CN103121712A - Method for preparation of super long fibrous titanium dioxide by taking cellulosic fibers as template - Google Patents
Method for preparation of super long fibrous titanium dioxide by taking cellulosic fibers as template Download PDFInfo
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- CN103121712A CN103121712A CN2013100707785A CN201310070778A CN103121712A CN 103121712 A CN103121712 A CN 103121712A CN 2013100707785 A CN2013100707785 A CN 2013100707785A CN 201310070778 A CN201310070778 A CN 201310070778A CN 103121712 A CN103121712 A CN 103121712A
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Abstract
The invention provides a method for the preparation of super long fibrous titanium dioxide by taking cellulosic fibers as a template, relates to the method for the preparation of the super long fibrous titanium dioxide, and aims to solve the problems caused by the existing method that the prepared fibrous material cannot reach more than 15mu m in length; and the process is complicated, the sources are single, the cost is high and the yield is low. The method provided by the invention comprises the following steps: 1) preparing a natural fiber dispersion liquid; 2) preparing the dispersion liquid of natural fibers bonded with TiOH<3+>; 3) preparing the dispersion liquid of the natural fibers bonded with TiOSO4; 4) preparing the natural fibers bonded with titanium dioxide; 5) preparing natural wet fibers with core-shell structures bonded with the titanium dioxide; 6) preparing organic-titanium dioxide fibers with the core-shell structures; and 7) sintering at a high temperature and demolding the template. The method is applied to the fields of photoelectric materials, sensors, medicine release, energy storage materials, single molecule probes, neural signal detection and the like.
Description
Technical field
The present invention relates to a kind of method for preparing overcut fibre shape titanium dioxide.
Background technology
The natural biomass fiber is natural polymer, comprises vegetable fibre and animal fibre, extensively is present in occurring in nature.The chief component material of vegetable fibre is Mierocrystalline cellulose, is called again native cellulose fibre.It is the fiber of being located to obtain by seed, fruit, stem, leaf etc. on plant.Except paper pulp fiber, the difference according to the position of growing up on herbaceous plant also is divided into: 1. seed hair (cotton, kapok etc.); 2. leaf fibres (sisal hemp, abaca etc.); 3. fasciated fiber (ramie, flax, hemp, jute, bamboo etc.).Animal fibre is natural protein fibre, is divided into 1. hair classes: sheep's wool, goathair, Pilus Cameli, the rabbit hair, yak hair etc.; With 2. glandular secretion things: mulberry silk, tussah silk etc.And the maturation process of textile industry and paper-making industry makes the annual production of natural biomass fiber very high, if prepare type material used as the template of inorganics, is cheap organic template material (than the electric spinning polymer fiber).Therefore, be badly in need of now this type of biomass resource is carried out new application and development preparation novel inorganic oxide material.
Inorganic nano-fiber has purposes widely at aspects such as photoelectric material, sensor, drug release, single molecule probe, energy storage material, nerve signal detections.In recent years, several different methods is used for preparing the inorganic fibrous material, comprises anodic oxidation, anodization, coating inorganic thing etc. on electrospinning fibre or multipolymer template.But the relative technical sophistication of these methods, the template cost is high, yields poorly and is difficult to a large amount of production, more than the fibrous material length that these methods are prepared is difficult to reach 15 μ m.
Summary of the invention
The present invention will solve more than fibrous material length that existing method prepares is difficult to reach 15 μ m, and complex process, the source is single, cost is high and the problem that yields poorly, and a kind of overcut fibre shape titanium dioxide method for preparing take cellulosic fibre as template is provided.
A kind of method for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template of the present invention, undertaken by following steps:
One, with after natural fiber cleaning, drying, be dispersed in deionized water, obtain the natural fiber dispersion liquid; Wherein, natural fiber is the fiber of cotton, fiber crops, hair, silk or bamboo;
Two, obtain adding titanium tetrachloride in the natural fiber dispersion liquid to step 1, under the ice-water bath condition, with the stir speed (S.S.) of 50r/min～300r/min, carry out magnetic agitation 0.5～2h, obtain being attached with TiOH
3+The dispersion liquid of natural fiber;
Three, under the condition of ice-water bath, adhere to TiOH to what step 2 obtained
3+The dispersion liquid of natural fiber in add (NH
4)
2SO
4With mass percent be 1%～3% HCl solution, then carry out magnetic agitation 0.5～2h with the stir speed (S.S.) of 50r/min～300r/min, then heated and stirred, obtain being attached with TiOSO
4The dispersion liquid of natural fiber;
Four, be the TiOSO that adheres to that obtains in 25～28% ammoniacal liquor regulating steps three that are with volumetric molar concentration
4The pH value to 7～11 of dispersion liquid of natural fiber, after heated and stirred, then the standing 12～48h of at room temperature ageing filters, and gets solid formation, obtains being attached with the natural fiber of titanium dioxide;
Five, the natural fiber that is attached with titanium dioxide that obtains in step 4 is cleaned, obtain the hygrometric state natural fiber that is attached with titanium dioxide of nucleocapsid structure;
Six, the hygrometric state natural fiber that is attached with titanium dioxide with the nucleocapsid structure that obtains in step 5 carries out drying, obtain nucleocapsid structure organic-titania fiber;
Seven, with the nucleocapsid structure that obtains in step 6 organic-titania fiber, carry out high temperature sintering, namely obtain overcut fibre shape shape titanium dioxide after removing template, namely complete the preparation for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template; Wherein in step 1 the mass volume ratio of natural fiber and deionized water be (0.1g～3g): 100mL, in step 2, the ratio of the volume of the deionized water of titanium tetrachloride and step 1 is (1～5): 100; (NH in step 3
4)
2SO
4, mass percent is that the mol ratio of titanium tetrachloride in 1%～3% HCl solution and step 2 is 2: 10: 1.
A kind of overcut fibre shape titanium dioxide method for preparing take cellulosic fibre as template provided by the invention has the following advantages:
One, the length of the fibrous shape titanium dioxide prepared of existing method is 0.3 μ m～20 μ m, and the length of the fibrous titanium dioxide of preparation method provided by the invention preparation can regulate and control according to the length of template, can reach 0.1mm～2cm;
Two, preparation method provided by the invention, preparation process is simple, does not need expensive device, extensive, the with low cost and environment-friendly and green of raw material sources, the preparation method is safe, can not bring pollution to environment; The diameter of the fibrous titanium dioxide of preparation is even, and the fibrous shape fiber of gained has regular pattern and structure;
Three, the fibrous shape titanium dioxide output of preparation method's preparation provided by the invention is large, productive rate can reach 100%, efficient is high, can produce in batch, and can again disperse, be prepared into film, or become new function material with fiber blend, have wide application prospects in directions such as super capacitor, solar cell, catalyzer.
Four, preparation method provided by the invention organic formwork used is the natural biomass fiber entirely, wide material sources, and cost is low.
Description of drawings
Fig. 1 is the photomacrograph figure of test 1 resulting overcut fibre shape titania fiber;
Fig. 2 is the scanning electron microscope (SEM) photograph of test 1 resulting overcut fibre shape titania fiber;
Fig. 3 is the high power scanning electron microscope (SEM) photograph of test 1 resulting overcut fibre shape titania fiber;
Fig. 4 is the X ray diffracting spectrum of the test 1 overcut fibre shape titania fiber that obtains, and wherein ■ is anatase titanium dioxide.
Embodiment
Embodiment one: a kind of method for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template of present embodiment, undertaken by following steps: one, with after natural fiber cleaning, drying, be dispersed in deionized water, obtain the natural fiber dispersion liquid; Wherein, natural fiber is the fiber of cotton, fiber crops, hair, silk or bamboo;
Two, obtain adding titanium tetrachloride in the natural fiber dispersion liquid to step 1, under the ice-water bath condition, with the stir speed (S.S.) of 50r/min～300r/min, carry out magnetic agitation 0.5～2h, obtain being attached with TiOH
3+The dispersion liquid of natural fiber;
Three, under the condition of ice-water bath, adhere to TiOH to what step 2 obtained
3+The dispersion liquid of natural fiber in add (NH
4)
2SO
4With mass percent be 1%～3% HCl solution, then carry out magnetic agitation 0.5～2h with the stir speed (S.S.) of 50r/min～300r/min, then heated and stirred, obtain being attached with TiOSO
4The dispersion liquid of natural fiber;
Four, be the TiOSO that adheres to that obtains in 25～28% ammoniacal liquor regulating steps three that are with volumetric molar concentration
4The pH value to 7～11 of dispersion liquid of natural fiber, after heated and stirred, then the standing 12～48h of at room temperature ageing filters, and gets solid formation, obtains being attached with the natural fiber of titanium dioxide;
Five, the natural fiber that is attached with titanium dioxide that obtains in step 4 is cleaned, obtain the hygrometric state natural fiber that is attached with titanium dioxide of nucleocapsid structure;
Six, the hygrometric state natural fiber that is attached with titanium dioxide with the nucleocapsid structure that obtains in step 5 carries out drying, obtain nucleocapsid structure organic-titania fiber;
Seven, with the nucleocapsid structure that obtains in step 6 organic-titania fiber, carry out high temperature sintering, namely obtain overcut fibre shape shape titanium dioxide after removing template, namely complete the preparation for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template; Wherein in step 1 the mass volume ratio of natural fiber and deionized water be (0.1g～3g): 100mL, in step 2, the ratio of the volume of the deionized water of titanium tetrachloride and step 1 is (1～5): 100; (NH in step 3
4)
2SO
4, mass percent is that the mol ratio of titanium tetrachloride in 1%～3% HCl solution and step 2 is 2: 10: 1.
A kind of overcut fibre shape titanium dioxide method for preparing take cellulosic fibre as template that present embodiment provides, have the following advantages: one, the length of the fibrous shape titanium dioxide prepared of existing method is 0.3 μ m～20 μ m, and the length of the fibrous titanium dioxide of the preparation method that present embodiment provides preparation can regulate and control according to the length of template, can reach 0.1mm～2cm;
Two, the preparation method that provides of present embodiment, preparation process is simple, does not need expensive device, extensive, the with low cost and environment-friendly and green of raw material sources, the preparation method is safe, can not bring pollution to environment; The diameter of the fibrous titanium dioxide of preparation is even, and the fibrous shape fiber of gained has regular pattern and structure;
Three, the fibrous shape titanium dioxide output of the preparation method preparation that provides of present embodiment is large, efficient is high, can produce in batch, and can again disperse, be prepared into film, or become new function material with fiber blend, have wide application prospects in directions such as super capacitor, solar cell, catalyzer.
Four, preparation method's organic formwork used of providing of present embodiment is the natural biomass fiber entirely, wide material sources, and cost is low.
Embodiment two: present embodiment is different from embodiment one is that the length of the natural fiber described in step 1 is grade or centimetre-sized, and diameter is at the fiber of cotton, fiber crops, hair, silk and the bamboo of 5～50 μ m.Other steps and parameter are identical with embodiment one.
Embodiment three: present embodiment is different from embodiment one or two is that cleaning in step 1 refers to make water or dehydrated alcohol to clean surface of natural fibers.Other steps and parameter are identical with embodiment one or two.
Embodiment four: present embodiment is different from one of embodiment one to three is that drying in step 1 refers to adopt dustless air-dry 48h.Other steps and parameter are identical with one of embodiment one to three.
Embodiment five: present embodiment is different from one of embodiment one to four is that heated and stirred concrete grammar in step 3 is as follows: at 95～99 ℃ of lower reflux 2h, stir speed (S.S.) is 50r/min～300r/min.Other steps and parameter are identical with one of embodiment one to four.
Embodiment six: present embodiment is different from one of embodiment one to five is that heated and stirred concrete grammar in the step step 4 is as follows: at 95～99 ℃ of lower reflux 1h, stir speed (S.S.) is 50r/min～300r/min.Other steps and parameter are identical with one of embodiment one to five.
Embodiment seven: present embodiment is different from one of embodiment one to six be the described purging method of step 5 for first washing with deionized water, then clean with dehydrated alcohol, repeat above-mentioned cleaning operation until do not measure Cl
-Till.Other steps and parameter are identical with one of embodiment one to six.
Embodiment eight: present embodiment is different from one of embodiment one to seven is that the method for the drying described in step 6 is vacuum lyophilization or the vacuum drying oven oven dry of 40～80 ℃.Other steps and parameter are identical with one of embodiment one to seven.
Embodiment nine: present embodiment is different from one of embodiment one to eight is that high temperature sintering concrete grammar in step 7 is: under air atmosphere, retort furnace is warmed up to 480～920 ℃ with 2 ℃/min, insulation 80～320min is cooled to 60 ℃ with 2 ℃/min.Other steps and parameter are identical with one of embodiment one to eight.
By following verification experimental verification beneficial effect of the present invention:
Test 1, a kind of method for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template of this test, undertaken by following steps:
One, with after cotton fiber cleaning, drying, be dispersed in deionized water, obtain the cotton fiber dispersion liquid;
Two, obtain adding the 5mL titanium tetrachloride in the cotton fiber dispersion liquid to step 1, under the ice-water bath condition, with the stir speed (S.S.) of 50r/min～300r/min, carry out magnetic agitation 0.5h, obtain being attached with TiOH
3+The dispersion liquid of cotton fiber;
Three, under the condition of ice-water bath, adhere to TiOH to what step 2 obtained
3+The dispersion liquid of cotton fiber in add (NH
4)
2SO
4With mass percent be 1%～3% HCl solution, then carry out magnetic agitation 0.5h with the stir speed (S.S.) of 50r/min～300r/min, then be heated to 95 ℃ and stir 2h, obtain being attached with TiOSO
4The dispersion liquid of cotton fiber;
Four, be the TiOSO that adheres to that obtains in the 25% ammoniacal liquor regulating step three that is with volumetric molar concentration
4The pH value to 7.5 of dispersion liquid of cotton fiber, be heated to 95 ℃ and stir 1h, with the standing 24h of at room temperature ageing of dispersion liquid, cross the cotton fiber that the leaching solid formation obtains being attached with titanium dioxide;
Five, the cotton fiber that is attached with titanium dioxide that obtains in step 4 is cleaned, obtain the hygrometric state cotton fiber that is attached with titanium dioxide of nucleocapsid structure; Purging method is: first wash 2 times with deionized water, and then clean 2 times with dehydrated alcohol, until till not measuring Cl-.
Six, with the hygrometric state cotton fiber that is attached with titanium dioxide of the nucleocapsid structure that obtains in step 5 60 ℃ of dryings 24 hours in vacuum drying oven, obtain nucleocapsid structure organic-titania fiber;
Seven, with the nucleocapsid structure that obtains in step 6 organic-titania fiber calcines 2h in 550 ℃ of air atmosphere in retort furnace, namely obtain overcut fibre shape shape titanium dioxide after removing template, namely complete the preparation for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template; Wherein in step 1, the mass volume ratio of natural fiber and deionized water is 0.5: 100mL; (NH in step 3
4)
2SO
4, mass percent is that the mol ratio of titanium tetrachloride in 1%～3% HCl solution and step 2 is 2: 10: 1.
The length of the overcut fibre shape shape titanium dioxide of this test preparation 〉=200 μ m, filamentary structure is intact, and the overcut fibre shape shape titanium dioxide that this test is prepared carries out SEM and XRD test, and result is as shown in Figure 1, Figure 2, Figure 3 and Figure 4.Fig. 1 is the photomacrograph figure of test 1 resulting overcut fibre shape titania fiber, and Fig. 2 is the low power scanning electron microscope (SEM) photograph of test 1 resulting overcut fibre shape titania fiber; Fig. 3 is the high power scanning electron microscope (SEM) photograph of test 1 resulting overcut fibre shape titania fiber; Fig. 4 is the X ray diffracting spectrum of the test 1 overcut fibre shape titania fiber that obtains, and wherein ■ is anatase titanium dioxide.
As shown in Figure 1, the titanium dioxide structural integrity after removing template still has fibrous texture; As shown in Figure 2, the titanium dioxide length of experiment preparation is at 0.5～1.5mm; As shown in Figure 3, the titanium dioxide diameter of experiment preparation is at 10～15 μ m, and whole fiber is to be formed by particle packing; Overcut fibre shape shape titanium dioxide to this test preparation carries out X-ray diffraction, result as shown in Figure 4, as shown in Figure 4, the titanium dioxide of experiment preparation is anatase structured.
Claims (9)
1. method for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template is characterized in that the method for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template undertaken by following steps:
One, with after natural fiber cleaning, drying, be dispersed in deionized water, obtain the natural fiber dispersion liquid; Wherein, natural fiber is the fiber of cotton, fiber crops, hair, silk or bamboo;
Two, obtain adding titanium tetrachloride in the natural fiber dispersion liquid to step 1, under the ice-water bath condition, with the stir speed (S.S.) of 50r/min～300r/min, carry out magnetic agitation 0.5～2h, obtain being attached with TiOH
3+The dispersion liquid of natural fiber;
Three, under the condition of ice-water bath, adhere to TiOH to what step 2 obtained
3+The dispersion liquid of natural fiber in add (NH
4)
2SO
4With mass percent be 1%～3% HCl solution, then carry out magnetic agitation 0.5～2h with the stir speed (S.S.) of 50r/min～300r/min, then heated and stirred, obtain being attached with TiOSO
4The dispersion liquid of natural fiber;
Four, be the TiOSO that adheres to that obtains in 25～28% ammoniacal liquor regulating steps three that are with volumetric molar concentration
4The pH value to 7～11 of dispersion liquid of natural fiber, after heated and stirred, then the standing 12～48h of at room temperature ageing filters, and gets solid formation, obtains being attached with the natural fiber of titanium dioxide;
Five, the natural fiber that is attached with titanium dioxide that obtains in step 4 is cleaned, obtain the hygrometric state natural fiber that is attached with titanium dioxide of nucleocapsid structure;
Six, the hygrometric state natural fiber that is attached with titanium dioxide with the nucleocapsid structure that obtains in step 5 carries out drying, obtain nucleocapsid structure organic-titania fiber;
Seven, with the nucleocapsid structure that obtains in step 6 organic-titania fiber, carry out high temperature sintering, namely obtain overcut fibre shape shape titanium dioxide after removing template, namely complete the preparation for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template; Wherein in step 1 the mass volume ratio of natural fiber and deionized water be (0.1g～3g): 100mL, in step 2, the ratio of the volume of the deionized water of titanium tetrachloride and step 1 is (1～5): 100; (NH in step 3
4)
2SO
4, mass percent is that the mol ratio of titanium tetrachloride in 1%～3% HCl solution and step 2 is 2: 10: 1.
2. a kind of method for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template according to claim 1, the length that it is characterized in that the natural fiber described in step 1 is grade or centimetre-sized, and diameter is at the fiber of cotton, fiber crops, hair, silk and the bamboo of 5～50 μ m.
3. a kind of method for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template according to claim 1 and 2, is characterized in that the cleaning in step 1 refers to make water or dehydrated alcohol to clean surface of natural fibers.
4. a kind of method for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template according to claim 1, is characterized in that the drying in step 1 refers to dustless air-dry 48h.
5. a kind of method for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template according to claim 1, it is characterized in that the heated and stirred concrete grammar in step 3 is as follows: at 95～99 ℃ of lower reflux 2h, stir speed (S.S.) is 50r/min～300r/min.
6. a kind of method for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template according to claim 1, it is characterized in that the heated and stirred concrete grammar in step 4 is as follows: at 95～99 ℃ of lower reflux 1h, stir speed (S.S.) is 50r/min～300r/min.
7. a kind of method for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template according to claim 1, it is characterized in that the described purging method of step 5 is for first washing with deionized water, then clean with dehydrated alcohol, repeat above-mentioned cleaning operation until do not measure Cl
-Till.
8. a kind of method for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template according to claim 1, the method that it is characterized in that the drying described in step 6 is that vacuum lyophilization or vacuum drying oven are dried under 40～80 ℃.
9. a kind of method for preparing overcut fibre shape titanium dioxide take cellulosic fibre as template according to claim 1, it is characterized in that the high temperature sintering concrete grammar in step 7 is: under air atmosphere, retort furnace is warmed up to 480～920 ℃ with 2 ℃/min, insulation 80～320min is cooled to 60 ℃ with 2 ℃/min.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104909405A (en) * | 2014-03-14 | 2015-09-16 | 中国科学院过程工程研究所 | Cellulose-based template based spindle-shaped nano-titanium dioxide and preparation method thereof |
| CN117886353A (en) * | 2024-03-15 | 2024-04-16 | 陕西燃气集团富平能源科技有限公司 | Method for preparing defective TiO by biological template method 2 Method for manufacturing micro-tube and defective TiO 2 Micro-tube and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051027A (en) * | 1989-10-17 | 1991-05-01 | 科尔-麦克基化学公司 | Produce the method for particulate titanium dioxide |
| CN1900410A (en) * | 2006-07-07 | 2007-01-24 | 陕西师范大学 | Method for preparing fiber with anti-violet and antibiotic property |
-
2013
- 2013-03-06 CN CN201310070778.5A patent/CN103121712B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1051027A (en) * | 1989-10-17 | 1991-05-01 | 科尔-麦克基化学公司 | Produce the method for particulate titanium dioxide |
| CN1900410A (en) * | 2006-07-07 | 2007-01-24 | 陕西师范大学 | Method for preparing fiber with anti-violet and antibiotic property |
Non-Patent Citations (1)
| Title |
|---|
| GIRI RABINDRA RAJ等: "A novel use of TiO2 fiber for photocatalytic ozonation of 2,4-dichlorophenoxyacetic acid in aqueous solution", 《JOURNAL OF ENVIRONMENTAL SCIENCES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104909405A (en) * | 2014-03-14 | 2015-09-16 | 中国科学院过程工程研究所 | Cellulose-based template based spindle-shaped nano-titanium dioxide and preparation method thereof |
| CN104909405B (en) * | 2014-03-14 | 2017-03-15 | 中国科学院过程工程研究所 | Spindle nano titanium oxide based on cellulose base template and preparation method thereof |
| CN117886353A (en) * | 2024-03-15 | 2024-04-16 | 陕西燃气集团富平能源科技有限公司 | Method for preparing defective TiO by biological template method 2 Method for manufacturing micro-tube and defective TiO 2 Micro-tube and application thereof |
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