CN103641165B - Method for preparing titanium dioxide nanotube by using natural mineral as formwork - Google Patents

Method for preparing titanium dioxide nanotube by using natural mineral as formwork Download PDF

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CN103641165B
CN103641165B CN201310684032.3A CN201310684032A CN103641165B CN 103641165 B CN103641165 B CN 103641165B CN 201310684032 A CN201310684032 A CN 201310684032A CN 103641165 B CN103641165 B CN 103641165B
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attapulgite
solution
nanotube
tio
distilled water
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CN103641165A (en
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孙露
严春杰
刘易彪
王洪权
王群英
李丹
张飞霞
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China University of Geosciences
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Abstract

The invention discloses a method for preparing titanium dioxide nanotube by using natural mineral as a formwork. The method comprises the following steps: modifying natural attapulgite which is used as the formwork, loading a titanium source on the surface of the attapulgite by virtue of a sol-gel method so as to obtain a titanium source-attapulgite mixture, calcining the titanium source-attapulgite mixture at a high temperature to obtain an attapulgite/TiO2 compound, reacting a NaOH solution with the attapulgite/TiO2 compound so as to remove the attapulgite formwork to obtain the TiO2 nanotube with a formwork structure feature. According to the natural attapulgite is used as the formwork, and the TiO2 nanotube is prepared by combining a formwork method and the sol-gel method. The attapulgite in the method is a natural substance and is wide in source and low in cost, the process flow is simple and easy to operate, the preparation cost is low, and the obtained TiO2 nanotube has good property.

Description

A kind of take natural mineral as the method for Template preparation titania nanotube
Technical field
The present invention relates to a kind of take natural mineral as the method for Template preparation titania nanotube, and refering in particular to natural attapulgite is the method for Template preparation titania nanotube, belongs to titania nanotube technical field.
Technical background
Titanium dioxide is a kind of important inorganic functional material, and it has broad application prospects in storage of solar energy and utilization, opto-electronic conversion, photochromic and photocatalytic degradation air and water pollutant etc.The raw material resources of titanium dioxide is abundant, low price and toxicological harmless, is the focus studied in the world in recent years.As one of the existence form of titanium dioxide, titania nanotube has larger specific surface area and stronger adsorptive power, thus higher hydrogen-sensitivity, electricity conversion and photocatalysis performance is shown, make it in gas sensing materials, solar cell, photochemical catalysis etc., have immeasurable potential using value, attract the extensive concern of various countries' researcher, have the preparation of a large amount of bibliographical informations titania nanotube and the research of application aspect thereof.
TiO 2the preparation method of nanotube mainly contains anonizing, hydrothermal method and template.Wherein, anonizing prepares the most frequently used, the easiest method of titania nanotube.But the titania nanotube adopting anonizing to prepare is attached in titanium sheet, this makes it be subject to certain restrictions in application, and the cost of the method is higher.Hydrothermal method can obtain the less TiO of caliber 2nanotube, and operating procedure is comparatively simple, but the scale topography of nanotube prepared by hydrothermal method and constitutional features depend on raw material TiO largely 2the size of particulate and crystalline phase, and hydrothermal method require that equipment is wanted can high temperature resistant and high pressure, thus to material with safety requirements is comparatively strict and cost is higher.
Template synthesis TiO 2nanotube is exactly utilize the material of a certain special appearance as template, then the technology such as combined with electrochemical method, vapour deposition process and sol-gel method prepares TiO 2nanotube.Li Xiaohong etc. (Li Xiaohong etc. SCI, 2001) with porous alumina (PAA) for template, prepare Detitanium-ore-type TiO in conjunction with sol-gel method 2nanotube, the caliber of obtained nanotube is 100nm, and thickness of pipe is 10nm.Test shows that the length of this nanotube, aperture and thickness of pipe can regulate according to template, and the time that control PAA template is immersed in colloidal solution can control TiO 2the length of nanotube and thickness of pipe.Michalloowski A etc. (Michail O.Aetal.Chemical Physics Letters, 2001) are with porous anodic aluminium oxide (PAO) for template, and preparing caliber is 50nm ~ 70nm, and wall thickness is the TiO of 3nm 2nanotube.The nanotube pattern rule obtained, the nanotube that performance is prepared with sol-gel method under being better than square one.Jong H.G etc. (Jong H J etal.Chem.Mater., 2002), using organogel as template, prepare spiral shape TiO 2the double-deck TiO of 8nm ~ 9nm is about with interlamellar spacing 2nanotube.The people (Dongxia Liu etal.Langmuir, 2007) such as Dongxia Liu with homemade bar-shaped calcite for Template preparation obtains the TiO of different tube diameters 2nanotube.These methods above-mentioned template used all needs to prepare in advance, and this makes preparation process become complicated to a great extent, adds preparation cost, thus limits these methods for TiO 2the extensive preparation of nanotube.Therefore, adopt easy method, prepare TiO with material cheap and easy to get 2nanotube becomes a kind of necessary.
Up to the present, be template with natural attapulgite, the method utilizing template to combine with sol-gel method is to prepare TiO 2the technology of nanotube there is not yet report.
Summary of the invention
The invention provides a kind of take natural mineral as the method for Template preparation titania nanotube, and the method take natural attapulgite as template, and the technology adopting template to combine with sol-gel method prepares TiO 2nanotube.Attapulgite in the method is crude substance, wide material sources and cheap, and technical process is simple to operation, and preparation cost is low, the TiO obtained 2nanotube performance is good.
Realizing the technical scheme that the object of the invention takes is:
Take natural mineral as a method for Template preparation titania nanotube, comprise the steps:
1) according to attapulgite: HCl solution, HNO 3solution or H 2sO 4the mass volume ratio of solution=1g:10mL ~ 1g:20mL, joins HCl solution, HNO that concentration is 1mol/L ~ 5mol/L by attapulgite 3solution or H 2sO 4in solution, stir under 60 DEG C ~ 70 DEG C conditions and modification was carried out to attapulgite in 2 ~ 3 hours, after filtration, obtain the attapulgite of modification, then the attapulgite of modification washed to neutrality and dry under 80 DEG C ~ 105 DEG C conditions;
2) attapulgite that is dry, modification is added in propyl carbinol, ultrasonic disperse makes attapulgite be well-dispersed in propyl carbinol, then cetyl trimethylammonium bromide and distilled water is added, stirring obtains attapulgite suspension, and wherein the ratio of attapulgite, propyl carbinol, cetyl trimethylammonium bromide and distilled water is attapulgite: propyl carbinol: cetyl trimethylammonium bromide: distilled water=1g:750mL ~ 1000mL:1g ~ 3g:25mL ~ 125mL;
3) obtain with propyl carbinol dilution tetrabutyl titanate the titanium precursor solution that concentration is 0.10 ~ 0.25mol/L, enough titanium precursor solution are added drop-wise in attapulgite suspension with the speed of 0.8mL/ hour ~ 5mL/ hour, stir and carry out condensation reaction in 12 ~ 15 hours, after having reacted, straight alcohol dispensing laundry is used by after the solution centrifugal of reaction gained, dry in a vacuum again, obtain titanium source-attapulgite mixture, wherein centrifugal rotating speed >=8000 rev/min;
4) titanium source-attapulgite mixture is calcined 2 ~ 3 hours under 350 DEG C ~ 950 DEG C conditions, then the product after calcining is cooled to room temperature, obtains TiO 2-attapulgite mixture;
5) by TiO 2it is in the NaOH solution of 2mol/L ~ 4mol/L that-attapulgite mixture joins enough concentration, react 2 ~ 3 hours under 70 DEG C ~ 90 DEG C water-baths and agitation condition, after having reacted, use distilled water dispensing laundry by after the solution centrifugal of reaction gained, last dry in a vacuum, obtain TiO 2nanotube, wherein centrifugal rotating speed>=8000 rev/min.
Technique scheme is further improved, step 2) in cetyl trimethylammonium bromide and distilled water addition sequence after first adding cetyl trimethylammonium bromide, add distilled water again; Repeat twice with straight alcohol dispensing laundry react the solution centrifugal of gained in step 3) to major general after; Step 4) in the calcining temperature of titanium source-attapulgite mixture be 550 DEG C ~ 950 DEG C; Repeat twice with distilled water dispensing laundry react the solution centrifugal of gained in step 5) to major general after.
Compared with prior art, advantage of the present invention and beneficial effect are:
1) the method processing step is simple to operation, and processing condition are simple and easy to control, required equipment and preparation cheap, preparation TiO 2with low cost needed for nanotube, is applicable to suitability for industrialized production.
2) template needed for the method is natural attapulgite, wide material sources and cheap.Attapulgite is a kind of Shuifu County's magnesium silicate that contains of tool fiber pattern layer chain transition structure is main clay mineral, and have natural nano-scale fiber profile, diameter, in nanometer range, is typical monodimension nanometer material.Use natural attapulgite just not need to prepare template in advance, save the human and material resources of preparation needed for template and time, saved preparation cost, simplified preparation technology's flow process.
3) attapulgite is zeopan, it can react with HF or NaOH, attapulgite as template is easy to just be removed, the titanium dioxide being carried on attapulgite surface just has attapulgite constitutional features after removing attapulgite template, namely obtains the TiO with attapulgite constitutional features 2nanotube.
4) show after tested, adopt TiO prepared by the present invention 2nanotube purity is high, and external diameter is about 20nm, and length is that hundreds of nanometer is to several microns.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of attapulgite.
Fig. 2 is the transmission electron microscope picture of attapulgite.
Fig. 3 is TiO prepared by embodiment 1 2the XRD figure spectrum of nanotube.
Fig. 4 is TiO prepared by embodiment 1 2the scanning electron microscope (SEM) photograph of nanotube.
Fig. 5 is TiO prepared by embodiment 1 2the transmission electron microscope picture of nanotube.
Fig. 6 is the EDS spectrogram of attapulgite.
Fig. 7 is TiO prepared by embodiment 1 2the EDS spectrogram of nanotube.
Fig. 8 is TiO prepared by embodiment 2 2the XRD figure spectrum of nanotube.
Fig. 9 is TiO prepared by embodiment 3 2the XRD figure spectrum of nanotube.
Figure 10 is that embodiment 4 prepares TiO 2the XRD figure spectrum of nanotube.
Embodiment
Embodiment 1
1) take attapulgite 10.00g, being joined 150mL concentration is in the HCl solution of 5mol/L, stirs 2 hours at 70 DEG C of condition lower magnetic forces, filter the attapulgite obtaining modification, again that the washing of the attapulgite of modification is extremely neutral, dry 24 hours in an oven, the temperature arranging baking oven is 80 DEG C;
2) take 0.04g drying, the attapulgite of modification joins in 32mL propyl carbinol, ultrasonic disperse, after 5 minutes, adds 0.04g cetyl trimethylammonium bromide and 1mL distilled water successively, slowly stirs after 45 minutes and obtains attapulgite suspension;
3) obtain with 20mL propyl carbinol dilution tetrabutyl titanate the titanium precursor solution that concentration is 0.10mol/L, again titanium precursor solution is added drop-wise in attapulgite suspension with the speed of 0.8mL/ hour, stir and carry out condensation reaction in 12 hours, after having reacted, first by the solution under 8000 revs/min of conditions centrifugal 5 minutes of reaction gained, then dispensing laundry in straight alcohol, in centrifugal and straight alcohol, the step of dispensing laundry in triplicate, dry in a vacuum again, obtain titanium source-attapulgite mixture;
4) titanium source-attapulgite mixture is placed in retort furnace and calcines, the temperature rise rate arranging stove is 10 DEG C/min, is warming up to 550 DEG C and is incubated 2 hours, then the product after calcining is naturally cooled to room temperature, obtains TiO 2-attapulgite mixture;
5) by TiO 2it is in the NaOH solution of 2mol/L that-attapulgite mixture joins concentration, react 2 hours under 80 DEG C of water-baths and agitation condition, after having reacted, first by the solution under 8000 revs/min of conditions centrifugal 5 minutes of reaction gained, dispensing laundry in distilled water again, the step of centrifugal and distilled water dispensing laundry is in triplicate, finally dry in a vacuum, obtains TiO2 nanotube.
Fig. 1 is the scanning electron microscope (SEM) photograph of attapulgite, and as can be seen from the figure attapulgite is based on club shaped structure, can't see other impurity, but the dispersiveness of attapulgite is not fine, has the phenomenon of reunion.
Fig. 2 is the transmission electron microscope picture of attapulgite, can observe the club shaped structure that attapulgite is one dimension clearly from figure, and the diameter of rod is all at about 10nm, and the length of rod is that hundreds of nanometer is to several microns.
Fig. 3 is TiO prepared by the present embodiment 2the XRD figure spectrum of nanotube, as can be seen from the figure this spectral line is that 25.2 °, 37.8 ° and 48.1 ° of places have 3 obvious absorption peaks at 2 θ, these three absorption peaks corresponding Detitanium-ore-type TiO respectively 2the feature diffraction of (101004200) crystal face, the particularly diffraction peak in (101) face, there is certain preferred orientation, show prepared sample mainly Anatase crystal, carry out retrieval through XRD software to learn: this collection of illustrative plates meets PDF card 89-4921, prepared sample is the TiO of Detitanium-ore-type 2nanotube.
Fig. 4 is TiO prepared by the present embodiment 2the scanning electron microscope (SEM) photograph of nanotube, as can be seen from the figure TiO 2mainly present tubular shape, the bonding phenomenon between tube and tube is relatively more serious, and this is mainly because attapulgite template has obvious agglomeration.
Fig. 5 is TiO prepared by the present embodiment 2the transmission electron microscope picture of nanotube, as can be seen from the figure prepared TiO 2clearly, its external diameter is about 20nm to the tubulose feature of nanotube, length be hundreds of nanometer to several microns, have very similar shape and diameter dimension with attapulgite.This illustrate prepared by TiO 2nanotube make use of this template of attapulgite well, in the process of carrying out collosol and gel, most titanium precursors is the outside surface being deposited on attapulgite template by the connection of CTAB, through calcining with after sloughing attapulgite template, is deposited on the TiO on attapulgite surface 2just define the tubular structure of hollow, namely define TiO 2nanotube.
Fig. 6 is the EDS spectrogram of attapulgite raw ore sample, and not containing titanium elements in the Chemical Composition of as can be seen from the figure attapulgite, its composition is (At%): O=61.68%, Si=23.62%, Mg=5.11%, Al=4.13%.
Fig. 7 is TiO 2the EDS spectrogram of nanotube, as can be seen from the figure, the Chemical Composition sloughing the nanotube after template is (At%): Ti=61.27%, O=19.41.68%, Au=4.63%, Cu=9.33%, Si=2.90%, C=2.47%.The wherein gold that sprays when sample preparation of Au element source, Cu element source is in loading copper platform, and C element derives from the conductive resin of sample preparation, is due to prepared TiO containing a small amount of Si in sample 2the specific surface area of nanotube is very large, and it adsorbs a small amount of Si on its surface, so only containing a large amount of Ti elements and O element in prepared sample, namely prepared material is TiO 2nanotube.
Known by analyzing above: take natural attapulgite as template, tetrabutyl titanate is titanium source, the method adopting sol-gel method and template to combine, has successfully prepared the highly purified TiO with natural attapulgite constitutional features 2nanotube.
Embodiment 2
1) take attapulgite 10.00g, being joined 150mL concentration was in the HCl solution of 1mol/L, 60 DEG C of magnetic agitation 3 hours, filter the attapulgite obtaining modification, washed to neutrality by the attapulgite of modification, dry 24 hours in an oven, the temperature arranging baking oven is 95 DEG C again;
2) take 0.04g drying, the attapulgite of gained of modification joins in 40mL propyl carbinol, ultrasonic disperse, after 5 minutes, adds 0.04g cetyl trimethylammonium bromide and 3mL distilled water successively, slowly stirs after 45 minutes and obtains attapulgite suspension;
3) obtain with 20mL propyl carbinol dilution tetrabutyl titanate the titanium precursor solution that concentration is 0.10mol/L, again titanium precursor solution is added drop-wise to step 2 with the speed of 2mL/ hour) in the attapulgite suspension that obtains, stir and carry out condensation reaction in 13 hours, after having reacted, by the solution under 8000 revs/min of conditions centrifugal 5 minutes of reaction gained, then dispensing laundry in straight alcohol, in centrifugal and straight alcohol, the step of dispensing laundry in triplicate, dry in a vacuum again, obtain titanium source-attapulgite mixture;
4) calcined in retort furnace by titanium source-attapulgite mixture, the temperature rise rate arranging stove is 10 DEG C/min, is warming up to 350 DEG C and is incubated 3 hours, then the product after calcining is naturally cooled to room temperature, obtains TiO 2-attapulgite mixture;
5) by TiO 2it is in the NaOH solution of 3mol/L that-attapulgite mixture joins concentration, react 3 hours under 70 DEG C of water-baths and agitation condition, after having reacted, first by the solution under 8000 revs/min of conditions centrifugal 5 minutes of reaction gained, dispensing laundry in distilled water again, in centrifugal and distilled water, the step of dispensing laundry in triplicate, finally dry in a vacuum, obtains TiO 2nanotube.
Product prepared by the present embodiment is through scanning electron microscope, transmission electron microscope and XRD analysis, and result display product is TiO 2for nanotube.
Fig. 8 is TiO prepared by the present embodiment 2the XRD figure spectrum of nanotube, as can be seen from the figure this spectral line is that 25.2 °, 37.8 ° and 48.1 ° of places have 3 faint absorption peaks, these three absorption peaks corresponding Detitanium-ore-type TiO respectively at 2 θ 2the feature diffraction of (101004200) crystal face.Because these three absorption peaks are very faint, the TiO obtained after 350 DEG C of calcinings is described 2the degree of crystallinity of nanotube is bad.
Embodiment 3
1) take attapulgite 10.00g, being joined 150mL concentration was in the HCl solution of 5mol/L, 70 DEG C of magnetic agitation 3 hours, filter the attapulgite obtaining modification, again that the washing of the attapulgite of modification is extremely neutral, dry 24 hours in an oven, the temperature arranging baking oven is 100 DEG C;
2) taking 0.04 attapulgite that is dry, modification joins in 50mL propyl carbinol, and ultrasonic disperse, after 5 minutes, adds 0.12g cetyl trimethylammonium bromide and 5mL distilled water successively, slowly stirs after 45 minutes and obtains attapulgite suspension;
3) obtain with 20mL propyl carbinol dilution tetrabutyl titanate the titanium precursor solution that concentration is 0.10mol/L, again titanium precursor solution is added drop-wise in attapulgite suspension with the speed of 4mL/ hour, stir and carry out condensation reaction in 14 hours, after having reacted, first by the solution under 8000 revs/min of conditions centrifugal 5 minutes of reaction gained, then dispensing laundry in straight alcohol, in centrifugal and straight alcohol, the step of dispensing laundry in triplicate, dry in a vacuum again, obtain titanium source-attapulgite mixture;
4) calcined in retort furnace by titanium source-attapulgite mixture, the temperature rise rate arranging stove is 10 DEG C/min, is warming up to 750 DEG C and is incubated 3 hours, then the product after calcining is naturally cooled to room temperature, obtains TiO 2-attapulgite mixture;
5) by TiO 2it is in the NaOH solution of 4mol/L that-attapulgite mixture joins concentration, react 3 hours under 90 DEG C of water-baths and agitation condition, first by the solution under 8000 revs/min of conditions centrifugal 5 minutes of reaction gained, dispensing laundry in distilled water again, the step of centrifugal and distilled water dispensing laundry in triplicate, last dry in a vacuum, obtain TiO 2nanotube.
Product prepared by the present embodiment is through scanning electron microscope, transmission electron microscope and XRD analysis, and result display product is TiO 2for nanotube.
Fig. 9 is TiO prepared by the present embodiment 2the XRD figure spectrum of nanotube, as can be seen from the figure, except corresponding to Detitanium-ore-type TiO 2the characteristic diffraction peak of (101004200) crystal face become more by force, more sharp-pointed outside, also there is in 2 θ=27.4 ° the peak that intensity is more weak in collection of illustrative plates, the feature diffraction of its Rutile Type corresponded to (110) crystal face.
Embodiment 4
1) attapulgite 10.00g is taken, being joined 150mL concentration is in the HCl solution of 1mol/L, 70 DEG C of magnetic agitation 2 hours, then filter the attapulgite obtaining modification, finally by the washing of the attapulgite of modification to neutral and dry 24 hours under 105 DEG C of conditions in an oven;
2) take 0.04g drying, the attapulgite of modification joins in 32mL propyl carbinol, ultrasonic disperse, after 5 minutes, adds 0.04g cetyl trimethylammonium bromide and 1mL distilled water successively, slowly stirs after 45 minutes and obtains attapulgite suspension;
3) obtain with 20mL propyl carbinol dilution tetrabutyl titanate the titanium precursor solution that concentration is 0.25mol/L, again titanium precursor solution is added drop-wise in attapulgite suspension with the speed of 5mL/ hour, stir and carry out condensation reaction in 15 hours, after having reacted, first by the solution under the condition of 8000 revs/min centrifugal 5 minutes of reaction gained, then dispensing laundry in straight alcohol, in centrifugal and straight alcohol, the step of dispensing laundry in triplicate, dry in a vacuum again, obtain titanium source-attapulgite mixture;
4) calcined in retort furnace by titanium source-attapulgite mixture, the temperature rise rate arranging stove is 10 DEG C/min, is warming up to 950 DEG C and is incubated 3 hours, the product after calcining is naturally cooled to room temperature, obtains TiO 2-attapulgite mixture;
5) by TiO 2it is in the NaOH solution of 3mol/L that-attapulgite mixture joins concentration, react 2 hours under 70 DEG C of water-baths and agitation condition, after having reacted, first by the solution under 8000 revs/min of conditions centrifugal 5 minutes of reaction gained, dispensing laundry in distilled water again, in centrifugal and distilled water, the step of dispensing laundry in triplicate, finally dry in a vacuum, obtains TiO 2nanotube.
Product prepared by the present embodiment is through scanning electron microscope, transmission electron microscope and XRD analysis, and result display product is TiO 2for nanotube.
Figure 10 is TiO prepared by this example 2the XRD figure spectrum of nanotube, as can be seen from the figure, the diffracted intensity of Anatase (101004200) crystal face greatly declines, the diffracted intensity of Rutile Type (110) crystal face strengthens greatly, and in 2 θ=36.1 ° and 2 θ=54.3 ° there is new characteristic peak, it is corresponding Rutile Type (101211) crystal face respectively.
HCl solution in embodiment 1, embodiment 2, embodiment 3 and embodiment 4 can use HNO 3solution or H 2sO 4solution replaces.

Claims (5)

1. be a method for Template preparation titania nanotube with natural mineral, it is characterized in that comprising the steps:
1) according to attapulgite: HCl solution, HNO 3solution or H 2sO 4the mass volume ratio of solution=1g:10mL ~ 1g:20mL, joins HCl solution, HNO that concentration is 1mol/L ~ 5mol/L by attapulgite 3solution or H 2sO 4in solution, stir under 60 DEG C ~ 70 DEG C conditions and modification was carried out to attapulgite in 2 ~ 3 hours, after filtration, obtain the attapulgite of modification, then the attapulgite of modification washed to neutrality and dry under 80 DEG C ~ 105 DEG C conditions;
2) attapulgite that is dry, modification is added in propyl carbinol, ultrasonic disperse makes attapulgite be well-dispersed in propyl carbinol, then cetyl trimethylammonium bromide and distilled water is added, stirring obtains attapulgite suspension, and wherein the ratio of attapulgite, propyl carbinol, cetyl trimethylammonium bromide and distilled water is attapulgite: propyl carbinol: cetyl trimethylammonium bromide: distilled water=1g:750mL ~ 1000mL:1g ~ 3g:25mL ~ 125mL;
3) obtain with propyl carbinol dilution tetrabutyl titanate the titanium precursor solution that concentration is 0.10 ~ 0.25mol/L, enough titanium precursor solution are added drop-wise in attapulgite suspension with the speed of 0.8mL/ hour ~ 5mL/ hour, stir and carry out condensation reaction in 12 ~ 15 hours, after having reacted, straight alcohol dispensing laundry is used by after the solution centrifugal of reaction gained, dry in a vacuum again, obtain titanium source-attapulgite mixture, wherein centrifugal rotating speed >=8000 rev/min;
4) titanium source-attapulgite mixture is calcined 2 ~ 3 hours under 350 DEG C ~ 950 DEG C conditions, then the product after calcining is cooled to room temperature, obtains TiO 2-attapulgite mixture;
5) by TiO 2it is in the NaOH solution of 2mol/L ~ 4mol/L that-attapulgite mixture joins enough concentration, react 2 ~ 3 hours under 70 DEG C ~ 90 DEG C water-baths and agitation condition, after having reacted, use distilled water dispensing laundry by after the solution centrifugal of reaction gained, last dry in a vacuum, obtain TiO 2nanotube, wherein centrifugal rotating speed>=8000 rev/min.
2. according to claim 1 take natural mineral as the method for Template preparation titania nanotube, it is characterized in that: step 2) in cetyl trimethylammonium bromide and distilled water addition sequence after first adding cetyl trimethylammonium bromide, add distilled water again.
3. according to claim 1 take natural mineral as the method for Template preparation titania nanotube, it is characterized in that: repeat twice with straight alcohol dispensing laundry react the solution centrifugal of gained in step 3) to major general after.
4. according to claim 1 take natural mineral as the method for Template preparation titania nanotube, it is characterized in that: step 4) in the calcining temperature of titanium source-attapulgite mixture be 550 DEG C ~ 950 DEG C.
5. according to claim 1 take natural mineral as the method for Template preparation titania nanotube, it is characterized in that: repeat twice with distilled water dispensing laundry react the solution centrifugal of gained in step 5) to major general after.
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Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105236364A (en) * 2015-08-27 2016-01-13 常州大学 Preparation method of tubular carbon nitride
CN105217677B (en) * 2015-10-27 2016-08-24 镇江纳微新材料科技有限公司 A kind of method preparing titanium nanotube for template with attapulgite clay
CN105920970B (en) * 2016-05-13 2017-11-28 浙江中环清新净化设备有限公司 A kind of air cleaning unit suitable for large-scale public place
CN105854430B (en) * 2016-05-13 2017-05-31 中环清新人工环境工程技术(北京)有限责任公司 A kind of preparation method of the nano composite material for purification of air
CN106311196B (en) * 2016-07-19 2019-01-01 天津大学 Tubular structure nano titanium dioxide photocatalyst and preparation method
CN108067236A (en) * 2018-01-30 2018-05-25 常州大学 A kind of preparation method of concave convex rod soil matrix catalyst
CN109896549B (en) * 2019-03-12 2021-04-23 淮阴工学院 Preparation method of fibrous amorphous ferric oxide
CN110882713B (en) * 2019-11-22 2022-04-26 常州纳欧新材料科技有限公司 Conductive attapulgite/titanium oxide/carbon nitride quantum dot composite material, preparation method thereof and application thereof in photocatalytic desulfurization

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
Facile synthesis of CeO2 nanotubes templated by modified attapulgite;Chen Zhigang et al.;《Journal of Rare Earths》;20100831;第28卷(第4期);第566-570页 *
负载TiO2凹凸棒石光催化氧化法处理酸性品红燃料废水;彭书传 等;《硅酸盐学报》;20061031;第34卷(第10期);第1208-1212页 *

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