CN107227510A - A kind of preparation method of modifying titanium dioxide fiber - Google Patents
A kind of preparation method of modifying titanium dioxide fiber Download PDFInfo
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- CN107227510A CN107227510A CN201710347896.4A CN201710347896A CN107227510A CN 107227510 A CN107227510 A CN 107227510A CN 201710347896 A CN201710347896 A CN 201710347896A CN 107227510 A CN107227510 A CN 107227510A
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- alkali lye
- titania fiber
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
- D01F9/08—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments of inorganic material
Abstract
The invention discloses a kind of preparation method of modifying titanium dioxide, comprise the following steps：S1. inorganic ti sources are added in alkali lye, then add urea and carry out hydro-thermal reaction, presoma is obtained after reaction washing；S2. the presoma obtained in S1 is added in alkali lye and reacted, filtering obtains titania fiber after washing；S3. titania fiber in S2 is dispersed in hydrochloric acid solution, adds Phenyl Acetic Acid (Powder) and ammonium persulfate acid, react, stand, discard upper strata acid solution, wash, after centrifugation, be dried to obtain modifying titanium dioxide, the utilization rate to visible ray is improved.The present invention prepares titania fiber by the two hot methods of step alkali, inorganic ti sources, alkali lye and urea are first obtained into TiO 2 precursor using hydrothermal deposition method by " treating different things alike ", TiO 2 precursor is washed through persalt again, then NaOH hydro-thermal process is passed through, it is scrubbed to obtain titania fiber, it is not required to by calcination processing, while obtained titania fiber has high-temperature stability.
Description
Technical field
The invention belongs to titanium dioxide preparing technical field, more particularly, to a kind of system of modifying titanium dioxide fiber
Preparation Method.
Background technology
The titanium dioxide that current titanium source is prepared with urea coprecipitation method is amorphous powder, and particle diameter is big and easily reunites,
Heat endurance is not also high, causes visible light catalysis activity low.
Existing use titanium source hydrolysis, or titania fiber is prepared mainly by the following steps with urea coprecipitation：（1）
Titanium source is hydrolyzed or the amorphous powder of titanium dioxide is prepared in co-precipitation；（2）Pass through highly basic（Such as KOH, NaOH）With titanium dioxide
Amorphous powder react the presoma for obtaining titania fiber（Such as sodium titanate, potassium titanate）；（3）By presoma through peracid
Change processing obtains fiber metatitanic acid, then obtains titania fiber by calcining.But the titania fiber in calcination process
Structure is easily destroyed, and fibre structure is imperfect.
Therefore, it is badly in need of a kind of new method that titania fiber is prepared with titanium source and urea coprecipitation, it is above-mentioned to overcome
Reunion is easily caused, and heat endurance is poor, and the low defect of visible light catalysis activity.
The content of the invention
It is an object of the invention to according to deficiency of the prior art, there is provided a kind of preparation of modifying titanium dioxide fiber
Method.
The present invention prepares titania fiber by the two hot methods of step alkali, and inorganic ti sources, alkali lye and urea first are used into hydro-thermal
The precipitation method obtain TiO 2 precursor by " treating different things alike "（That is potassium titanate）, then TiO 2 precursor washed through persalt
Wash, it is scrubbed to obtain titania fiber then by NaOH hydro-thermal process, it is not required to the titanium dioxide by calcination processing, obtained
Titanium fiber has high-temperature stability.
The purpose of the present invention is achieved through the following technical solutions：
The invention provides a kind of preparation method of modifying titanium dioxide, comprise the following steps：
S1. inorganic ti sources are added in alkali lye, then add urea and carry out hydro-thermal reaction, presoma is obtained after reaction washing；
S2. the presoma obtained in S1 is added in alkali lye and reacted, filtering obtains titania fiber after washing；
S3. titania fiber in S2 is dispersed in hydrochloric acid solution, adds Phenyl Acetic Acid (Powder) and ammonium persulfate acid, react, stand, abandon
Upper strata acid solution is gone, washs, after centrifugation, is dried to obtain modifying titanium dioxide.
Compared with prior art, the present invention obtains TiO 2 precursor by " treating different things alike "（That is potassium titanate）, without two
Step, reactions steps are reduced, in addition, the present invention is reacted by adding alkali liquor hydrothermal in presoma, to improve the thermally-stabilised of product
Property, need not move through calcining.
Preferably, the mass volume ratio of inorganic ti sources and alkali lye is 1 in the S1：（5~8）, the concentration of the alkali lye is 14
~16mol/L。
Preferably, the mol ratio of inorganic ti sources and urea is 1 in the S1：（0.5~1.5）.
Preferably, the temperature of hydro-thermal reaction is 160 ~ 200 DEG C in S1, and the reaction time is 40 ~ 50h.
Preferably, the mass volume ratio of presoma and alkali lye is 1 in S2：（45~55）, the concentration of alkali lye is 9 ~ 11mol/L.
Preferably, reaction temperature is 160 ~ 200 DEG C in S2, and the reaction time is 18 ~ 28h.
Preferably, the inorganic ti sources are titanium sulfate, and the alkali lye is sodium hydroxide solution.
The present invention has found simultaneously, during the two hot methods of step alkali prepare titania fiber, only by appropriate inorganic titanium
At the correct ratio, and the concentration of alkali lye carries out appropriate control during two step alkali lye for source and urea, could synthesize obtain compared with
The titania fiber product of good pattern.
Preferably, in S3, the aniline and ammonium persulfate are first dissolved in hydrochloric acid solution in advance, and ammonium persulfate and aniline rub
You are than being 1:1；The mass ratio of titania fiber and aniline is（1~5）：1000.
Preferably, reaction is 3 ~ 5h in S3.
Compared with prior art, the present invention has advantages below and beneficial effect：
The present invention obtains TiO 2 precursor by " treating different things alike "（That is potassium titanate）, without two steps, reactions steps are reduced, separately
Outside, the present invention is reacted by adding alkali liquor hydrothermal in presoma, to improve the heat endurance of product, needs not move through calcining.
Brief description of the drawings
Fig. 1 is titanium sulfate and the XRD of urea different mol ratio.
Fig. 2 is that titanium sulfate and the SEM of urea different mol ratio scheme.
Fig. 3 is the XRD that PANI is modified before and after F-TiO2 particles.
Fig. 4 is the ultraviolet-visible absorption spectroscopy figure that PANI is modified before and after F-TiO2 particles.
Embodiment
The present invention is further illustrated below in conjunction with specific embodiments and the drawings, but embodiment does not do any to the present invention
The restriction of form.Unless stated otherwise, the reagent of the invention used, method and apparatus is the art conventional reagent, methods
And equipment.
Unless stated otherwise, agents useful for same and material of the present invention are purchased in market.
Embodiment 1：
（1）The preparation of titania fiber
8 g titanium sulfates are dissolved in the mol/L of 50 ml 15 KOH, 70 DEG C of water-baths, magnetic agitation 30 minutes, after dissolving according to
1:1 mol ratio adds urea, and persistently stirring is placed in reactor 180 DEG C for 30 minutes and reacted 48 hours, by obtained sample
With 1 mol/L salt acid elution to neutrality.In 60 DEG C of drying, then the NaOH for taking 1 g samples to be added to the mol/L of 50 ml 10
In, and magnetic agitation 30 minutes, it is placed in 180 DEG C and reacts 24 hours, and filtration washing, it is washed with water to neutrality, 60 DEG C of dryings
Obtain TiO2Fiber（F- TiO2）.
（2）TiO2The preparation of/PANI fibers
0.0186 g aniline is taken, is dissolved with a little 1 mol/L HCl solution, by n（Ammonium persulfate）：n（Aniline）=1:1 adds
0.0456 g ammonium persulfates, and dissolved with a little 1 mol/L HCl.According to PANI/TiO2Mass ratio weighs 5.58 for 1/300
G nano-TiOs2, it is dispersed in the hydrochloric acid of certain volume, with ultrasonically treated 20 minutes after magnetic agitation half an hour, in ice-water bath
Aniline acid solution and ammonium persulfate acid solution are successively added dropwise under magnetic agitation, question response takes out after 4 hours, and reaction suspends
Liquid is stood, and discards upper strata acid solution, and washed with massive laundering, finally with ethanol wash one time, after centrifugation, is deposited in 45 DEG C of vacuum
It is drying for one day to obtain sample P ANI/F-TiO2, and by sample take out be placed in it is standby in desiccator.
Comparative example 1：
8 g titanium sulfates are dissolved in the mol/L of 50 ml 15 KOH, 70 DEG C of water-baths, magnetic agitation 30 minutes, after dissolving according to
1:2 mol ratio adds urea, and persistently stirring is placed in reactor 180 DEG C for 30 minutes and reacted 48 hours, by obtained sample
With 1 mol/L salt acid elution to neutrality.In 60 DEG C of drying, then the NaOH for taking 1 g samples to be added to the mol/L of 50 ml 10
In, and magnetic agitation 30 minutes, it is placed in 180 DEG C and reacts 24 hours, and filtration washing, it is washed with water to neutrality, 60 DEG C of dryings
Obtain TiO2Fiber.
Comparative example 2：
8 g titanium sulfates are dissolved in the mol/L of 50 ml 15 KOH, 70 DEG C of water-baths, magnetic agitation 30 minutes, after dissolving according to
1:3 mol ratio adds urea, and persistently stirring is placed in reactor 180 DEG C for 30 minutes and reacted 48 hours, by obtained sample
With 1 mol/L salt acid elution to neutrality.In 60 DEG C of drying, then the NaOH for taking 1 g samples to be added to the mol/L of 50 ml 10
In, and magnetic agitation 30 minutes, it is placed in 180 DEG C and reacts 24 hours, and filtration washing, it is washed with water to neutrality, 60 DEG C of dryings
Obtain TiO2Fiber.
Comparative example 3：
8 g titanium sulfates are dissolved in the mol/L of 50 ml 10 KOH, 70 DEG C of water-baths, magnetic agitation 30 minutes, after dissolving according to
1:1 mol ratio adds urea, and persistently stirring is placed in reactor 180 DEG C for 30 minutes and reacted 48 hours, by obtained sample
With 1 mol/L salt acid elution to neutrality.In 60 DEG C of drying, then the NaOH for taking 1 g samples to be added to the mol/L of 50 ml 15
In, and magnetic agitation 30 minutes, it is placed in 180 DEG C and reacts 24 hours, and filtration washing, it is washed with water to neutrality, 60 DEG C of dryings
Obtain TiO2Fiber（F- TiO2）.
In comparative example 3, as different from Example 1, concentration is employed in a step alkali hot stage slightly lower（10 mol/
L）KOH solution, and it is slightly higher to employ concentration in two step alkali lye stages（15 mol/L）KOH solution, synthesis phase shows,
Titania fiber can not be obtained under the preparation condition.
Wherein Fig. 1（a）n（Ti(SO4)2）:n（(NH2)2CO）=1:0；（b） n（Ti(SO4)2）:n（(NH2)2CO）=1:1；
（c）n（Ti(SO4)2）:n（(NH2)2CO）=1:2；（d） n（Ti(SO4)2）:n（(NH2)2CO）=1:3.By compareing X rays
Diffraction standard card JCPDS No.21-1272 understand that 2 θ values are 25.3（101）、37.9（103）、48.0（200）、54.6
（105）With 62. 8（204）Correspondence TiO2The diffraction maximum of anatase.Illustrate that by sample prepared by the hot method of two step alkali be sharp
Titanium ore type TiO2.But constantly increase with the mol ratio of precursor titanium sulfate and urea, the urea amount of addition increases, hydro-thermal body
PH increases in system so that Ti (SO4)2Middle Ti4+Hydrolysis is towards being conducive to the direction of nucleation to carry out, thus nucleation rate
Increase, so obtained TiO2The grain size of powder reduces.
Fig. 2（a）n（Ti(SO4)2）:n（(NH2)2CO）=1:0；（b） n（Ti(SO4)2）:n（(NH2)2CO）=1:1；（c）n
（Ti(SO4)2）:n（(NH2)2CO）=1:2；（d） n（Ti(SO4)2）:n（(NH2)2CO）=1:3；Fig. 2 is adjusted in the hot method of two step alkali
The SEM figures that section titanium sulfate and urea different mol ratio are obtained.It is 1 in the mol ratio of titanium sulfate and urea:What is obtained when 0 is " soil
The Detitanium-ore-type TiO of beans shape "2（With reference to Fig. 1 XRD）, and be 1 in the mol ratio of titanium sulfate and urea:The rutile titania obtained when 1
Ore deposit fiber type shape F-TiO2, it is 1 in mol ratio:2 and 1:The TiO obtained when 32Pattern is irregular, illustrates titanium sulfate and urea not
With mol ratio to TiO2Pattern play the role of it is important.
Given in Fig. 3 in embodiment 1 in F-TiO2/ PANI mass ratio be 1/300 when with PANI to F-TiO2Particle enters
Row is modified.By compareing X ray diffraction standard card JCPDS No.21-1272 anatases TiO2Knowable to characteristic diffraction peak,
The modified M-TiO with before modified2The diffraction pattern of particle coincide substantially, and the position at peak type and peak is all without significant change, this table
Bright PANI modification does not have change F-TiO2Its original crystal structure.
Fig. 4 is polyaniline-modified TiO in embodiment 12Ultraviolet-visible absorption spectroscopy figure before and after particle, Fig. 4（a）To prepare
Nanometer titanium dioxide fiber；（b）Titania fiber after polyaniline-modified, figure 4, it is seen that TiO2It is fine
Wiener rice corpuscles mainly has absorption to ultraviolet light, and absorbing boundary there is not absorption to visible region substantially in ultraviolet region, this with
TiO2The energy gap of nano-particle is larger relevant, and because polyaniline energy gap is relatively low（2.8 eV）, being capable of table to visible ray
Reveal stronger absorption, possess and carry out modifying semiconductor TiO as photosensitizer2Ability.And as polyaniline and TiO2Answered
After conjunction, compound particle absorbs to visible region to be remarkably reinforced, and absorbing boundary has very big red shift, reaches 750 nm,
The absorption in visible region can be greatly improved, the utilization rate of sunshine is improved.
The present invention is not limited to the detail of above implementation, can be with the range of the technology design of the present invention
A variety of simple variants are carried out to technical scheme, these belong to protection scope of the present invention.
Claims (9)
1. a kind of preparation method of modifying titanium dioxide, it is characterised in that comprise the following steps：
S1. inorganic ti sources are added in alkali lye, then add urea and carry out hydro-thermal reaction, presoma is obtained after reaction washing；
S2. the presoma obtained in S1 is added in alkali lye and reacted, filtering obtains titania fiber after washing；
S3. titania fiber in S2 is dispersed in hydrochloric acid solution, adds Phenyl Acetic Acid (Powder) and ammonium persulfate acid, react, stand, abandon
Upper strata acid solution is gone, washs, after centrifugation, is dried to obtain modifying titanium dioxide.
2. preparation method according to claim 1, it is characterised in that the quality volume of inorganic ti sources and alkali lye in the S1
Than for 1：（5~8）, the concentration of the alkali lye is 14 ~ 16mol/L.
3. preparation method according to claim 1, it is characterised in that the mol ratio of inorganic ti sources and urea is in the S1
1：（0.5~1.5）.
4. preparation method according to claim 1, it is characterised in that the temperature of hydro-thermal reaction is 160 ~ 200 DEG C in S1, instead
It is 40 ~ 50h between seasonable.
5. preparation method according to claim 1, it is characterised in that the mass volume ratio of presoma and alkali lye is 1 in S2：
（45~55）, the concentration of alkali lye is 9 ~ 11mol/L.
6. preparation method according to claim 1, it is characterised in that reaction temperature is 160 ~ 200 DEG C, reaction time in S2
For 18 ~ 28h.
7. preparation method according to claim 1, it is characterised in that the inorganic ti sources are titanium sulfate, the alkali lye is
Sodium hydroxide solution.
8. preparation method according to claim 1, it is characterised in that in S3, the aniline and ammonium persulfate dissolve in advance
In hydrochloric acid solution, the mol ratio of ammonium persulfate and aniline is 1:1；The mass ratio of titania fiber and aniline is（1~5）：
1000。
9. preparation method according to claim 1, it is characterised in that reaction is 3 ~ 5h in S3.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6330400A (en) * | 1986-07-21 | 1988-02-09 | Ishihara Sangyo Kaisha Ltd | Production of potassium titanate fiber |
| JPH01115824A (en) * | 1987-10-28 | 1989-05-09 | S T K Ceramics Kenkyusho:Kk | Production of alkali titanate fiber |
| CN1400169A (en) * | 2002-08-19 | 2003-03-05 | 西安华创纳米化合物技术研究发展有限责任公司 | Preparation method of titanium oxide nano fibre |
| CN102531050A (en) * | 2010-12-30 | 2012-07-04 | 北京大学 | Method for preparing TiO2 (B) nano wires and application of prepared TiO2 (B) nano wires |
| CN102992394A (en) * | 2011-09-08 | 2013-03-27 | 战继香 | Titanium dioxide low-temperature hydrothermal synthesis method |
| CN105837053A (en) * | 2015-01-13 | 2016-08-10 | 广东工业大学 | Titanium dioxide/polyaniline nano-composite structure and preparation method thereof |
| CN106800308A (en) * | 2016-12-24 | 2017-06-06 | 张家港大塚化学有限公司 | The preparation method and applications of potassium titanate nanofiber |
-
2017
- 2017-05-17 CN CN201710347896.4A patent/CN107227510B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6330400A (en) * | 1986-07-21 | 1988-02-09 | Ishihara Sangyo Kaisha Ltd | Production of potassium titanate fiber |
| JPH01115824A (en) * | 1987-10-28 | 1989-05-09 | S T K Ceramics Kenkyusho:Kk | Production of alkali titanate fiber |
| CN1400169A (en) * | 2002-08-19 | 2003-03-05 | 西安华创纳米化合物技术研究发展有限责任公司 | Preparation method of titanium oxide nano fibre |
| CN102531050A (en) * | 2010-12-30 | 2012-07-04 | 北京大学 | Method for preparing TiO2 (B) nano wires and application of prepared TiO2 (B) nano wires |
| CN102992394A (en) * | 2011-09-08 | 2013-03-27 | 战继香 | Titanium dioxide low-temperature hydrothermal synthesis method |
| CN105837053A (en) * | 2015-01-13 | 2016-08-10 | 广东工业大学 | Titanium dioxide/polyaniline nano-composite structure and preparation method thereof |
| CN106800308A (en) * | 2016-12-24 | 2017-06-06 | 张家港大塚化学有限公司 | The preparation method and applications of potassium titanate nanofiber |
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