CN102145918A - Method for preparing rutile titanium dioxide nanoparticles by using highly strong acid - Google Patents
Method for preparing rutile titanium dioxide nanoparticles by using highly strong acid Download PDFInfo
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- CN102145918A CN102145918A CN 201110097134 CN201110097134A CN102145918A CN 102145918 A CN102145918 A CN 102145918A CN 201110097134 CN201110097134 CN 201110097134 CN 201110097134 A CN201110097134 A CN 201110097134A CN 102145918 A CN102145918 A CN 102145918A
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Abstract
The invention relates to a method for preparing rutile titanium dioxide nanoparticles by using highly strong acid. The method comprises the following steps of: dropwise adding titanate into a highly strong acid solution with the concentration between 1.26 M and 5 M to form a solution of which the titanium ion concentration is 0.25 M; stirring for 15-20 minutes to obtain a transparent solution; transferring the solution into a reaction kettle to undergo a hydrothermal reaction; naturally cooling to room temperature; centrifugally removing supernatant; and repeatedly washing the product with deionized water to obtain the rutile titanium dioxide nanoparticles. The method is easy and convenient to operate and has high repeatability; and the prepared titanium dioxide nanoparticles have high particle size uniformity in every batch, and have the advantages of controllable particle size, high dispersity and the like. By adopting the method, good foundations can be laid for the preparation and application of rutile titanium dioxide nanoparticles with different particle sizes.
Description
Technical field
The invention belongs to the preparation field of titanium dioxide nanoparticle, the high strong acid of particularly a kind of employing prepares rutile type nano titanic oxide particulate method.
Background technology
In recent years, the special property of nano material has been subjected to common concern, and this has attracted synthetic the carried out extensive studies of large quantities of scholars to nano material.Because the slight change of particle size, specific surface area sharply increases.Nano titanium oxide has that particle diameter is little, specific surface area is big, photochemical catalysis, absorption property are good, uv-absorbing rate advantages of higher forms and is important inorganic functional material, be widely used in fields such as coating, photocatalyst, makeup, electronic material and function ceramics, rutile-type thermotolerance, thermostability and chemical stability are better than Detitanium-ore-type TiO
2[high Lian, Zheng Shan, Zhang Qinghong. nanometer titanium dioxide photocatalysis material and application [M]. Beijing: Chemical Industry Press, 2002:16-20].Rutile type nano TiO
2Has the ultraviolet function of better absorption, it all has effective ultraviolet filtering ability in whole ultraviolet regions, add that its chemical property is stable (fusing point＞1800 ℃, heat decomposition temperature above 2000 ℃), the nontoxic (LD50 of rat＞5000mg/lg) be widely used with better weather resistance.For example in varnish, contain 0.5%～4% nano-TiO
2, can prevent that just timber is subjected to turn black after the illumination; In the used for packing foods plastics film, add 0.1%～0.5% nano-TiO
2Can prevent that food is subjected to the illumination rear oxidation, and food such as meat is subjected to the variable color of fluorescent lamp rear oxidation in show window; In plastics, use and to prevent that plastics itself are by day photodegradation and aging; In agricultural film, use and to improve its intensity and weather resistance; Use the sun-proof and anti-ultraviolet ability that can improve makeup at makeup.In addition, rutile type nano TiO
2Because its special electric property not only can be used for wet quick and pressure-active element, can also detect multiple gases as sensor material.As nano-TiO
2Can detect H
2, inflammable gas and O such as CO
2,,, can control the efficient of motor car engine by measuring the oxygen level in the vehicle exhaust in particular as automobile exhaust sensor.And because rutile type nano TiO
2Better weather resistance and pigment performance, thus have aspect coating and the coating proper value more increased [Deng Jie, Wu Lifeng. titanium dioxide application manual [M]. Beijing: Chemical Industry Press, 2005].
Preparation of nanomaterials is a lot, and the operational path that liquid-phase precipitation method adopts usually is with ammoniacal liquor, (NH
4)
2CO
3Or alkaloids such as NaOH joins in the titanium salt solution, generates unbodied Ti (OH)
4, after the sedimentation and filtration that generates, washing, drying, the difference of controlled temperature obtains Detitanium-ore-type or rutile type nano TiO through calcining
2Powder [Shen Yi, Zhang Zhidan, Shen Shangyue. the preparation of titanium dioxide micron spheroidal particle and research [J]. silicate circular, 2005, (3): 96-101].Though this method apparatus and process is simple, the sample preparation time is shorter, and technical requirements is not high, and low cost and other advantages, purity are not high, and particle diameter control aspect is not introduced.Hydrolysis temperatures such as Zu Yong are 33 ℃, n (butyl (tetra) titanate): n (ethanol): n (water): n (hydrochloric acid)=1: 9: 3: 0.28, prepared median size 8nm～25nm, the TiO that particle form is spherical in shape
2Powder, 550 ℃ of calcination are Detitanium-ore-type, 800 ℃ of calcination be rutile-type [Zu Yong, Li Xiaoe, Wei Zhixian. superfine Ti O
2Study on the synthesis: sol-gel method [J]. Northwest University's journal, 1998,28 (1): 51-56].This method still is unrealized to the control of grain diameter.People such as Yin Lisong add people's Glacial acetic acid as intercalating agent in above-mentioned system, with the hydrolysis rate of control metatitanic acid fourth vinegar, system thinking H
2The mole system of O/ titanium alkoxide, pH value, ethanol/metatitanic acid fourth vinegar mole when factor such as hydrolysis temperature to the influence of gelation time.[Yin Lisong, divergent of week, Tang Xingui, etc. sol-gel method prepares the gelatinization process mechanism research [J] of nanometer. functional materials, 1999,30 (4): 407-409].This method synthetic nano-powder uniform particles, purity height, shape are easy to control, but can not control size.Zhao Tieliu does precipitation agent with ammoniacal liquor earlier, joins in the titanium isobutoxide ethanolic soln, makes Ti (OH)
4Throw out dissolves in the nitric acid again, is heated to 80 ℃, and constant temperature 2h makes ultra-fine rutile type nano titanic oxide.[Zhao TieLiu, Yao Shushan.Preparation and characterizationof highly dispersed nanocrystalline rutile powders[J] .Materials Letters, 2007, (61): 2798-2803] at TiCl such as Pedraza
3Direct oxidation method is prepared rutile type nano titanic oxide [Pedraza F, Vazquez A.Ostentationof TiO2 rutile at room temperature through direct oxidation of TiCl3[J] .J Phys Chem Solids, 1999,60:445-448]; Zhang Yanfeng is by TiOCl
2Homogeneous phase solution adopts low temperature (room temperature～60 ℃) ageing directly to prepare nano-titanium oxide aciculiform aggregate particle [Zhang Yanfeng, Wei Yu, the refined .TiOCl2 solution of Jia Zhen low temperature hydrolysis titania type Preparation of Nanocrystal TiO [J]. Journal of Inorganic Materials, 2001,16 (6): 1217-1219].TiCl such as Zhao Xiaohong
3Hydrothermal reaction at low temperature prepare rutile type nano titanic oxide [Zhao Xiaohong, Zhang Yuanming, etc. hydrothermal reaction at low temperature prepares high-activity nano red schorl phase titanium dioxide [J]. chemical research and application, 2006,18 (3): 235-238].These methods are and relate to particle diameter control.
On the other hand, existing report shows, by anatase nanometer crystal kind control anatase octahedrite nano particle diameter [Park N G, Lagemaat van de J, Frank A J.Comparison of dye-sensitized rutile and anatase based TiO
2Solarcells[J] .J.Phys.Chem.B, 2000,104 (38): 8989-8994].Should consider that anatase octahedrite crystal seed quantity controls the gold redrock nano-titanium dioxide granular size by using rutile, simultaneously prepared nano particle diameter homogeneous.Simultaneously, can be under identical conditions such as pH, the suitable gold redrock nano particle of preparation productive rate.
Summary of the invention
Technical problem to be solved by this invention provides the high strong acid of a kind of employing and prepares rutile type nano titanic oxide particulate method, and this method is easy and simple to handle, good reproducibility, and every batch particle size uniformity is good, and it is controlled to have a particle diameter, advantages such as good dispersity.
The high strong acid of a kind of employing of the present invention prepares rutile type nano titanic oxide particulate method, comprising:
In the high strong acid solution of 1.26M～5M, dropwise adding titanic acid ester formation titanium ion concentration is the solution of 0.25M, stir 15～20min, obtain clear solution, solution is transferred to reactor carry out hydro-thermal reaction, naturally cool to room temperature, the centrifugal supernatant liquid that removes, use deionized water repetitive scrubbing product then, promptly.
Described high strong acid is perchloric acid, sulfuric acid or nitric acid.
Described titanic acid ester is titanium isopropylate or tetrabutyl titanate.
Described hydro-thermal reaction actual conditions is in 100～120 ℃ of ageing 24～32h, is warming up to 140～160 ℃ of ageing 72～80h again.
Beneficial effect
(1) the present invention is easy and simple to handle, good reproducibility, and every batch particle size uniformity is good;
(2) it is controlled that the present invention has particle diameter, and advantages such as good dispersity can be prepared the rutile type nano titanic oxide superfine powder of different-grain diameter, for the rutile type nano particulate preparation of different-grain diameter is laid a good foundation with application.
Description of drawings
Fig. 1 is the rutile type nano particulate transmission electron microscope picture of embodiment 1 gained;
Fig. 2 is the rutile type nano particulate XRD figure sheet of embodiment 1 gained;
Fig. 3 is the rutile type nano particulate transmission electron microscope picture of embodiment 2 gained.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used to the present invention is described and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims institute restricted portion equally.
Embodiment 1
The perchloric acid solution 18.5mL of preparation 1.26M～5M, dropwise add the 1.5mL titanium isopropylate, stir 15min, obtain clear solution, titanium ion concentration is 0.25M, 20mL solution is transferred to the tetrafluoroethylene reactor carry out hydro-thermal reaction, is heated to 100 ℃ of ageing 24h, be warmed up to 140 ℃ of ageing 72h again, naturally cool to room temperature.White emulsion carries out centrifugally operated by whizzer, removes supernatant liquid.Use the deionized water repetitive scrubbing then, finally obtain white TiO
2Nanoparticle.
Scheme 1 is respectively that a is 1.26M in perchloric acid concentration, b is 1.63M, and c is 1.88M, and d is 2.00M, e is 4.00M, f makes the transmission electron microscope picture of nanoparticles of rutile during for 5.00M and sees Fig. 1, and the median size that is estimated particle by figure is about 70nm * 13nm, 85nm * 13nm respectively, 125nm * 18nm, 135nm * 19nm, 150nm * 16nm, 230nm * 17nm dispersing property is better.Fig. 2 is 1.26M for XRD figure a, and b is 1.88M, and c is 2.00M, and d is 4.00M, and e is 5.00M.
Embodiment 2
The perchloric acid solution 18.3mL of preparation 1.26M～5M, dropwise add the 1.7mL tetrabutyl titanate, stir 15min, obtain clear solution, titanium ion concentration is 0.25M, 20mL solution is transferred to the tetrafluoroethylene reactor carry out hydro-thermal reaction, is heated to 100 ℃ of ageing 24h, be warmed up to 140 ℃ of ageing 72h again, naturally cool to room temperature.White emulsion carries out centrifugally operated by whizzer, removes supernatant liquid.Use the deionized water repetitive scrubbing then, finally obtain white TiO
2Nanoparticle.
Scheme 2 is respectively that a is 4M adding different quantities crystal seed perchloric acid concentration, and b prepares the transmission electron microscope picture of nanoparticles of rutile during for 2M and sees Fig. 3, estimates the 200nm * 15nm that is respectively of particle, 100nm * 20nm by figure.
The perchloric acid solution 18.3mL of preparation 1.26M～5M, dropwise add the 1.7mL tetrabutyl titanate, stir 20min, obtain clear solution, titanium ion concentration is 0.25M, 20mL solution is transferred to the tetrafluoroethylene reactor carry out hydro-thermal reaction, is heated to 120 ℃ of ageing 32h, be warmed up to 160 ℃ of ageing 80h again, naturally cool to room temperature.White emulsion carries out centrifugally operated by whizzer, removes supernatant liquid.Use the deionized water repetitive scrubbing then, finally obtain white TiO
2Nanoparticle.
Claims (4)
1. one kind is adopted high strong acid to prepare rutile type nano titanic oxide particulate method, comprising:
In the high strong acid solution of 1.26M～5M, dropwise adding titanic acid ester formation titanium ion concentration is the solution of 0.25M, stir 15～20min, obtain clear solution, solution is transferred to reactor carry out hydro-thermal reaction, naturally cool to room temperature, the centrifugal supernatant liquid that removes, use deionized water repetitive scrubbing product then, promptly.
2. the high strong acid of a kind of employing according to claim 1 prepares rutile type nano titanic oxide particulate method, and it is characterized in that: described high strong acid is perchloric acid, sulfuric acid or nitric acid.
3. the high strong acid of a kind of employing according to claim 1 prepares rutile type nano titanic oxide particulate method, and it is characterized in that: described titanic acid ester is titanium isopropylate or tetrabutyl titanate.
4. the high strong acid of a kind of employing according to claim 1 prepares rutile type nano titanic oxide particulate method, it is characterized in that: described hydro-thermal reaction actual conditions is warming up to 140～160 ℃ of ageing 72～80h again in 100～120 ℃ of ageing 24～32h.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786085A (en) * | 2012-08-06 | 2012-11-21 | 东华大学 | Method for preparing rutile type titanium dioxide nanorod microsphere |
| CN103214083A (en) * | 2013-04-24 | 2013-07-24 | 河海大学 | TiO2-loaded packing and preparation method thereof |
| CN110627116A (en) * | 2019-09-06 | 2019-12-31 | 吉林大学 | Hydrogen-doped TiO (titanium dioxide)2Phase-change nano material and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546384A (en) * | 2003-12-03 | 2004-11-17 | 苏州大学 | Method for preparing rutile nano titanium dioxide |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1546384A (en) * | 2003-12-03 | 2004-11-17 | 苏州大学 | Method for preparing rutile nano titanium dioxide |
Non-Patent Citations (1)
| Title |
|---|
| 《东华大学学报( 自然科学版)》 20100430 王美文等 水热法可控合成的高径向比金红石型纳米TiO2颗粒 第148-152页 1-4 第36卷, 第2期 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102786085A (en) * | 2012-08-06 | 2012-11-21 | 东华大学 | Method for preparing rutile type titanium dioxide nanorod microsphere |
| CN102786085B (en) * | 2012-08-06 | 2014-07-02 | 东华大学 | Method for preparing rutile type titanium dioxide nanorod microsphere |
| CN103214083A (en) * | 2013-04-24 | 2013-07-24 | 河海大学 | TiO2-loaded packing and preparation method thereof |
| CN103214083B (en) * | 2013-04-24 | 2014-12-31 | 河海大学 | Preparation method of TiO2-loaded packing |
| CN110627116A (en) * | 2019-09-06 | 2019-12-31 | 吉林大学 | Hydrogen-doped TiO (titanium dioxide)2Phase-change nano material and application thereof |
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Application publication date: 20110810 |