氧化钛与酸溶液的混合物在密封条件下进行加热反应，获得含有结晶性纳米二氧化钛粒子的固体二氧化钛材料，该固体二氧化钛材料可在水中自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液。
  2. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于，还包括：对所述分离并干燥后的氢氧化钛进行处理，获得含有纳米晶种的氢氧化钛；所述处理方式选自热液处理、退火处理、混入晶种的方式中的一种或者几种方式的组合。
  3. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：所述钛醇盐选自甲醇钛、乙醇钛、异丙醇钛、正丙醇钛、钛酸四丁酯、异丁醇钛、戊醇钛、异戊醇钛、己醇钛、乙二醇钛、丙三醇钛中的一种或者几种。
  4. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：所述钛醇盐与水反应的条件为钛醇盐与水直接接触反应；所述直接接触反应包括钛醇盐直接加入水中、水直接加入钛醇盐中、水汽直接通入钛醇盐中、钛醇盐气体直接通入水中、水汽与钛醇盐气体直接接触中的一种或者几种方式的组合。
  5. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：所述少量的酸溶液与氢氧化钛的质量百分比为百分之二至百分之百；优选的质量百分比为百分之五至百分之五十。
  6. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：所述酸溶液选自盐酸溶液、高氯酸溶液、次氯酸溶液、硝酸溶液、氢氟酸溶液、四氯化钛溶液、三氯化钛溶液中的一种或者几种的组合；所述酸溶液中酸的质量分数为百分之一至百分之五十。
  7. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：所述密封为将氢氧化钛与酸溶液的混合物放入体积固定的容器中密封；所述体积固定的容器在加热的情况下不发生体积变化。
  8. 如权利要求1所述的一种二氧化钛材料的制备方法，其特征在于：所述加热反应的温度为100摄氏度至200摄氏度；所述加热反应的时间为2小时至24小时。
  9. 一种采用权利要求1至8任意一项所述制备方法所制备的二氧化钛材料，其特征在于，所述二氧化钛材料为固体；所述二氧化钛材料含有结晶性纳米二氧化钛粒子；所述二氧化钛材料与水混合可自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液。
  10. 如权利要求9所述的一种二氧化钛材料，其特征在于：所述二氧化钛材料表面为酸性；所述二氧化钛材料不含有机物。
  11. 如权利要求9所述的一种二氧化钛材料，其特征在于：所述二氧化钛材料由纳米级二氧化钛粒子团聚体构成；所述纳米级二氧化钛粒子的粒径为3纳米至20纳米。
  12. 如权利要求9所述的一种二氧化钛材料，其特征在于：所述二氧化钛材料固体为微米尺度以上颗粒，振实密度高于0.8克每毫升；所述二氧化钛材料固体的形态为粉末状固体、颗粒状固体或粉末与颗粒的混合状固体。
  13. 如权利要求9所述的一种二氧化钛材料，其特征在于：所述结晶性纳米二氧化钛粒子的晶相包括锐钛矿相、金红石相、板钛矿相中的一种或者几种的组合。
  14. 如权利要求9所述的一种二氧化钛材料，其特征在于：所述自发分散的条件为直接投入水中不经过搅拌即可形成分散液。
  15. 如权利要求9所述的一种二氧化钛材料，其特征在于：所述自发分散的条件为水中不含添加剂或分散剂中的一种或者几种的组合。
  16. 如权利要求9所述的一种二氧化钛材料，其特征在于：所述自发分散的条件为无二氧化钛材料表面修饰。
  17. 如权利要求9所述的一种二氧化钛材料，其特征在于：所述纳米二氧化钛粒子稳定悬浮的水分散液为胶体分散液；所述纳米二氧化钛粒子稳定悬浮的时间超过6个月。
  18. 一种二氧化钛材料，其特征在于，所述二氧化钛材料为固体；所述二氧化钛材料含有结晶性纳米二氧化钛粒子；所述二氧化钛材料与水混合可自发分散形成纳米二氧化钛粒子稳定悬浮的水分散液。
  19. 一种如权利要求1-18任意一项所述的一种二氧化钛材料的应用，其特征在于：
    将所述二氧化钛材料分散于溶剂中；
    将所述分散后的纳米二氧化钛与其它材料结合形成复合材料；所述结合的方式选自物理混合或化学反应的方式形成复合材料。
  20. 一种如权利要求1-18任意一项所述的一种二氧化钛材料的应用，其特征在于：
    将所述二氧化钛材料直接加入水中形成纳米二氧化钛粒子稳定悬浮的水分散液；
    将所述纳米二氧化钛粒子稳定悬浮的水分散液应用于空气净化、水质净化、抗菌消 毒、自清洁、防晒护肤领域中的一种或者多种。
  21. 一种提升如权利要求1-18任意一项所述的二氧化钛分散性的方法，其特征在于，包括以下步骤：
    将前驱物固体二氧化钛A放置于容器内；
    将所述放置前驱物固体二氧化钛A的容器内充注氯化氢气体并进行低温加热处理，获得分散性二氧化钛B产物。
  22. 如权利要求21所述的一种提升二氧化钛分散性的方法，其特征在于：与前驱物二氧化钛A相比，所述分散性二氧化钛B产物在水中的分散度提高十倍以上。
  23. 如权利要求21所述的一种提升二氧化钛分散性的方法，其特征在于：与前驱物二氧化钛A相比，所述分散性二氧化钛B产物在水中的分散稳定性提高十倍以上。
  24. 如权利要求21所述的一种提升二氧化钛分散性的方法，其特征在于：与前驱物二氧化钛A相比，所述分散性二氧化钛B产物在水中分散后的透明度提高十倍以上。
  25. 如权利要求21所述的一种提升二氧化钛分散性的方法，其特征在于：所述分散性二氧化钛B产物在不含添加剂或分散剂的纯水中可自发分散形成稳定的分散液；所述分散液主要为胶体状分散。
  26. 如权利要求21所述的一种提升二氧化钛分散性的方法，其特征在于：所述分散性二氧化钛B产物为粒径小于100纳米的纳米级二氧化钛粒子或粒径小于100纳米的纳米级二氧化钛粒子团聚体；所述分散性二氧化钛B产物的表面为酸性。
  27. 如权利要求21所述的一种提升二氧化钛分散性的方法，其特征在于：所述分散性二氧化钛B产物为结晶性纳米二氧化钛；所述结晶性纳米二氧化钛的晶相为锐钛矿相、金红石相、板钛矿相中的一种或者几种的组合。
  28. 如权利要求21所述的一种提升二氧化钛分散性的方法，其特征在于：所述前驱物固体二氧化钛A为粒径小于100纳米的纳米级二氧化钛粒子或粒径小于100纳米的纳米级二氧化钛粒子团聚体，优选的，所述前驱物固体二氧化钛A为粒径小于50纳米的纳米级二氧化钛粒子或粒径小于50纳米的纳米级二氧化钛粒子团聚体。
  29. 如权利要求21所述的一种提升二氧化钛分散性的方法，其特征在于：所述前驱物固体二氧化钛A为结晶性二氧化钛颗粒或无定型二氧化钛颗粒。
  30. 如权利要求21所述的一种提升二氧化钛分散性的方法，其特征在于：所述前驱物固体二氧化钛A还包括氢氧化钛、氢氧化钛水合物、钛酸、钛酸水合物中的一种或者几种的组合。
  31. 如权利要求21所述的一种提升二氧化钛分散性的方法，其特征在于：所述氯化氢气氛中还含有水汽；所述水汽的压力为0.1个大气压至10个大气压。
  32. 如权利要求21所述的一种提升二氧化钛分散性的方法，其特征在于：所述氯化氢气氛中氯化氢气体的压力为0.5个大气压至20个大气压，优选的，所述氯化氢气氛中氯化氢气体的压力为21个大气压至10个大气压。
  33. 如权利要求21所述的一种提升二氧化钛分散性的方法，其特征在于：所述氯化氢气氛中氯化氢气体在预定压力范围内波动；所述氯化氢气氛由持续的方式提供；所述氯化氢气氛由外部输入提供。
  34. 如权利要求21所述的一种提升二氧化钛分散性的方法，其特征在于：所述热处理的温度为80摄氏度至300摄氏度；优选的热处理温度为100摄氏度至200摄氏度；所述热处理的时间为2小时至48小时。
PCT/CN2021/104577 2020-07-06 2021-07-05 二氧化钛材料及其制备方法、分散性提升方法、应用 WO2022007756A1 (zh)

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