CN1298633C - Preparation method of anatase phase mesohole nano-titanium dioxide powder - Google Patents
Preparation method of anatase phase mesohole nano-titanium dioxide powder Download PDFInfo
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- CN1298633C CN1298633C CNB2005100187697A CN200510018769A CN1298633C CN 1298633 C CN1298633 C CN 1298633C CN B2005100187697 A CNB2005100187697 A CN B2005100187697A CN 200510018769 A CN200510018769 A CN 200510018769A CN 1298633 C CN1298633 C CN 1298633C
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Abstract
The present invention discloses a production method of anatase phase mesoporous nanometer titanium dioxide powder. The present invention comprises the following steps: firstly, titanium sulfate and alkylamine hydrochloride are weighed, alcohol is added by magnetic stirring, and water is added; secondly, the pH value of the solution is regulated, and the solution is aged at room temperature; thirdly, the reaction vessel is sealed by using proof fabric, and continuously aged at the temperature of 100DEG C; fourthly, after centrifugal separation and washing, the template agent is removed by using a saturated alcohol solution of sodium chloride; fifthly, washing, drying and heat treating at different temperatures are carried out. The present invention has the advantages of easy operation, moderate production conditions, low energy consumption and low cost, and is applied to the industrial production. The prepared titanium dioxide powder integrates the characteristics of nanometer size, nanometer anatase crystals and mesopores, and has wide application prospects in the fields of pollutant degradation by photocatalysis, hydrogen preparation by photolytic water, solar energy photoelectrochemical cells, etc.
Description
Technical field
The present invention relates to field of fine chemical, more specifically relate to a kind of preparation method of anatase phase mesohole nano-titanium dioxide powder, be with a wide range of applications in fields such as photocatalytic degradation pollutent, photoelectrochemical cell, photolysis water hydrogens.Use this method can prepare the nano-titanium dioxide powder with high-specific surface area and height crystallization anatase octahedrite hole wall of high heat stability.
Background technology
Nano titanium oxide (TiO
2) be meant the titanium dioxide product of particle size less than 100 nanometers, because its particle is little, specific surface area is big, thereby higher chemically reactive is arranged, and is widely used in fields such as Chemical Manufacture, photoelectrochemistry conversion, photochemical catalysis.Prepare TiO at present
2Method generally adopt TiCl
4Hydrolysis or high temperature annealing method prepare.As German P25 product is TiCl
4Flame method prepares, and particle diameter is 30nm, and anatase octahedrite and rutile ratio mutually are 80: 20.TiCl
4The TiO that hydrolysis method prepares
2In the time of 700 ℃, begin to rutile transform and granularity greater than 100nm.The TiO of traditional sol-gel method preparation
2, cost is too high, only suits in prepared in laboratory and use.
Common TiO
2Three kinds of crystal formations are arranged: anatase octahedrite phase, rutile mutually and brookite mutually, preceding two kinds is present widely used crystalline phase.The tinting strength of rutile is better than the anatase octahedrite phase, is widely used in coating, makeup, the paint.And the photocatalytic activity of anatase octahedrite is better than rutile TiO
2, be widely used in aspects such as photoelectrochemical cell, photochemical catalysis decontamination, photo-catalyst, photolysis water hydrogen.Anatase octahedrite TiO
2At cryostatic stabilization, but generally just begin to transform to rutile at 600 ℃, 800 ℃ is main crystalline phase with rutile mostly mutually.In order to utilize anatase octahedrite TiO
2Photochemical catalysis decontamination, sterilizing ability, need it is solidificated in glass or ceramic surface and plays easy to clean and the antimicrobial characteristics, but its thermal treatment temp is generally more than 800 ℃, therefore require at high temperature stable and keep nanocrystalline anatase octahedrite TiO
2And in order to improve anatase octahedrite phase TiO
2Photodissociation water and photoelectrochemistry efficiency of conversion, need TiO
2Have more avtive spot and bigger surface-area and be beneficial to the transmission and the exchange of particle.This shows that the mesoporous material that preparation has the anatase octahedrite hole wall of high thermal stability, high-specific surface area, height crystallization has important practical significance.And with nano-scale, anatase nanometer crystal and mesoporous feature set meso-porous nano TiO
2Will show wide application prospect at aspects such as photocatalytic degradation pollutent, photolysis water hydrogen and solar energy electrochemical cells.Yet, with the porous TiO of surfactant templates method preparation
2Be generally the amorphous structure that does not have catalytic activity, in its crystallization is the process of anatase octahedrite, can cause subsiding of vesicular structure, greatly reduced the specific surface area of nano material.Therefore, at present both at home and abroad about having the nano-TiO of crystallization anatase octahedrite meso-hole structure
2Unexposed or use.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of anatase phase mesohole nano-titanium dioxide powder, this method is easy and simple to handle, and cost is low, and the anatase octahedrite phase and the meso-hole structure of preparing product have higher thermostability.A kind of preparation method of anatase phase mesohole nano-titanium dioxide powder comprises the following steps:
1. select the primary amine of different concns and alkyl chain length for use, prepare the TiO of different apertures and particle size
2Nano powder.
At first take by weighing 1.6-1.8g titanium sulfate [Ti (SO
4)
2] and 1.1-1.3g dodecyl primary amine hydrochloride (or by Ti: the primary amine mol ratio is 2: 1 or 1: 1, take by weighing respectively 12 or the octadecyl amine hydrochlorate); Next is the hard glass reaction vessel that above-mentioned raw materials is placed 500ml, adds 18-24ml ethanol under magnetic agitation, continues to add 18-24ml secondary water; The 3rd is that regulator solution pH is 0.5-0.7, room temperature (20-25 ℃) ageing 46-50h; The 4th is to use the adhesive plaster sealed reaction vessel, and 100-110 ℃ is continued ageing 46-50h; The 5th is centrifugation under the 1200-1400r/min rotating speed, secondary water washing, with 1-2% nitrate of baryta [Ba (NO
3)
2] detect to there not being SO
4 2-The 6th is the washing with alcohol after drying, with the ethanolic soln stripper plate agent of saturated sodium-chloride; The 7th is once more with secondary water, washing with alcohol after drying, 300 ℃, 400 ℃, 500 ℃ thermal treatment 2-3h.
Can obtain the mesoporous TiO of anatase octahedrite of high-specific surface area by above-mentioned steps
2Nano-powder.Along with the increase of the concentration and the alkyl chain length of primary amine hydrochloride, the grain diameter of product, specific surface area and mean pore size increase.The median size of preparing product is at 25-40nm, and mean pore size is at 3-5nm, and specific surface area is at 210-300m
2/ g, the average grain size of mesoporous wall are local adjustable in 3-4nm scopes such as (being the anatase octahedrite phase of crystallization).See following table 1 for details.
2. obtain the anatase phase mesohole TiO of different specific surface areas and crystallization degree after the heat treatments at different
2Nano powder.
The mesoporous TiO that obtains by above-mentioned steps
2Nano powder, anatase octahedrite phase crystallization degree is lower before the calcining or during 300 ℃ of following heat-treated, and residual have an organic matters.After 2 hours, obtain the anatase phase mesohole TiO of different specific surface areas, height crystallization through 300-500 ℃ of calcining
2Nano powder; Along with the rising of calcining temperature, the specific surface area and the particle size of nano-powder reduce gradually; Crystallization degree, grain-size and mean pore size increase gradually, do not find the characteristic peak (seeing following table 2 for details) of any rutile.After the calcining of 500 ℃ and above temperature, meso-hole structure subsides gradually, intraparticle mesoporous structure completely dissolve after 700 ℃ of calcinings.Principal crystalline phase is the anatase octahedrite phase still after 900 ℃ of calcinings, has micro-rutile to form mutually, and grain-size is still less than 10nm, and specific surface area is at 40m
2More than/the g; All change the rutile phase into after 1100 ℃ of calcinings.
The primary amine of table 1. different concns and alkyl chain length prepares TiO
2The physical and chemical indexes of nano powder
| Primary amine kind and consumption (mol ratio) | Specific surface area [a] (m 2/g) | Mean pore size [b] (nm) | Total pore volume [c] (cm -3/g) | Average particle size particle size [d] (nm) | Grain-size [e] (nm) |
| Dodecyl Ti: primary amine=2: 1 Ti: primary amine=1: 1 octadecyl Ti: primary amine=2: 1 Ti: primary amine=1: 1 | 212.0 241.9 246.5 296.6 | 3.3 3.9 4.4 5.0 | 0.23 0.35 0.30 0.44 | 25.0 28.7 32.6 38.3 | 3.9 3.2 4.0 3.4 |
The TiO of table 2. lauryl amine preparation
2The physical and chemical indexes of nano powder after heat treatments at different
| Calcining temperature (℃) Ti: primary amine=2: 1 | Specific surface area [a] (m 2/g) | Mean pore size [b] (nm) | Total pore volume [c] (cm -3/g) | Average particle size particle size [d] (nm) | Grain-size [e] (nm) |
| Calcine preceding 300 400 500 | 196.3 212.0 189.2 151.0 | 2.4 3.3 3.4 3.9 | 0.19 0.23 0.20 0.21 | 26.9 25.0 23.6 20.7 | 2.3 3.9 4.2 4.9 |
[a] liquid nitrogen absorption BET surface-area .[b] the adsorption isothermal line desorption props up and calculates .[c] in that to press relatively be 0.98 single-point total pore volume .[d] TEM statistics size distribution .[e] calculate with the Scherrer formula from the XRD halfwidth.
The present invention compared with prior art has the following advantages and effect:
1. starting material sources is wide, working condition is gentle, energy consumption and cost are low, is fit to suitability for industrialized production.
2. utilize the template action of tensio-active agent, realize nano-TiO by the concentration and the alkyl chain length of regulating primary amine
2The particle diameter of powder and the partial controllable of pore size distribution thereof.
3. adopt adhesive tape sealing thermal aging technology, the low temperature that is beneficial to the anatase octahedrite phase forms.Greatly improve TiO
2The thermostability of anatase octahedrite phase, with anatase octahedrite to the transition of rutile temperature bring up to 900 ℃.Principal crystalline phase still is the anatase octahedrite phase after 900 ℃ of pyroprocessing, and grain-size is less than 10nm, and specific surface area is at 40m
2More than/the g.
4.300-500 a ℃ calcining time can keep meso-hole structure when making mesoporous wall crystallization, thereby obtains high surface-area.And the mesoporous of usual method preparation subsided when 300 ℃ of calcinings fully.
5. the titanium dioxide powder of this law preparation with nano-scale, anatase nanometer crystal and mesoporous feature set has broad application prospects at aspects such as photocatalytic degradation pollutent, photolysis water hydrogen and solar energy electrochemical cells.
Description of drawings
Fig. 1 is the TEM photo of the present invention at 300 ℃ of calcining products obtained therefroms.Particle distribution is more even, and median size is 25nm, and mean pore size is 3.3nm, and average grain size is 3.9nm;
Fig. 2 is HRTEM photo and the selected area electron diffraction speckle of the present invention at 300 ℃ of calcining products obtained therefroms.Particle distribution is more even, and median size is 25nm, and mean pore size is 3.3nm, and average grain size is 3.9nm, and the crystallization degree of hole wall is higher;
Fig. 3 is HRTEM photo and the selected area electron diffraction speckle of the present invention at 400 ℃ of calcining products obtained therefroms.Particle distribution is more even, and median size is 23.6nm, and mean pore size is 3.4nm, and average grain size is 4.2nm, and the crystallization degree of hole wall improves;
Fig. 4 is the HRTEM photo of the present invention at 400 ℃ of calcining products obtained therefroms.Can observe the coexistence of tangible lattice fringe and vesicular structure.Along with the rising of temperature, particle inside mesoporous reduces gradually and subsides;
Fig. 5 is the HRTEM photo of the present invention at 500 ℃ of calcining products obtained therefroms.Particle distribution is more even, and median size is 20.7nm, and mean pore size is 3.9nm, and average grain size is 4.9nm;
Fig. 6 is the HRTEM photo of the present invention at 700 ℃ of calcining products obtained therefroms.The meso-hole structure completely dissolve of product causes reducing of specific surface area and particle size, but grain-size in the nanoparticle and crystallization degree increase.
Embodiment
Preparation flow of the present invention is as follows:
Its basic step is: take by weighing titanium sulfate and kiber alkyl amine hydrochloride, add ethanol under the magnetic agitation, add entry then; Next is regulator solution pH, the room temperature ageing; The 3rd is to use the adhesive plaster sealed reaction vessel, and 100-110 ℃ is continued ageing; The 4th be centrifugation, the washing after, with the ethanolic soln stripper plate agent of saturated sodium-chloride; The 5th be washing, after the drying, heat treatments at different.
The embodiment for preparing a kind of anatase phase mesohole nano-titanium dioxide powder is as follows:
(1) takes by weighing 1.6-1.8g titanium sulfate [Ti (SO
4)
2] and the 1.1-1.3g alkylamine hydrochloride (or by Ti: the primary amine mol ratio is 2: 1 or 1: 1, take by weighing respectively 12 or the octadecyl amine hydrochlorate);
(2) above-mentioned raw materials is placed in the hard glass reaction vessel of 500ml, under magnetic agitation, added 18-24ml ethanol, behind the stirring 10min, add 18-24ml secondary water again;
(3) be 0.5～0.7 with 14-16%NaOH or HCl regulator solution pH, room temperature (20-25 ℃) ageing 46-50h;
(4) use the adhesive plaster sealed reaction vessel, 100-110 ℃ is continued ageing 46-50h;
(5) under the 1200-1400r/min rotating speed, 1-2% nitrate of baryta [Ba (NO is washed, used to centrifugation, secondary water washing
3)
2] detect to there not being SO
4 2-
(6) washing with alcohol after drying is sloughed template with the alcohol solution dipping of saturated sodium-chloride;
(7) once more with after secondary water, the washing with alcohol, drying, 300 ℃, 400 ℃, 500 ℃ thermal treatment 2-3h obtain specific surface area and particle size and reduce the mesoporous nano TiO that crystallization degree, grain-size and mean pore size increase gradually gradually
2Powder.
Select different alkylamine hydrochlorides as required for use, the size in particle size and aperture is relevant with the length of the concentration of alkylamine and alkyl chain.In certain scope, the concentration of alkylamine and alkyl chain are big more, and particle size, aperture and specific surface area are big more.In 300-800 ℃ scope, the setting of specific surface area, crystallization degree, pore size distribution, grain-size and warm area is relevant with the kind and the concentration of tensio-active agent.
Promptly formed anatase octahedrite TiO before the calcining
2, the main diffraction peak of x-ray diffraction pattern is: 25.3 °, 37.9 °, 48.0 °, 53.9 °, 55.1 ° are waited the characteristic peak of anatase octahedrite all to occur, and just peak intensity is lower, and the peak shape broadening shows that the anatase octahedrite phase grain-size of formation is less, and crystallization degree is lower.300-800 ℃ of calcining can obtain specific surface area and particle size reduces gradually; The nano-powder that crystallization degree, grain-size and mean pore size increase is not gradually found the characteristic peak [27.5 °] of any rutile.900 ℃ of calcinings are after 2 hours, and principal crystalline phase is the anatase octahedrite phase still, has micro-rutile to form mutually.Fig. 1-6 is respectively 300,400, the TEM photo of 500,700 ℃ of calcination product.As seen from the figure, the dispersiveness of sample is better, and granular size is more even; The meso-hole structure of 300-400 ℃ of calcination product keeps better, and the selected area electron diffraction style shows that crystallization degree is higher, and the HRTEM of Fig. 4 shows tangible lattice fringe and vesicular structure coexistence.Along with the rising of temperature, particle inside mesoporous reduces gradually and subsides, and the meso-hole structure completely dissolve of product cause reducing of specific surface area and particle size, but grain-size and crystallization degree in the nanoparticle increases gradually after 700 ℃ of calcinings.
Embodiment 1: take by weighing 1.7600g Ti (SO
4)
2With 1.2172g dodecyl amine hydrochlorate, add 20ml ethanol under the magnetic agitation, behind the stirring 10min, slowly add 20ml secondary water again, behind the stirring 30min.Room temperature ageing 48 hours.Use rubber belt sealing then, 100 ℃ of ageings 48 hours.After the cooling, centrifugation, secondary water washing is extremely with 2% nitrate of baryta [Ba (NO
3)
2] detect to there not being SO
4 2-, ethanol is washed after drying.Ethanolic soln with saturated sodium-chlor is sloughed template, once more with secondary water, washing with alcohol after drying.
Calcined 2 hours for 300 ℃, the pattern that obtains product is seen Fig. 1 and Fig. 2, and particle distribution is more even, and median size is 25nm, and mean pore size is 3.3nm, and average grain size is 3.9nm, and specific surface area is 212m
2/ g, the crystallization degree of hole wall is higher.Calcined 2 hours for 400 ℃, the particle distribution that obtains product is more even, and median size is 23.6nm, and mean pore size is 3.4nm, and average grain size is 4.2nm, and specific surface area is 189.2m
2/ g, the crystallization degree of hole wall improves.The particle distribution of 500 ℃ of calcinings acquisition in 2 hours product is more even, and median size is 20.7nm, and mean pore size is 3.9nm, and average grain size is 4.9nm, and specific surface area is 151m
2/ g, the hole wall complete crystallization.
Embodiment 2: take by weighing 1.7600g Ti (SO
4)
2With 3.3605g octadecyl amine hydrochlorate, add 20ml ethanol under the magnetic agitation, behind the stirring 10min, slowly add 20ml secondary water again, behind the stirring 30min.Room temperature ageing 48 hours.Use rubber belt sealing then, 100 ℃ of ageings 48 hours.After the cooling, centrifugation, secondary water washing is extremely with 2% nitrate of baryta [Ba (NO
3)
2] detect to there not being SO
4 2-, ethanol is washed after drying.Ethanolic soln with saturated sodium-chlor is sloughed template, once more secondary water, washing with alcohol after drying.
The particle distribution of 300 ℃ of calcinings acquisition in 2 hours product is more even, and median size is 38.3nm, and mean pore size is 5.0nm, and average grain size is 3.4nm, and specific surface area is 296.6m
2/ g, the crystallization degree of hole wall is higher.Calcined 2 hours for 400 ℃, the particle distribution that obtains product is more even, and median size is 37.4nm, and mean pore size is 5.1nm, and average grain size is 3.7nm, and specific surface area is 211.3m
2/ g, the crystallization degree of hole wall improves.The particle distribution of 500 ℃ of calcinings acquisition in 2 hours product is more even, and median size is 35.9nm, and mean pore size is 5.5nm, and average grain size is 4.5nm, and specific surface area is 178.4m
2/ g, the hole wall complete crystallization.
Embodiment 3: take by weighing 1.7600g Ti (SO
4)
2With 2.4365g dodecyl amine hydrochlorate, add 4ml ethanol under the magnetic agitation, behind the stirring 10min, slowly add 4ml secondary water again, behind the stirring 30min.Room temperature ageing 48 hours.Use rubber belt sealing then, 100 ℃ of ageings 48 hours.After the cooling, centrifugation, secondary water washing is extremely with 2% nitrate of baryta [Ba (NO
3)
2] detect to there not being SO
4 2-, ethanol is washed after drying.Ethanolic soln with saturated sodium-chlor is sloughed template, once more secondary water, washing with alcohol after drying.
The particle distribution of 300 ℃ of calcinings acquisition in 2 hours product is more even, and median size is 28.7nm, and mean pore size is 3.9nm, and average grain size is 3.2nm, and specific surface area is 241.9m
2/ g, the crystallization degree of hole wall is higher.Calcined 2 hours for 400 ℃, the particle distribution that obtains product is more even, and median size is 27.6nm, and mean pore size is 4.1nm, and average grain size is 3.3nm, and specific surface area is 178.7m
2/ g, the crystallization degree of hole wall improves.The particle distribution of 500 ℃ of calcinings acquisition in 2 hours product is more even, and median size is 25.1nm, and mean pore size is 4.6nm, and average grain size is 3.9nm, and specific surface area is 135.3m
2/ g, the hole wall complete crystallization.
Claims (1)
1, a kind of preparation method of anatase phase mesohole nano-titanium dioxide powder comprises the following steps:
A, take by weighing 1.6-1.8g titanium sulfate and 1.1-1.3g dodecyl amine hydrochlorate or by Ti: the primary amine mol ratio is 2: 1 or 1: 1, takes by weighing 12 or the octadecyl amine hydrochlorate respectively;
B, above-mentioned raw materials is placed in the hard glass reaction vessel of 500ml, under magnetic agitation, adds 18-24ml ethanol, stir 10min after, add 18-24ml secondary water again;
C, be 0.5～0.7 with 14-16%NaOH or HCl regulator solution pH, room temperature ageing 46-50h;
D, use the adhesive plaster sealed reaction vessel, 100-110 ℃ is continued ageing 46-50h;
E, under the 1200-1400r/min rotating speed, centrifugation, secondary water washing wash, detect to there not being SO with the 1-2% nitrate of baryta
4 2-
F, washing with alcohol after drying are sloughed template with the alcohol solution dipping of saturated sodium-chloride;
G, once more with secondary water, washing with alcohol after drying, 300 ℃, 400 ℃ or 500 ℃ of thermal treatment 2-3h obtain mesoporous nano TiO
2Powder.
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| WO2011056150A2 (en) * | 2009-11-05 | 2011-05-12 | National University Of Singapore | Crystalline mesoporous titanium dioxide and the use thereof in electrochemical devices |
| CN104787799B (en) * | 2015-05-13 | 2017-03-22 | 武汉理工大学 | Web-type three-dimensional perforated macroporous-mesoporous-structure titanium dioxide material, and preparation method and application thereof |
| CN109052468B (en) * | 2018-08-29 | 2020-10-13 | 湖北工业大学 | Mesoporous titanium dioxide microsphere and preparation method thereof |
| CN109364949A (en) * | 2018-09-25 | 2019-02-22 | 武汉大学苏州研究院 | Ultraviolet-visible-near infrared light response PbS/TiO2Nanotube reunion microballoon hetero-junctions, preparation method and use |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1135459A (en) * | 1995-01-20 | 1996-11-13 | 泰奥塞集团服务有限公司 | Detitanium-ore-type preparation of titanium dioxide |
| CN1146976A (en) * | 1996-09-18 | 1997-04-09 | 中国科学院固体物理研究所 | Process for preparing nm. titania |
| CN1287878A (en) * | 2000-08-24 | 2001-03-21 | 中国科学院上海硅酸盐研究所 | Process for preparing mesopore titania photocatalyst |
| KR20030021291A (en) * | 2001-09-05 | 2003-03-15 | (주)이앤비코리아 | Manufacturing method and device on anatase type TiO2 sol |
| CN1491897A (en) * | 2002-10-23 | 2004-04-28 | 中国科学院化学研究所 | Low temperature preparing process for anatase phase nano crystal titanium dioxide of light catalystic activity |
-
2005
- 2005-05-24 CN CNB2005100187697A patent/CN1298633C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1135459A (en) * | 1995-01-20 | 1996-11-13 | 泰奥塞集团服务有限公司 | Detitanium-ore-type preparation of titanium dioxide |
| CN1146976A (en) * | 1996-09-18 | 1997-04-09 | 中国科学院固体物理研究所 | Process for preparing nm. titania |
| CN1287878A (en) * | 2000-08-24 | 2001-03-21 | 中国科学院上海硅酸盐研究所 | Process for preparing mesopore titania photocatalyst |
| KR20030021291A (en) * | 2001-09-05 | 2003-03-15 | (주)이앤비코리아 | Manufacturing method and device on anatase type TiO2 sol |
| CN1491897A (en) * | 2002-10-23 | 2004-04-28 | 中国科学院化学研究所 | Low temperature preparing process for anatase phase nano crystal titanium dioxide of light catalystic activity |
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Effective date of registration: 20170522 Address after: 436070 No. 2 Renmin Road, Gedian Economic Development Zone, Ezhou, Hubei Patentee after: Hubei Tieshen Chemical Co., Ltd. Address before: 430223 Hubei Province, Wuhan city Jiangxia District Temple Hill District Shiyuan Hua Road No. 13 Patentee before: Wuhan Tieshen Chemical Co., Ltd. |
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