CN103121712B - 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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- CN103121712B CN103121712B CN201310070778.5A CN201310070778A CN103121712B CN 103121712 B CN103121712 B CN 103121712B CN 201310070778 A CN201310070778 A CN 201310070778A CN 103121712 B CN103121712 B CN 103121712B
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- titanium dioxide
- natural fabric
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- dispersion liquid
- overcut
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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 preparing overcut fibre shape titanium dioxide.
Background technology
Natural biomass fiber is natural polymer, comprises string and animal fiber, is extensively present in occurring in nature.The main component of string is cellulose, is also called native cellulose fibre.It is the fiber obtained by seed, fruit, stem, leaf on plant etc.Except paper pulp fiber, according to the difference at the position of growing up on herbaceous plant, be also divided into: 1. seed fiber (cotton, kapok etc.); 2. leaf fibre (sisal hemp, abaca etc.); 3. fasciated fiber (ramie, flax, hemp, jute, bamboo etc.).Animal fiber is natural protein fibre, is divided into 1. hair classes: sheep's wool, goats hair, camel hair, 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 used as the Template preparation new material of inorganic matter, be cheap organic template material (comparatively electric spinning polymer fiber).Therefore, be badly in need of now carrying out new opplication exploitation to this type of biomass resource, prepare novel inorganic oxide material.
Inorganic nano-fiber has purposes widely in photoelectric material, sensor, insoluble drug release, single molecule probe, energy storage material, nerve signal detection etc.In recent years, multiple method is used for preparation inorganic fibrous material, comprises anodic oxidation, anodization, coating inorganic thing etc. on electrospinning fibre or copolymer template.But these method relative skill are complicated, and template cost is high, yield poorly and be difficult to a large amount of production, the fibrous material length that these methods are prepared is difficult to reach more than 15 μm.
CN1900410A discloses and a kind ofly prepares the method with uvioresistant, anti-microbial property fiber, said method comprising the steps of: ramee is added preliminary treatment in NaOH and dimethyl sulfoxide (DMSO), then pretreated ramee is added ultrasonic reaction in sodium chloroacetate, and adjust ph 2-3, add catalyst again, and carry out water treatment, finally add DMSO, absolute ethyl alcohol and Butyl Phthalate ultrasonic reaction, namely obtain the fiber with uvioresistant, anti-microbial property.
Summary of the invention
The present invention will solve the fibrous material length that existing method prepares to be difficult to reach more than 15 μm, and complex process, originate single, cost is high and the problem that yields poorly, providing a kind of is Template preparation overcut fibre shape titanium dioxide method with cellulose fibre.
The present invention is a kind of take cellulose fibre as the method for Template preparation overcut fibre shape titanium dioxide, is undertaken by following steps:
One, by after natural fabric cleaning, drying, dispersion in deionized water, obtains natural fabric dispersion liquid; Wherein, natural fabric is the fiber of cotton, fiber crops, hair, silk or bamboo;
Two, obtain adding titanium tetrachloride in natural fabric dispersion liquid to step one, under 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 fabric;
Three, under the condition of ice-water bath, to the attachment TiOH that step 2 obtains
3+natural fabric dispersion liquid in add (NH
4)
2sO
4hCl solution with mass percent is 1% ~ 3%, then carries out magnetic agitation 0.5 ~ 2h with the stir speed (S.S.) of 50r/min ~ 300r/min, then adds thermal agitation, obtain being attached with TiOSO
4the dispersion liquid of natural fabric;
Four, with the attachment TiOSO obtained in the molar concentration ammoniacal liquor regulating step three that to be 25 ~ 28% be
4pH value to 7 ~ 11 of dispersion liquid of natural fabric, after adding thermal agitation, at room temperature ageing leaves standstill 12 ~ 48h, then filters, gets solid formation, obtains the natural fabric being attached with titanium dioxide;
Five, the natural fabric being attached with titanium dioxide obtained in step 4 is cleaned, obtain the hygrometric state natural fabric being attached with titanium dioxide of nucleocapsid structure;
Six, the hygrometric state natural fabric being attached with titanium dioxide of the nucleocapsid structure obtained in step 5 is carried out drying, obtain nucleocapsid structure organic-titania fiber;
Seven, by 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 completing with cellulose fibre is the preparation of Template preparation overcut fibre shape titanium dioxide; Wherein in step one, the mass volume ratio of natural fabric and deionized water is (0.1g ~ 3g): 100mL, and in step 2, the ratio of the volume of the deionized water of titanium tetrachloride and step one is (1 ~ 5): 100; (NH in step 3
4)
2sO
4, mass percent be 1% ~ 3% HCl solution and step 2 in the mol ratio of titanium tetrachloride be 2:10:1.
One provided by the invention take cellulose fibre as Template preparation overcut fibre shape titanium dioxide method, has the following advantages:
One, the length of fibrous shape titanium dioxide that existing method is prepared is 0.3 μm ~ 20 μm, and the length of fibrous titanium oxide prepared by preparation method provided by the invention 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, and preparation method's security is high, can not bring pollution to environment; The uniform diameter of the fibrous titanium oxide of preparation, gained threadiness shape fiber has regular pattern and structure;
Three, the fibrous shape titanium dioxide output prepared of preparation method provided by the invention is large, productive rate can reach 100%, efficiency 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, catalyst.
Four, the organic formwork that preparation method provided by the invention is used is natural biomass fiber entirely, and wide material sources, cost is low.
Accompanying drawing explanation
The photomacrograph figure of the overcut fibre shape titania fiber that Fig. 1 obtains for test 1;
The scanning electron microscope (SEM) photograph of the overcut fibre shape titania fiber that Fig. 2 obtains for test 1;
The high power scanning electron microscope (SEM) photograph of the overcut fibre shape titania fiber that Fig. 3 obtains for test 1;
Fig. 4 is the X ray diffracting spectrum of the overcut fibre shape titania fiber that test 1 obtains, and wherein ■ is anatase titanium dioxide.
Detailed description of the invention
Detailed description of the invention one: present embodiment is a kind of take cellulose fibre as the method for Template preparation overcut fibre shape titanium dioxide, undertaken by following steps: one, by after natural fabric cleaning, drying, dispersion in deionized water, obtains natural fabric dispersion liquid; Wherein, natural fabric is the fiber of cotton, fiber crops, hair, silk or bamboo;
Two, obtain adding titanium tetrachloride in natural fabric dispersion liquid to step one, under 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 fabric;
Three, under the condition of ice-water bath, to the attachment TiOH that step 2 obtains
3+natural fabric dispersion liquid in add (NH
4)
2sO
4hCl solution with mass percent is 1% ~ 3%, then carries out magnetic agitation 0.5 ~ 2h with the stir speed (S.S.) of 50r/min ~ 300r/min, then adds thermal agitation, obtain being attached with TiOSO
4the dispersion liquid of natural fabric;
Four, with the attachment TiOSO obtained in the molar concentration ammoniacal liquor regulating step three that to be 25 ~ 28% be
4pH value to 7 ~ 11 of dispersion liquid of natural fabric, after adding thermal agitation, at room temperature ageing leaves standstill 12 ~ 48h, then filters, gets solid formation, obtains the natural fabric being attached with titanium dioxide;
Five, the natural fabric being attached with titanium dioxide obtained in step 4 is cleaned, obtain the hygrometric state natural fabric being attached with titanium dioxide of nucleocapsid structure;
Six, the hygrometric state natural fabric being attached with titanium dioxide of the nucleocapsid structure obtained in step 5 is carried out drying, obtain nucleocapsid structure organic-titania fiber;
Seven, by 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 completing with cellulose fibre is the preparation of Template preparation overcut fibre shape titanium dioxide; Wherein in step one, the mass volume ratio of natural fabric and deionized water is (0.1g ~ 3g): 100mL, and in step 2, the ratio of the volume of the deionized water of titanium tetrachloride and step one is (1 ~ 5): 100; (NH in step 3
4)
2sO
4, mass percent be 1% ~ 3% HCl solution and step 2 in the mol ratio of titanium tetrachloride be 2:10:1.
The one that present embodiment provides take cellulose fibre as Template preparation overcut fibre shape titanium dioxide method, have the following advantages: the length of fibrous shape titanium dioxide that one, existing method is prepared is 0.3 μm ~ 20 μm, and the length of fibrous titanium oxide prepared by the preparation method that present embodiment provides can regulate and control according to the length of template, 0.1mm ~ 2cm can be reached;
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, and preparation method's security is high, can not bring pollution to environment; The uniform diameter of the fibrous titanium oxide of preparation, gained threadiness shape fiber has regular pattern and structure;
Fibrous shape titanium dioxide output prepared by the preparation method that three, present embodiment provides is large, efficiency 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, catalyst.
Four, the organic formwork that the preparation method that provides of present embodiment is used is natural biomass fiber entirely, and wide material sources, cost is low.
Detailed description of the invention two: present embodiment and detailed description of the invention one are grade or Centimeter Level unlike the length of the natural fabric described in step one, diameter 5 ~ 50 μm cotton, fiber crops, hair, silk and bamboo fiber.Other steps are identical with detailed description of the invention one with parameter.
Detailed description of the invention three: present embodiment and detailed description of the invention one or two refer to unlike the cleaning in step one and use water or washes of absolute alcohol surface of natural fibers.Other steps are identical with detailed description of the invention one or two with parameter.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three refer to unlike the drying in step one and adopt dustless air-dry 48h.Other steps are identical with one of detailed description of the invention one to three with parameter.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four are as follows unlike the heating Stirring device body method in step 3: reflux heating 2h at 95 ~ 99 DEG C, and stir speed (S.S.) is 50r/min ~ 300r/min.Other steps are identical with one of detailed description of the invention one to four with parameter.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five are as follows unlike the heating Stirring device body method in step step 4: reflux heating 1h at 95 ~ 99 DEG C, and stir speed (S.S.) is 50r/min ~ 300r/min.Other steps are identical with one of detailed description of the invention one to five with parameter.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six for first to wash with deionized water, then use washes of absolute alcohol unlike the cleaning method described in step 5, repeats above-mentioned cleaning operation until do not measure Cl-.Other steps are identical with one of detailed description of the invention one to six with parameter.
Detailed description of the invention eight: one of present embodiment and detailed description of the invention one to seven are vacuum freeze drying unlike the method for the drying described in step 6 or dry at the vacuum drying oven of 40 ~ 80 DEG C.Other steps are identical with one of detailed description of the invention one to seven with parameter.
Detailed description of the invention nine: one of present embodiment and detailed description of the invention one to eight unlike the high temperature sintering concrete grammar in step 7 are: under air atmosphere, Muffle furnace is warmed up to 480 ~ 920 DEG C with 2 DEG C/min, insulation 80 ~ 320min, is cooled to 60 DEG C with 2 DEG C/min.Other steps are identical with one of detailed description of the invention one to eight with parameter.
By following verification experimental verification beneficial effect of the present invention:
Test 1, this test is a kind of take cellulose fibre as the method for Template preparation overcut fibre shape titanium dioxide, is undertaken by following steps:
One, by after cotton fiber cleaning, drying, dispersion in deionized water, obtains cotton fiber dispersion liquid;
Two, obtain adding 5mL titanium tetrachloride in cotton fiber dispersion liquid to step one, under ice-water bath condition, with the stir speed (S.S.) of 50r/min ~ 300r/min, carry out magnetic agitation 0.5h, obtain the dispersion liquid of the cotton fiber being attached with TiOH3+;
Three, under the condition of ice-water bath, to the attachment TiOH that step 2 obtains
3+cotton fiber dispersion liquid in add (NH
4)
2sO
4hCl solution with mass percent is 1% ~ 3%, then carries out magnetic agitation 0.5h with the stir speed (S.S.) of 50r/min ~ 300r/min, is then heated to 95 DEG C and stirs 2h, obtain being attached with TiOSO
4the dispersion liquid of cotton fiber;
Four, by molar concentration be the attachment TiOSO obtained in the 25% ammoniacal liquor regulating step three being
4the pH value to 7.5 of dispersion liquid of cotton fiber, be heated to 95 DEG C and stir 1h, dispersion liquid at room temperature ageing is left standstill 24h, cross leaching solid formation and obtain the cotton fiber being attached with titanium dioxide;
Five, the cotton fiber being attached with titanium dioxide obtained in step 4 is cleaned, obtain the hygrometric state cotton fiber being attached with titanium dioxide of nucleocapsid structure; Cleaning method is: first wash 2 times with deionized water, and then with washes of absolute alcohol 2 times, till not measuring Cl-.
Six, by the 60 DEG C of dryings 24 hours in vacuum drying oven of the hygrometric state cotton fiber being attached with titanium dioxide of the nucleocapsid structure obtained in step 5, obtain nucleocapsid structure organic-titania fiber;
Seven, by the nucleocapsid structure obtained in step 6 organic-titania fiber calcines 2h in Muffle furnace in 550 DEG C of air atmosphere, namely obtain overcut fibre shape shape titanium dioxide after removing template, namely completing with cellulose fibre is the preparation of Template preparation overcut fibre shape titanium dioxide; Wherein in step one, the mass volume ratio of natural fabric and deionized water is 0.5:100mL; (NH in step 3
4)
2sO
4, mass percent be 1% ~ 3% HCl solution and step 2 in the mol ratio of titanium tetrachloride be 2:10:1.
Length >=200 μm of the overcut fibre shape shape titanium dioxide of this test preparation, filamentary structure is intact, and carry out SEM and XRD test to the overcut fibre shape shape titanium dioxide of this test preparation, result as shown in Figure 1, Figure 2, Figure 3 and Figure 4.The photomacrograph figure of the overcut fibre shape titania fiber that Fig. 1 obtains for test 1, the low power scanning electron microscope (SEM) photograph of the overcut fibre shape titania fiber that Fig. 2 obtains for test 1; The high power scanning electron microscope (SEM) photograph of the overcut fibre shape titania fiber that Fig. 3 obtains for test 1; Fig. 4 is the X ray diffracting spectrum of the overcut fibre shape titania fiber that test 1 obtains, and wherein ■ is anatase titanium dioxide.
As shown in Figure 1, the titania structure after removing template is complete, still has fibre structure; 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 μm, and whole fiber is formed by particle packing; Carry out X-ray diffraction to the overcut fibre shape shape titanium dioxide of this test preparation, as shown in Figure 4, as shown in Figure 4, the titanium dioxide of experiment preparation is anatase structured to result.
Claims (9)
1. be a method for Template preparation overcut fibre shape titanium dioxide with cellulose fibre, it is characterized in that being that the method for Template preparation overcut fibre shape titanium dioxide is undertaken by following steps with cellulose fibre:
One, by after natural fabric cleaning, drying, dispersion in deionized water, obtains natural fabric dispersion liquid; Wherein, natural fabric is the fiber of cotton, fiber crops, hair, silk or bamboo;
Two, obtain adding titanium tetrachloride in natural fabric dispersion liquid to step one, under 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 fabric;
Three, under the condition of ice-water bath, to the attachment TiOH that step 2 obtains
3+natural fabric dispersion liquid in add (NH
4)
2sO
4hCl solution with mass percent is 1% ~ 3%, then carries out magnetic agitation 0.5 ~ 2h with the stir speed (S.S.) of 50r/min ~ 300r/min, then adds thermal agitation, obtain being attached with TiOSO
4the dispersion liquid of natural fabric;
Four, by molar concentration be 25 ~ 28% ammoniacal liquor regulating step three in the attachment TiOSO that obtains
4pH value to 7 ~ 11 of dispersion liquid of natural fabric, after adding thermal agitation, at room temperature ageing leaves standstill 12 ~ 48h, then filters, gets solid formation, obtains the natural fabric being attached with titanium dioxide;
Five, the natural fabric being attached with titanium dioxide obtained in step 4 is cleaned, obtain the hygrometric state natural fabric being attached with titanium dioxide of nucleocapsid structure;
Six, the hygrometric state natural fabric being attached with titanium dioxide of the nucleocapsid structure obtained in step 5 is carried out drying, obtain nucleocapsid structure organic-titania fiber;
Seven, by the nucleocapsid structure that obtains in step 6 organic-titania fiber, carry out high temperature sintering, namely obtain overcut fibre shape titanium dioxide after removing template, namely completing with cellulose fibre is the preparation of Template preparation overcut fibre shape titanium dioxide; Wherein in step one, the mass volume ratio of natural fabric and deionized water is (0.1g ~ 3g): 100mL, and in step 2, the volume ratio of the deionized water of titanium tetrachloride and step one is (1 ~ 5): 100; (NH in step 3
4)
2sO
4, mass percent be 1% ~ 3% HCl solution and step 2 in the mol ratio of titanium tetrachloride be 2: 10: 1.
2. according to claim 1 a kind of take cellulose fibre as the method for Template preparation overcut fibre shape titanium dioxide, it is characterized in that the length of the natural fabric described in step one is grade or Centimeter Level, diameter 5 ~ 50 μm cotton, fiber crops, hair, silk and bamboo fiber.
3. according to claim 1 and 2 a kind of take cellulose fibre as the method for Template preparation overcut fibre shape titanium dioxide, the cleaning that it is characterized in that in step one refers to and uses water or washes of absolute alcohol surface of natural fibers.
4. according to claim 1 a kind of take cellulose fibre as the method for Template preparation overcut fibre shape titanium dioxide, it is characterized in that the drying in step one refers to dustless air-dry 48h.
5. according to claim 1 a kind of take cellulose fibre as the method for Template preparation overcut fibre shape titanium dioxide, it is characterized in that the heating Stirring device body method in step 3 is as follows: reflux heating 2h at 95 ~ 99 DEG C, stir speed (S.S.) is 50r/min ~ 300r/min.
6. according to claim 1 a kind of take cellulose fibre as the method for Template preparation overcut fibre shape titanium dioxide, it is characterized in that the heating Stirring device body method in step 4 is as follows: at 95 ~ 99 DEG C, add hot reflux 1h, stir speed (S.S.) is 50r/min ~ 300r/min.
7. according to claim 1 a kind of take cellulose fibre as the method for Template preparation overcut fibre shape titanium dioxide, it is characterized in that cleaning method described in step 5 is for first to wash with deionized water, then use washes of absolute alcohol, repeat above-mentioned cleaning operation until do not measure Cl
-till.
8. according to claim 1 a kind of take cellulose fibre as the method for Template preparation overcut fibre shape titanium dioxide, it is characterized in that the method for the drying described in step 6 is that vacuum freeze drying or vacuum drying oven are dried at 40 ~ 80 DEG C.
9. according to claim 1 a kind of take cellulose fibre as the method for Template preparation overcut fibre shape titanium dioxide, it is characterized in that the high temperature sintering concrete grammar in step 7 is: under air atmosphere, Muffle furnace is warmed up to 480 ~ 920 DEG C with 2 DEG C/min, insulation 80 ~ 320min, is cooled to 60 DEG C with 2 DEG C/min.
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| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1900410A (en) * | 2006-07-07 | 2007-01-24 | 陕西师范大学 | Method for preparing fiber with anti-violet and antibiotic property |
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| US5030439A (en) * | 1989-10-17 | 1991-07-09 | Kerr-Mcgee Chemical Corporation | Method for producing particulate titanium oxides |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| 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 |
|---|
| A novel use of TiO2 fiber for photocatalytic ozonation of 2,4-dichlorophenoxyacetic acid in aqueous solution;GIRI Rabindra Raj等;《Journal of Environmental Sciences》;20081231;第20卷;第1138-1145页 * |
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