CN103243387A - Preparation method of anatase TiO2 monocrystal having high-activity (110) face - Google Patents
Preparation method of anatase TiO2 monocrystal having high-activity (110) face Download PDFInfo
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- CN103243387A CN103243387A CN2012100221791A CN201210022179A CN103243387A CN 103243387 A CN103243387 A CN 103243387A CN 2012100221791 A CN2012100221791 A CN 2012100221791A CN 201210022179 A CN201210022179 A CN 201210022179A CN 103243387 A CN103243387 A CN 103243387A
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Abstract
The invention provides a preparation method of an anatase TiO2 monocrystal having a high-activity (110) face. The method comprises the following steps: 1, sequentially adding water, hydrofluoric acid and hydrogen peroxide to titanium powder, and stirring to obtain a titanium-containing solution; 2, reacting the titanium-containing solution in an autoclave at 120-220DEG C for 1-40h; 3, washing a reaction product obtained in step 2 with water and an organic solvent until the pH value is 6.5-7.5, and drying to obtain a solid; and 4, grinding the solid obtained in step 3, and calcining the ground solid at 120-900DEG C for 1-6h to obtain the anatase TiO2 monocrystal having a high-activity face. The preparation method has the advantages of low cost, simplicity, mild reaction, full utilization of above reaction raw materials, no generation of harmful gasses, and strong process repeatability.
Description
Technical field
The present invention relates to a kind of preparation method of titanic oxide material, particularly a kind of anatase octahedrite TiO with high reactivity (110) face
2The preparation method of monocrystalline.
Background technology
Titanium dioxide is stable, the conductor oxidate cheaply of a kind of safety non-toxic, chemical property, has a wide range of applications in fields such as photochemical catalysis, sewage disposal and solar cells.
The application of titanium dioxide and its crystalline structure and surface properties have close contacting.Have document to prove, the surface energy size order of each crystal face of anatase single crystal is: 1.09J/m
2((110) face)＞0.90J/m
2((001) face)＞0.53J/m
2((100) face)＞0.44J/m
2((101) face) (physical review B, 2002,65,119901).In the process of crystal growth, the surface energy of crystal can be tending towards minimizing, and the high energy face reduces very soon and disappears, and therefore is difficult to prepare the anatase titania monocrystalline with (110) face.
2008, this respect research make a breakthrough (Nature, 2008,453,638-641), the investigator utilizes fluorion to the control action kou of titanium oxide crystal face, has synthesized multiple anatase single crystal with vast scale (110) face.For example [J.Am.Chem.Soc., 2009,131,4078], [J.Am.Chem.Soc., 2009,131,12868], [Chem.Commun., 2009,4381.], [Chem.Commun., 2010,46,755.], [Chem.Commun., 2010,46,1644.], [J.Phys.Chem.C, 2009,113,12954] and [Cryst.Growth Des., 2010,10,1130].Yet the synthesizing of anatase single crystal that up to the present, has (110) face do not seen patent report all the time.
Summary of the invention
Therefore, the purpose of this invention is to provide a kind of is raw material with cheap titanium source, has high reactivity (110) face anatase octahedrite TiO by simple, gentle reaction process preparation
2The method of monocrystalline.
The objective of the invention is to be achieved through the following technical solutions.
The invention provides the anatase octahedrite TiO that a kind of preparation has high reactivity (110) face
2The method of monocrystalline, this method may further comprise the steps:
(1) add water successively in the titanium valve, hydrofluoric acid and hydrogen peroxide, stir and obtain titaniferous solution;
(2) make described titaniferous solution in reactor in 120～220 ℃ of following confined reactions 1～40 hour;
(3) reaction product water and the organic solvent washing that step (2) is obtained is 7 ± 0.5 until its pH value, and be dry then, obtains solid;
(4) calcined 1～6 hour down in 120～900 ℃ behind the solid abrasive that step (3) is obtained, namely obtain having the anatase octahedrite TiO of high reactivity (110) face
2Monocrystalline.
According to preparation method provided by the invention, wherein, described titanium valve can be the powder of various titaniferous simple substance or compound, for example, can be selected from powder, titanium dioxide powder, the TiCl of metal titanium
4Powder and Ti (SO
4)
2In the powder one or more.
In described step (1), with respect to the titanium of 1mol, the volume of water can be 50000～250000ml, is preferably 100000～200000ml; The concentration of hydrofluoric acid can be 50～56mol/L, and volume can be 240～960ml, is preferably 360～600ml; The volume of hydrogen peroxide (aqueous solution of 30 weight %) can be 2400～48000ml, is preferably 4800～24000ml.Wherein, described water is preferably high purity water.Described hydrofluoric acid can be the hydrofluoric acid of routine, also can be by the fluorochemical of adding basic metal or ammonium and the hydrofluoric acid of nitric acid or sulfuric acid reaction generation.
Preferably, in step (1), described stirring is induction stirring, and churning time can be 5～30 minutes.
According to preparation method provided by the invention, wherein, in described step (2), temperature of reaction is preferably 150～200 ℃, and the reaction times is preferably 10～20 hours.
In preparation method of the present invention, preferably, the washing in the step (3) is to use deionized water rinsing 1～10 time, uses 10～2000ml deionized water at every turn; Use organic solvent washing 1～10 time afterwards again, use 10～2000ml organic solvent at every turn.Organic solvent described in the step (3) can be in ethanol, methyl alcohol and the acetone one or more, is preferably ethanol.
According to preparation method provided by the invention, in described step (3), dry mode comprises the dry and vacuum drying oven drying of a conventional oven, or two kinds are used alternatingly.Dry temperature can be 70～160 ℃, and the dry time can be 2～24 hours.Vacuum tightness when vacuum drying oven is dry can be 0.005～0.5MPa.
According to preparation method provided by the invention, wherein, in described step (4), calcining temperature is preferably 400～600 ℃, and calcination time is preferably 1～3 hour.
The present invention compared with prior art has following advantage and characteristics:
1, preparation method of the present invention is with low cost, and method is simple, reaction temperature and, the reaction raw materials utilization is abundant, can not produce obnoxious flavour, process repeatable strong.
2, preparation method of the present invention can prepare the monocrystalline with high energy face (110) face, and can prepare the controlled monocrystalline of (110) face ratio by regulating preparation condition.
3, preparation method of the present invention can prepare that (110) face, (001) face and (100) face coexist simultaneously and each face ratio and the controlled monocrystalline of particle diameter.
4, preparation method of the present invention can effectively suppress the easy intersection of the normal product that occurs or aggregation phenomenon in the hydro-thermal reaction.
Description of drawings
Below, describe embodiment of the present invention by reference to the accompanying drawings in detail, wherein:
The anatase octahedrite TiO with high reactivity (110) face that Fig. 1 embodiment 1 makes
2The scanning electron microscope diagram of monocrystalline;
The anatase octahedrite TiO with high reactivity (110) face that Fig. 2 embodiment 1 makes
2The X ray diffracting spectrum of monocrystalline;
The anatase octahedrite TiO with high reactivity (110) face that Fig. 3 embodiment 2 makes
2The scanning electron microscope diagram of monocrystalline;
The anatase octahedrite TiO with high reactivity (110) face that Fig. 4 embodiment 2 makes
2The X ray diffracting spectrum of monocrystalline;
The anatase octahedrite TiO with high reactivity (110) face that Fig. 5 embodiment 3 makes
2The scanning electron microscope diagram of monocrystalline;
The anatase octahedrite TiO with high reactivity (110) face that Fig. 6 embodiment 3 makes
2The X ray diffracting spectrum of monocrystalline;
The anatase octahedrite TiO with high reactivity (110) face that Fig. 7 embodiment 4 makes
2The scanning electron microscope diagram of monocrystalline;
The anatase octahedrite TiO with high reactivity (110) face that Fig. 8 embodiment 4 makes
2The X ray diffracting spectrum of monocrystalline;
The anatase octahedrite TiO with high reactivity (110) face that Fig. 9 embodiment 5 makes
2The scanning electron microscope diagram of monocrystalline;
The anatase octahedrite TiO with high reactivity (110) face that Figure 10 embodiment 5 makes
2The X ray diffracting spectrum of monocrystalline.
Embodiment
Below in conjunction with embodiment the present invention is further described in detail, the embodiment that provides is only in order to illustrate the present invention, rather than in order to limit the scope of the invention.
Embodiment 1
Present embodiment is used for explanation preparation method provided by the invention.
(1) the powder 10mg of weighing metal titanium, it is joined in the polytetrafluoro reactor inner bag, add 27ml high purity water, 0.08ml hydrofluoric acid (concentration is the aqueous solution of 54mol/L) and 1.5ml hydrogen peroxide (concentration is the aqueous solution of 30 weight %) successively in the reactor inner bag, induction stirring 10min obtains titaniferous solution.
(2) titaniferous solution that step (1) is made places the 100mL autoclave, and reactor is airtight, reacts 15 hours down in 160 ℃.
(3) after reaction finishes, products therefrom is cleaned 8 times with the 500ml high purity water, clean 3 times with 150ml ethanol again, reach 7 until its pH value.Product was placed baking oven dry 2 hours.
(4) product after will drying grinds evenly, in 450 ℃ of calcinings 2 hours down, namely obtains having the anatase octahedrite TiO of high reactivity (110) face
2Monocrystalline.
The anatase octahedrite TiO with high reactivity face that Fig. 1 makes for present embodiment
2The sem photograph of monocrystalline.Figure 2 shows that the anatase octahedrite TiO with high reactivity face that present embodiment makes
2The X ray diffracting spectrum of monocrystalline.By Fig. 1 and Fig. 2 as can be seen, the TiO that present embodiment makes
2Have good anatase structuredly, and have (110) crystal face.
Embodiment 2
Present embodiment is used for explanation preparation method provided by the invention.
(1) the powder 10mg of weighing metal titanium, it is joined in the polytetrafluoro reactor inner bag, add 25ml high purity water, 0.1ml hydrofluoric acid (concentration is the aqueous solution of 56mol/L) and 5ml hydrogen peroxide (aqueous solution of 30 weight %) successively in the reactor inner bag, induction stirring 10min obtains titaniferous solution.
(2) titaniferous solution that step (1) is made places the 100mL autoclave, and reactor is airtight, reacts 10 hours down in 200 ℃.
(3) after reaction finishes, products therefrom is cleaned 5 times with the 500ml high purity water, clean 5 times with 200ml ethanol again, reach 7 until its pH value.Product was placed baking oven dry 2 hours.
(4) product after will drying grinds evenly, in 500 ℃ of calcinings 3 hours down, namely obtains having the anatase octahedrite TiO of high reactivity (110) face
2Monocrystalline.
The anatase octahedrite TiO with high reactivity face that Fig. 3 makes for present embodiment
2The sem photograph of monocrystalline.The anatase octahedrite TiO with high reactivity face that Fig. 4 makes for present embodiment
2The X ray diffracting spectrum of monocrystalline.By Fig. 3 and Fig. 4 as can be seen, the TiO that present embodiment makes
2Have good anatase structuredly, and have (110) crystal face.
Embodiment 3
Present embodiment is used for explanation preparation method provided by the invention.
(1) the powder 20mg of weighing metal titanium, it is joined in the polytetrafluoro reactor inner bag, add 20ml high purity water, 0.5ml hydrofluoric acid (concentration is the aqueous solution of 50mol/L) and 3ml hydrogen peroxide (aqueous solution of 30 weight %) successively in the reactor inner bag, induction stirring 10min obtains titaniferous solution.
(2) titaniferous solution that step (1) is made places the 100mL autoclave, and reactor is airtight, reacts 18 hours down in 180 ℃.
(3) after reaction finishes, products therefrom is cleaned 6 times with the 600ml high purity water, clean 5 times with 150ml ethanol again, reach 7 until its pH value.Product was placed baking oven dry 2 hours.
(4) product after will drying grinds evenly, in 600 ℃ of calcinings 1 hour down, namely obtains having the anatase octahedrite TiO of high reactivity (110) face
2Monocrystalline.
The anatase octahedrite TiO with high reactivity face that Fig. 5 makes for present embodiment
2The sem photograph of monocrystalline.The anatase octahedrite TiO with high reactivity face that Fig. 6 makes for present embodiment
2The X ray diffracting spectrum of monocrystalline.By Fig. 5 and Fig. 6 as can be seen, the TiO that present embodiment makes
2Have good anatase structuredly, and have (110) crystal face.
Embodiment 4
Present embodiment is used for explanation preparation method provided by the invention.
(1) the powder 10mg of weighing metal titanium, it is joined in the polytetrafluoro reactor inner bag, add 30ml high purity water, 0.08ml hydrofluoric acid (concentration is the aqueous solution of 52mol/L) and 5ml hydrogen peroxide (aqueous solution of 30 weight %) successively in the reactor inner bag, induction stirring 20min obtains titaniferous solution.
(2) titaniferous solution that step (1) is made places the 100mL autoclave, and reactor is airtight, reacts 20 hours down in 150 ℃.
(3) after reaction finishes, products therefrom is cleaned 8 times with the 500ml high purity water, clean 3 times with 150ml ethanol again, reach 7 until its pH value.Product was placed baking oven dry 2 hours.
(4) product after will drying grinds evenly, in 450 ℃ of calcinings 2 hours down, namely obtains having the anatase octahedrite TiO of high reactivity (110) face
2Monocrystalline.
The anatase octahedrite TiO with high reactivity face that Fig. 7 makes for present embodiment
2The sem photograph of monocrystalline.The anatase octahedrite TiO with high reactivity face that Fig. 8 makes for present embodiment
2The X ray diffracting spectrum of monocrystalline.By Fig. 7 and Fig. 8 as can be seen, the TiO that present embodiment makes
2Have good anatase structuredly, and have (110) crystal face.
Embodiment 5
Present embodiment is used for explanation preparation method provided by the invention.
(1) the powder 10mg of weighing metal titanium, it is joined in the polytetrafluoro reactor inner bag, add 1ml concentrated nitric acid, 20ml high purity water, 10mg NaF and 2ml hydrogen peroxide (aqueous solution of 30 weight %) successively in the reactor inner bag, induction stirring 10min obtains titaniferous solution.
(2) titaniferous solution that step (1) is made places the 100mL autoclave, and reactor is airtight, reacts 10 hours down in 200 ℃.
(3) after reaction finishes, products therefrom is cleaned 8 times with the 500ml high purity water, clean 3 times with 150ml ethanol again, reach 7 until its pH value.Product was placed baking oven dry 2 hours.
(4) product after will drying grinds evenly, in 450 ℃ of calcinings 2 hours down, namely obtains having the anatase octahedrite TiO of high reactivity (110) face
2Monocrystalline.
The anatase octahedrite TiO with high reactivity face that Fig. 9 makes for present embodiment
2The sem photograph of monocrystalline.The anatase octahedrite TiO with high reactivity face that Figure 10 makes for present embodiment
2The X ray diffracting spectrum of monocrystalline.By Fig. 9 and Figure 10 as can be seen, the TiO that present embodiment makes
2Have good anatase structuredly, and have (110) crystal face.
Should be noted that and understand, under the situation that does not break away from the desired the spirit and scope of the present invention of accompanying Claim, can make various modifications and improvement to the present invention of foregoing detailed description.Therefore, the scope of claimed technical scheme is not subjected to the restriction of given any specific exemplary teachings.
Claims (7)
1. anatase octahedrite TiO who prepares (110) face that has high reactivity
2The method of monocrystalline, this method may further comprise the steps:
(1) add water successively in the titanium valve, hydrofluoric acid and hydrogen peroxide, stir and obtain titaniferous solution;
(2) described titaniferous solution was reacted 1～40 hour in autoclave down in 120～220 ℃;
(3) reaction product water and the organic solvent washing that step (2) is obtained is 7 ± 0.5 until its pH value, is dried then, obtains solid;
(4) calcined 1～6 hour down in 120～900 ℃ behind the solid abrasive that step (3) is obtained, namely obtain having the anatase octahedrite TiO of high reactivity (110) face
2Monocrystalline.
2. preparation method according to claim 1, wherein, described titanium valve is selected from powder, titanium dioxide powder, the TiCl of metal titanium
4Powder and Ti (SO
4)
2In the powder one or more.
3. preparation method according to claim 1 and 2, wherein, in described step (1), with respect to the titanium of 1mol, the volume of water is 50000～250000ml, is preferably 100000～200000ml; The concentration of hydrofluoric acid is 50～56mol/L, and volume is 240～960ml, is preferably 360～600ml; The volume of hydrogen peroxide is 2400～48000ml, is preferably 4800～24000ml.
4. according to each described preparation method in the claim 1 to 3, wherein, in described step (2), temperature of reaction is 150～200 ℃, and the reaction times is 10～20 hours.
5. according to each described preparation method in the claim 1 to 4, wherein, organic solvent is one or more in ethanol, methyl alcohol and the acetone described in the step (3), is preferably ethanol.
6. according to each described preparation method in the claim 1 to 5, in described step (4), calcining temperature is 400～600 ℃, and calcination time is 1～3 hour.
7. according to each described preparation method in the claim 1 to 6, in step (1), described stirring is induction stirring, and churning time is 5～30 minutes.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104419976A (en) * | 2013-08-29 | 2015-03-18 | 国家纳米科学中心 | TiO2 single crystal and preparation method thereof |
| CN106048722A (en) * | 2016-07-13 | 2016-10-26 | 上海工程技术大学 | Method for recycling exposed (001) crystal face TiO2 from titanium-containing waste liquid |
| CN110433834A (en) * | 2019-08-30 | 2019-11-12 | 福建工程学院 | A kind of MXene/TiO of two-dimensional slice material modification2The preparation and application of composite material |
| CN110526289A (en) * | 2019-07-16 | 2019-12-03 | 南京碧盾环保科技股份有限公司 | A kind of blue Anatase TiO2Nanocrystal and preparation method thereof |
| CN111808443A (en) * | 2020-07-16 | 2020-10-23 | 江苏华力索菲新材料有限公司 | Preparation method of delustering agent for chemical fibers |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101949053A (en) * | 2010-07-14 | 2011-01-19 | 中国科学院电工研究所 | Method for preparing anatase TiO2 single crystal |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101949053A (en) * | 2010-07-14 | 2011-01-19 | 中国科学院电工研究所 | Method for preparing anatase TiO2 single crystal |
Non-Patent Citations (1)
| Title |
|---|
| MIN LIU ET AL.: "Anatase TiO2 single crystals with exposed {001} and {110} facets:facile synthesis and enhanced photocatalysis", 《CHEMICAL COMMUNICATIONS》, vol. 46, 5 February 2010 (2010-02-05), pages 1664 - 1666 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104419976A (en) * | 2013-08-29 | 2015-03-18 | 国家纳米科学中心 | TiO2 single crystal and preparation method thereof |
| CN106048722A (en) * | 2016-07-13 | 2016-10-26 | 上海工程技术大学 | Method for recycling exposed (001) crystal face TiO2 from titanium-containing waste liquid |
| CN106048722B (en) * | 2016-07-13 | 2018-07-24 | 上海工程技术大学 | One kind recycling exposure (001) crystal face TiO from titaniferous waste liquid2Method |
| CN110526289A (en) * | 2019-07-16 | 2019-12-03 | 南京碧盾环保科技股份有限公司 | A kind of blue Anatase TiO2Nanocrystal and preparation method thereof |
| CN110526289B (en) * | 2019-07-16 | 2021-10-08 | 南京碧盾环保科技股份有限公司 | Blue anatase phase TiO2Nanocrystals and methods of making the same |
| CN110433834A (en) * | 2019-08-30 | 2019-11-12 | 福建工程学院 | A kind of MXene/TiO of two-dimensional slice material modification2The preparation and application of composite material |
| CN111808443A (en) * | 2020-07-16 | 2020-10-23 | 江苏华力索菲新材料有限公司 | Preparation method of delustering agent for chemical fibers |
| CN111808443B (en) * | 2020-07-16 | 2021-11-30 | 江苏华力索菲新材料有限公司 | Preparation method of delustering agent for chemical fibers |
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