CN102502808A - Preparation method of nano-grade titanium dioxide - Google Patents
Preparation method of nano-grade titanium dioxide Download PDFInfo
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- CN102502808A CN102502808A CN2011103115357A CN201110311535A CN102502808A CN 102502808 A CN102502808 A CN 102502808A CN 2011103115357 A CN2011103115357 A CN 2011103115357A CN 201110311535 A CN201110311535 A CN 201110311535A CN 102502808 A CN102502808 A CN 102502808A
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Abstract
The invention provides a preparation method of nano-grade titanium dioxide, which belongs to the field of titanium dioxide preparation. The invention aims to provide the preparation method of the nano-grade titanium dioxide. The preparation method of the invention comprises the following steps of: taking titanium trichloride as a titanium source and taking polystyrene sulfonates as a surfactant to obtain the nano-grade titanium dioxide through adjusting pH value of a reaction system and carrying out hydrothermal treatment at a temperature in a range of 110-180 DEG C for different reaction periods of time including 0.5-24 h and the like. The preparation method has the advantages of cheap raw materials, simple equipment and simplicity in operation. Products comprise nano-grade particles with a certain crystalline phase and flower-shaped titanium dioxide, which have the advantages of some excellent performances of a nano material, good product dispersibility, stable structure and high yield, so that the nano-grade titanium dioxide is applicable to large scale production and can be used for a plurality of fields including environmental catalysis, cosmetics, coating, chemical fibers and the like.
Description
Technical field
The invention belongs to the titanium oxide preparation field.
Background technology
In recent years, the nano material development is very fast, and nano titanium oxide also becomes the focus of research day by day because it has many premium propertiess that are different from macroscopic material.As everyone knows; Titanium oxide has three kinds of crystalline phases at occurring in nature: be respectively rutile, anatase octahedrite and brookite; It has been generally acknowledged that anatase octahedrite has higher photocatalytic activity; But we can find out from Degussa P25 and some bibliographical informations, and the titanium oxide with a certain proportion of mixed phase helps the chargeseparated in light induced electron and hole (mixed crystal effect), also can improve photocatalytic activity.Along with deep day by day research can be known; The photocatalytic activity of titanium oxide not only receives the influence of its crystalline phase; Also receive simultaneously factor affecting such as grain-size, pattern and percent crystallinity; The titanium oxide that more particularly has hierarchy is easy to other arrowband breath semi-conductor or precious metal compoundly because of having higher specific surface area and moderate size, and the photochemical catalysis effect is improved a lot.So in regulation and control titanium oxide crystalline phase,, therefrom find the best combination of photochemical catalysis effect, will be highly significant if can change its pattern simultaneously.But in compound method in the past, people often only pay attention to the size or the difference of regulation and control crystalline phase of simple change particle or change its pattern, and the method that can simultaneously triplicity got up also rarely has report.
Summary of the invention
The objective of the invention is for the THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method is provided, is the titanium source with titanous chloride cheap and easy to get, adopts simple Hydrothermal Preparation to go out the Nano titanium dioxide of different crystalline phase different-shapes.
The THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method is undertaken by following step among the present invention: will be to add poly styrene sulfonate in the Titanium Trichloride Solution of 0.01～0.06g/mL to obtain mixture A to concentration; Wherein the concentration of poly styrene sulfonate in mixture A is 0.005～0.05g/mL; Using mineral acid or mineral alkali to regulate the pH value then is 0.1～5.0; Under 110～180 ℃ of conditions, carry out hydro-thermal reaction 0.5～24h again, behind filtration or centrifugal removal liquid, the solid that obtains is washed till the pH value with zero(ppm) water then and equals 7, wash 1～3 time with ethanol again; Place the constant temperature air dry oven, freeze-day with constant temperature 5～12h under 60～80 ℃ of conditions; Promptly obtain Nano titanium dioxide.
The present invention is simple to operate, passes through the time of the pH value and the control hydro-thermal reaction of conditioned reaction system in the reaction process respectively, all can obtain out of phase TiO
2, the pattern of product also changes thereupon, for example the flower-shaped TiO of the hierarchy of the nanoparticle of anatase octahedrite phase, anatase octahedrite and rutile mixed phase
2And the flower-like structure of pure rutile phase, realized that the crystalline phase controllable appearance is adjustable; What deserves to be mentioned is the flower-shaped TiO of the prepared mixed phase that goes out of present method
2, containing two kinds of different crystalline phases of rutile and anatase octahedrite, these two kinds of crystalline phases have different energy gaps and form heterojunction, help the raising of the separation efficiency in light induced electron and hole, are suitable for using photocatalyst.Low in raw material cost of the present invention, conversion unit is simple, and reaction conditions is gentle, and experimental implementation and aftertreatment are simple, are suitable for batch production production.Products therefrom of the present invention is nano-scale; Possess some excellent properties such as surface effects that nano material has, quantum effect, small-size effect, macro quanta tunnel effect; Product property is stable; Good dispersivity can be widely used in various fields such as photocatalytic degradation pollutent, makeup, coating, plastics.
Description of drawings
Fig. 1 is the sem photograph that test one method prepares Nano titanium dioxide; Fig. 2 is the sem photograph that test two methods prepare Nano titanium dioxide; Fig. 3 is the sem photograph of test three preparation Nano titanium dioxides; Fig. 4 is the sem photograph of test four preparation Nano titanium dioxides; Fig. 5 is the transmission electron microscope picture that test two methods prepare Nano titanium dioxide; Fig. 6 is the not XRD spectra under the roasting condition of test one to four, and A representes to test one among Fig. 6, and B representes to test two, and C representes to test three, and D representes to test four; Fig. 7 is the not XRD spectra under the roasting condition of test five to eight, and A representes to test five among Fig. 6, and B representes to test six, and C representes to test seven, and D representes to test eight.
Embodiment
Technical scheme of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method is undertaken by following step in this embodiment: will be to add poly styrene sulfonate in the Titanium Trichloride Solution of 0.01～0.06g/mL to obtain mixture A to concentration; Wherein the concentration of poly styrene sulfonate in mixture A is 0.005～0.05g/mL; Using mineral acid or mineral alkali to regulate the pH value then is 0.1～5.0; Under 110～180 ℃ of conditions, carry out hydro-thermal reaction 0.5～24h again; Behind filtration or centrifugal removal liquid, the solid that obtains is washed till the pH value with zero(ppm) water then and equals 7; Wash 1～3 time with ethanol again, place the constant temperature air dry oven, freeze-day with constant temperature 5～12h under 60～80 ℃ of conditions; Promptly obtain Nano titanium dioxide.
Obtain the crystalline phase and the pattern table of Nano titanium dioxide under table 1 different condition
Embodiment two: what this embodiment and embodiment one were different is: said poly styrene sulfonate is a Lewatit.Other step is identical with embodiment one with parameter.
Embodiment three: what this embodiment and embodiment two were different is: the molecular-weight average of said Lewatit is 5000～700000.Other step is identical with embodiment two with parameter.
Embodiment four: what this embodiment was different with one of embodiment one to three is: described mineral acid is a kind of or wherein several kinds the mixing in hydrochloric acid, sulfuric acid or the nitric acid.Other step is identical with one of embodiment one to three with parameter.
Embodiment five: what this embodiment was different with one of embodiment one to three is: described mineral alkali is a kind of or wherein several kinds the mixing in sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus or the ammoniacal liquor.Other step is identical with one of embodiment one to three with parameter.
Embodiment six: what this embodiment was different with one of embodiment one to five is: using mineral acid or mineral alkali to regulate the pH value is 0.3～3.0.Other step is identical with one of embodiment one to five with parameter.
Embodiment seven: what this embodiment was different with one of embodiment one to five is: using mineral acid or mineral alkali to regulate the pH value is 2.0.Other step is identical with one of embodiment one to five with parameter.
Embodiment eight: what this embodiment was different with one of embodiment one to eight is: the hydro-thermal reaction time is 1～12h.Other step is identical with one of embodiment one to eight with parameter.
Embodiment nine: what this embodiment was different with one of embodiment one to eight is: the hydro-thermal reaction time is 5h.Other step is identical with one of embodiment one to eight with parameter.
Adopt following verification experimental verification invention effect:
Test one: the THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method is following in the test one: measure 4ml Titanium Trichloride Solution (wt:15%-20%) and join in the 25ml zero(ppm) water; Mix the back and add the 0.15g Lewatit, magnetic agitation makes its dissolving, obtains the purple clear solution; This moment, the pH value of reaction system was 0.2; Add sodium hydroxide solution its pH value is adjusted to 3.0, it is transferred to put into the autoclave that is lined with tetrafluoroethylene and be heated to 120 ℃ of insulation 12h, reaction is centrifugal with products therefrom after finishing, wash 3 times, alcohol washes 2 times; In 60 ℃ of baking 12h, treat to get Nano titanium dioxide after nature is reduced to room temperature under the air atmosphere.Test through the XRD diffractometer can know that products obtained therefrom is pure anatase octahedrite phase (Fig. 6), can know through the test of ESEM, and product is the mixture of tens nanoparticles and rod, and pattern is as shown in Figure 1.
Test two: this test with test one and different be: the adding sodium hydroxide solution is adjusted to 2.0 with its pH value.Other step is identical with test one with parameter.Test through XRD diffractometer and Electronic Speculum can know, products obtained therefrom be rutile mutually with anatase octahedrite mixing mutually, and the ratio suitable (Fig. 6) of rutile and anatase octahedrite in the mixed phase, product is the particle about 30nm, pattern is as shown in Figure 2.
Test three: this test with test one and different be: the adding sodium hydroxide solution is adjusted to 0.2 with its pH value.Other step is identical with test one with parameter.Test through XRD diffractometer and Electronic Speculum can be known; Product also is the mixed phase of rutile and anatase octahedrite; The content of rutile increases (Fig. 6, Fig. 7) in the products therefrom mixed phase but test in two; Product is the flower-like structure about 300nm, and its scanning electron microscope image is as shown in Figure 3, and transmission electron microscope picture is as shown in Figure 5.
Test four: the THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method is following in this test: measure 4ml Titanium Trichloride Solution (wt:15%-20%) and join in the 25ml zero(ppm) water; Mix the back and add the 0.15g Lewatit, magnetic agitation makes its dissolving, obtains the purple clear solution; This moment, the pH value of reaction system was 0.2; Add concentrated hydrochloric acid its pH value is adjusted to 0.1, it is transferred to put into the autoclave that is lined with tetrafluoroethylene and be heated to 120 ℃ of insulation 12h, reaction is centrifugal with products therefrom after finishing, wash 3 times, alcohol washes 2 times; In 60 ℃ of baking 12h, treat to get Nano titanium dioxide after nature is reduced to room temperature under the air atmosphere.Test through XRD diffractometer and Electronic Speculum can know that products therefrom is pure rutile phase (Fig. 6), and the product pattern is the another kind of flower-like structure that differs from embodiment 3, and pattern is as shown in Figure 4.
Test five: the THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method is following in this test: measure 4ml Titanium Trichloride Solution (wt:15-20%) and join in the 25ml zero(ppm) water; Mix the back and add the 0.15g Lewatit; Magnetic agitation makes its dissolving, obtains the purple clear solution, and this moment, the pH value of reaction system was 0.2; With solution transfer to put into the autoclave that is lined with tetrafluoroethylene be heated to 120 ℃ the insulation 0.5h; After reaction finishes that products therefrom is centrifugal, washing 3 times, alcohol are washed 2 times, under the air atmosphere in 60 ℃ of baking 12h, treat nature reduce to after the room temperature product.Test through XRD diffractometer and Electronic Speculum can know that products obtained therefrom is no obvious diffraction peak (Fig. 7) on XRD, explains that this moment, products therefrom was unbodied TiO
2Or its hydrate, product is the particle about 10nm.
Test six: this test with test five and different be: the hydro-thermal time is 1h.Other step is identical with test five with parameter.Can know that through dependence test product is the mixed phase of anatase octahedrite and rutile, and the content of anatase octahedrite higher (Fig. 7) in the mixed phase, explain that initial reaction stage is main with anatase octahedrite, the product pattern is mainly the globoid about 300nm, also has a spot of particle to exist.
Test seven: this test with test five and different be: the hydro-thermal time is 5h.Other step is identical with test five with parameter.Can know that through dependence test product also is the mixed phase of anatase octahedrite and rutile, but relatively the content of the product rutile among the embodiment 6 increases, the content of anatase octahedrite reduces, and rutile accounts for staple (Fig. 7), and it is fluffy that spherome surface also begins to become.
Test eight: this test with test five and different be: the hydro-thermal time is 24h.Other step is identical with test five with parameter.Can know that through dependence test product is pure rutile phase, anatase octahedrite disappears.Regulation and control through the time can know that along with the prolongation in reaction times, rutile content increases in the product, and anatase octahedrite reduces, last completely dissolve (Fig. 7), and the basic no change of product among the relative embodiment 3 of pattern of product has kept original flower-like structure at this moment.
Claims (9)
1. THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method; It is characterized in that the THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method undertaken by following step: will in concentration is the Titanium Trichloride Solution of 0.01～0.06g/mL, add poly styrene sulfonate and obtain mixture A; Wherein the concentration of poly styrene sulfonate in mixture A is 0.005～0.05g/mL; Using mineral acid or mineral alkali to regulate the pH value then is 0.1～5.0; Under 110～180 ℃ of conditions, carry out hydro-thermal reaction 0.5～24h again, behind filtration or centrifugal removal liquid, the solid that obtains is washed till the pH value with zero(ppm) water then and equals 7, wash 1～3 time with ethanol again; Place the constant temperature air dry oven, freeze-day with constant temperature 5～12h under 60～80 ℃ of conditions; Promptly obtain Nano titanium dioxide.
2. THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method according to claim 1 is characterized in that said poly styrene sulfonate is a Lewatit.
3. THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method according to claim 2, the molecular-weight average that it is characterized in that said Lewatit is 5000～700000.
4. THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method according to claim 3 is characterized in that described mineral acid is a kind of or wherein several kinds the mixing in hydrochloric acid, sulfuric acid or the nitric acid.
5. THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method according to claim 3 is characterized in that described mineral alkali is a kind of or wherein several kinds the mixing in sodium hydroxide, Pottasium Hydroxide, yellow soda ash, salt of wormwood, sodium hydrogencarbonate, saleratus or the ammoniacal liquor.
6. according to the described THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method of each claim of claim 1 to 5, it is characterized in that using mineral acid or mineral alkali to regulate the pH value is 0.3～3.0.
7. according to the described THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method of each claim of claim 1 to 5, it is characterized in that using mineral acid or mineral alkali to regulate the pH value is 2.0.
8. according to the described THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method of each claim of claim 1 to 5, it is characterized in that the hydro-thermal reaction time is l～12h.
9. according to the described THE PREPARATION OF NANOMETER TITANIUM DIOXIDE method of each claim of claim 1 to 5, it is characterized in that the hydro-thermal reaction time is 5h.
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| CN107139298A (en) * | 2017-06-13 | 2017-09-08 | 浙江省林业科学研究院 | A kind of manufacture method of bamboo material surface load nano-titanium dioxide material |
| CN109603918A (en) * | 2018-11-12 | 2019-04-12 | 东莞理工学院 | A kind of preparation method of the compound golden light catalyst of poly- 3- hexyl thiophene cladding titanium dioxide |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103964500A (en) * | 2014-05-12 | 2014-08-06 | 宿州学院 | Preparation method of flowery rutile titanium dioxide nanostructure |
| CN106277044A (en) * | 2015-05-15 | 2017-01-04 | 南京创绿家环保科技有限公司 | A kind of nano-TiO2the preparation method of photocatalyst microgranule |
| CN107139298A (en) * | 2017-06-13 | 2017-09-08 | 浙江省林业科学研究院 | A kind of manufacture method of bamboo material surface load nano-titanium dioxide material |
| CN109603918A (en) * | 2018-11-12 | 2019-04-12 | 东莞理工学院 | A kind of preparation method of the compound golden light catalyst of poly- 3- hexyl thiophene cladding titanium dioxide |
| CN109603918B (en) * | 2018-11-12 | 2022-01-25 | 东莞理工学院 | Preparation method of poly 3-hexylthiophene coated titanium dioxide composite gold photocatalyst |
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