CN103641165A - Method for preparing titanium dioxide nanotube by using natural mineral as formwork - Google Patents
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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
Technical field
The present invention relates to a kind ofly take natural mineral and prepare the method for titania nanotube as template, refer in particular to and take natural attapulgite and prepare the method for titania nanotube as template, belong to titania nanotube technical field.
Technical background
Titanium dioxide is a kind of important inorganic functional material, and it has broad application prospects at storage of solar energy and utilization, opto-electronic conversion, the photochromic and aspect such as photocatalytic degradation atmosphere and water pollutant.The raw material resources of titanium dioxide is abundant, low price and toxicological harmless, is the focus of studying in the world in recent years.As one of existence form of titanium dioxide, titania nanotube has larger specific surface area and stronger adsorptive power, thereby show higher hydrogen-sensitivity, electricity conversion and photocatalysis performance, make it at aspects such as gas sensing materials, solar cell, photochemical catalysis, there is immeasurable potential using value, attracted the extensive concern of various countries' researchers, the had a large amount of bibliographical informations preparation of titania nanotube and the research of application aspect thereof.
TiO
2the preparation method of nanotube mainly contains anonizing, hydrothermal method and template.Wherein, anonizing is to prepare the most frequently used, the easiest method of titania nanotube.But the titania nanotube that adopts anonizing to prepare is attached on titanium sheet, this is subject to certain restrictions it in application, and the cost of the method is higher.Hydrothermal method can make the TiO that caliber is less
2nanotube, and operating procedure is simpler, but size pattern and the constitutional features of the prepared nanotube of hydrothermal method depend on raw material TiO largely
2the size of particulate and crystalline phase, and hydrothermal method requirement equipment can high temperature resistant and high pressure, thereby to material with safety requirements is strict and cost is higher.
Template synthesis TiO
2nanotube is exactly to 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) to take porous alumina (PAA) be template, in conjunction with sol-gel method, prepares Detitanium-ore-type TiO
2nanotube, the caliber of obtained nanotube is 100nm, thickness of pipe is 10nm.Test shows that length, aperture and the thickness of pipe of this nanotube can regulate according to template, and the time that control PAA template is immersed in colloidal solution can be controlled TiO
2the length of nanotube and thickness of pipe.It is template that Michalloowski A etc. (Michail O.A etal.Chemical Physics Letters, 2001) be take porous anodic aluminium oxide (PAO), and preparing caliber is 50nm～70nm, the TiO that wall thickness is 3nm
2nanotube.Resulting nanotube pattern rule, the nanotube that performance is better than preparing with sol-gel method under square one.Jong H.G etc. (Jong H J etal.Chem.Mater., 2002) are usingd organogel as template, prepare spiral shape TiO
2be about the double-deck TiO of 8nm～9nm with interlamellar spacing
2nanotube.The people (Dongxia Liu etal.Langmuir, 2007) such as Dongxia Liu be take homemade bar-shaped calcite and are prepared the TiO of different tube diameters as template
2nanotube.Above-mentioned these methods template used all needs to prepare in advance, and this makes preparation process become complicated to a great extent, has increased preparation cost, thereby has limited these methods for TiO
2the extensive preparation of nanotube.Therefore, adopt easy method, with material cheap and easy to get, prepare TiO
2nanotube becomes a kind of necessity.
Up to the present, take natural attapulgite as template, the method for utilizing template to combine with sol-gel method is prepared TiO
2the technology of nanotube there is not yet report.
Summary of the invention
The invention provides and a kind ofly take natural mineral and prepare the method for titania nanotube as template, the method be take natural attapulgite as template, and the technology that adopts template to combine with sol-gel method is prepared 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 obtaining
2nanotube performance is good.
Realizing the technical scheme that the object of the invention takes is:
The natural mineral of take is prepared the method for titania nanotube as template, comprises the steps:
1) according to attapulgite: HCl solution, HNO
3solution or H
2sO
4the mass volume ratio of solution=1g:10mL～1g:20mL, joins by attapulgite HCl solution, the HNO that concentration is 1mol/L～5mol/L
3solution or H
2sO
4in solution, under 60 ℃～70 ℃ conditions, stir and attapulgite was carried out to modification in 2～3 hours, after filtration, obtain the attapulgite of modification, then the attapulgite of modification washed to neutrality and dry under 80 ℃～105 ℃ conditions;
2) attapulgite dry, modification is added in propyl carbinol, ultrasonic dispersion is well-dispersed in propyl carbinol attapulgite, then add cetyl trimethylammonium bromide and distilled water, 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) with propyl carbinol dilution tetrabutyl titanate, obtain the titanium precursor solution that concentration is 0.10～0.25mol/L, speed by enough titanium precursor solution with 0.8mL/ hour～5mL/ hour is added drop-wise in attapulgite suspension, stir and within 12～15 hours, carry out condensation reaction, after having reacted, to after the solution centrifugal of reaction gained, with straight alcohol, disperse washing, 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 ℃～950 ℃ conditions, then the product after calcining is cooled to room temperature, obtain TiO
2-attapulgite mixture;
5) by TiO
2-attapulgite mixture joins in the NaOH solution that enough concentration is 2mol/L～4mol/L, under 70 ℃～90 ℃ water-baths and agitation condition, react 2～3 hours, after having reacted, will after the solution centrifugal of reaction gained, with distilled water, disperse washing, finally dry in a vacuum, obtain TiO
2nanotube, wherein centrifugal rotating speed>=8000 rev/min.
Technique scheme is further improved to step 2) in cetyl trimethylammonium bromide and distilled water addition sequence after first adding cetyl trimethylammonium bromide, add again distilled water; In step 3), after reacting the solution centrifugal of gained, major general disperse washing to repeat twice with straight alcohol; Step 4) in, the calcining temperature of titanium source-attapulgite mixture is 550 ℃～950 ℃; In step 5), after reacting the solution centrifugal of gained, major general disperse washing to repeat twice with distilled water.
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, and required equipment and preparation are cheap, preparation TiO
2required with low cost of nanotube, is applicable to suitability for industrialized production.
2) the required template of the method is natural attapulgite, wide material sources and cheap.Attapulgite is that a kind of Shuifu County's magnesium silicate that contains of tool fiber pattern layer chain transition structure is main clay mineral, has natural nano-scale fiber profile, and diameter, in nanometer range, is typical monodimension nanometer material.Use natural attapulgite just not need to prepare in advance template, saved preparation required human and material resources and the time of template, 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 that is carried on attapulgite surface just has attapulgite constitutional features after removing attapulgite template, obtains having the TiO of attapulgite constitutional features
2nanotube.
4) show after tested the TiO that adopts the present invention to prepare
2nanotube purity is high, and external diameter is 20nm left and right, 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 the TiO of embodiment 1 preparation
2the XRD figure spectrum of nanotube.
Fig. 4 is the TiO of embodiment 1 preparation
2the scanning electron microscope (SEM) photograph of nanotube.
Fig. 5 is the TiO of embodiment 1 preparation
2the transmission electron microscope picture of nanotube.
Fig. 6 is the EDS spectrogram of attapulgite.
Fig. 7 is the TiO of embodiment 1 preparation
2the EDS spectrogram of nanotube.
Fig. 8 is the TiO of embodiment 2 preparations
2the XRD figure spectrum of nanotube.
Fig. 9 is the TiO of embodiment 3 preparations
2the XRD figure spectrum of nanotube.
Figure 10 is embodiment 4 preparation 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, at 70 ℃ of condition lower magnetic forces, stirs 2 hours, filtration obtains the attapulgite of modification, again that the attapulgite washing of modification is extremely neutral, in baking oven, to dry 24 hours, the temperature that baking oven is set is 80 ℃;
2) take that 0.04g is dry, the attapulgite of modification joins in 32mL propyl carbinol, ultrasonic dispersion, after 5 minutes, adds 0.04g cetyl trimethylammonium bromide and 1mL distilled water successively, slowly stirs after 45 minutes and obtains attapulgite suspension;
3) with 20mL propyl carbinol dilution tetrabutyl titanate, obtain the titanium precursor solution that concentration is 0.10mol/L, by titanium precursor solution, the speed with 0.8mL/ hour is added drop-wise in attapulgite suspension again, stir and within 12 hours, carry out condensation reaction, after having reacted, first by the solution of reaction gained under 8000 revs/min of conditions centrifugal 5 minutes, then in straight alcohol, disperse washing, in centrifugal and straight alcohol, disperse the step of washing in triplicate, dry in a vacuum again, obtain titanium source-attapulgite mixture;
4) titanium source-attapulgite mixture is placed in to retort furnace and calcines, the temperature rise rate that stove is set is 10 ℃/min, is warming up to 550 ℃ and be incubated 2 hours, then the product after calcining is naturally cooled to room temperature, obtains TiO
2-attapulgite mixture;
5) by TiO
2-attapulgite mixture joins in the NaOH solution that concentration is 2mol/L, under 80 ℃ of water-baths and agitation condition, react 2 hours, after having reacted, first by the solution of reaction gained under 8000 revs/min of conditions centrifugal 5 minutes, in distilled water, disperse again washing, the centrifugal step that dispersion is washed with distilled water 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 be take club shaped structure as main, 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, from figure, can observe clearly the club shaped structure that attapulgite is one dimension, and the diameter of rod is all in 10nm left and right, 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 25.2 °, 37.8 ° and 48.1 ° at 2 θ and has located 3 obvious absorption peaks, these three absorption peaks are corresponding Detitanium-ore-type TiO respectively
2the feature diffraction of (101004200) crystal face, the diffraction peak of (101) face particularly, there is certain preferred orientation, show that prepared sample is mainly Anatase crystal, through XRD software, retrieve and learn: this collection of illustrative plates meets PDF card 89-4921, the TiO that prepared sample is 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 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
2the tubulose feature of nanotube is very obvious, and its external diameter is 20nm left and right, and length is that hundreds of nanometer arrives several microns, has very similarly shape and diameter dimension with attapulgite.This illustrates prepared TiO
2nanotube has utilized this template of attapulgite well, in carrying out the process of collosol and gel, most titanium precursor body is by the connection of CTAB, to be deposited on the outside surface of attapulgite template, through calcining and sloughing after attapulgite template, is deposited on the TiO on attapulgite surface
2just form the tubular structure of hollow, formed TiO
2nanotube.
Fig. 6 is the EDS spectrogram of attapulgite raw ore sample, as can be seen from the figure in the Chemical Composition of attapulgite, does not contain titanium elements, and 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 of 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 gold spraying when wherein Au element derives from sample preparation, Cu element derives from loading copper platform, and C element derives from the conductive resin that sample preparation is used, and in sample, containing a small amount of Si is due to prepared TiO
2the specific surface area of nanotube is very large, and it has adsorbed a small amount of Si on its surface, so only contain a large amount of Ti elements and O element in prepared sample, prepared material is TiO
2nanotube.
Known by above analysis: take natural attapulgite as template, tetrabutyl titanate is titanium source, to adopt sol-gel method and template to combine method, has successfully prepared the highly purified TiO with natural attapulgite constitutional features
2nanotube.
1) take attapulgite 10.00g, being joined 150mL concentration was in the HCl solution of 1mol/L, 60 ℃ of magnetic agitation 3 hours, filtration obtains the attapulgite of modification, the attapulgite of modification is washed to neutrality again, dry 24 hours in baking oven, the temperature that baking oven is set is 95 ℃;
2) take that 0.04g is dry, the attapulgite of the gained of modification joins in 40mL propyl carbinol, ultrasonic dispersion, after 5 minutes, adds 0.04g cetyl trimethylammonium bromide and 3mL distilled water successively, slowly stirs after 45 minutes and obtains attapulgite suspension;
3) with 20mL propyl carbinol dilution tetrabutyl titanate, obtain 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 within 13 hours, carry out condensation reaction, after having reacted, by the solution of reaction gained under 8000 revs/min of conditions centrifugal 5 minutes, then in straight alcohol, disperse washing, in centrifugal and straight alcohol, disperse the step of washing in triplicate, dry in a vacuum again, obtain titanium source-attapulgite mixture;
4) titanium source-attapulgite mixture is calcined in retort furnace, the temperature rise rate that stove is set is 10 ℃/min, is warming up to 350 ℃ and be incubated 3 hours, then the product after calcining is naturally cooled to room temperature, obtains TiO
2-attapulgite mixture;
5) by TiO
2-attapulgite mixture joins in the NaOH solution that concentration is 3mol/L, under 70 ℃ of water-baths and agitation condition, react 3 hours, after having reacted, first by the solution of reaction gained under 8000 revs/min of conditions centrifugal 5 minutes, in distilled water, disperse again washing, in centrifugal and distilled water, disperse the step of washing in triplicate, finally 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 shows that 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 25.2 °, 37.8 ° and 48.1 ° at 2 θ and locates 3 faint absorption peaks, these three absorption peaks are corresponding Detitanium-ore-type TiO respectively
2the feature diffraction of (101004200) crystal face.Because these three absorption peaks are very faint, the TiO obtaining is described after 350 ℃ of calcinings
2the degree of crystallinity of nanotube is bad.
1) take attapulgite 10.00g, being joined 150mL concentration was in the HCl solution of 5mol/L, 70 ℃ of magnetic agitation 3 hours, filtration obtains the attapulgite of modification, again that the attapulgite washing of modification is extremely neutral, in baking oven, to dry 24 hours, the temperature that baking oven is set is 100 ℃;
2) take 0.04 attapulgite dry, modification and join in 50mL propyl carbinol, ultrasonic dispersion, after 5 minutes, adds 0.12g cetyl trimethylammonium bromide and 5mL distilled water successively, slowly stirs after 45 minutes and obtains attapulgite suspension;
3) with 20mL propyl carbinol dilution tetrabutyl titanate, obtain the titanium precursor solution that concentration is 0.10mol/L, by titanium precursor solution, the speed with 4mL/ hour is added drop-wise in attapulgite suspension again, stir and within 14 hours, carry out condensation reaction, after having reacted, first by the solution of reaction gained under 8000 revs/min of conditions centrifugal 5 minutes, then in straight alcohol, disperse washing, in centrifugal and straight alcohol, disperse the step of washing in triplicate, dry in a vacuum again, obtain titanium source-attapulgite mixture;
4) titanium source-attapulgite mixture is calcined in retort furnace, the temperature rise rate that stove is set is 10 ℃/min, is warming up to 750 ℃ and be incubated 3 hours, then the product after calcining is naturally cooled to room temperature, obtains TiO
2-attapulgite mixture;
5) by TiO
2-attapulgite mixture joins in the NaOH solution that concentration is 4mol/L, under 90 ℃ of water-baths and agitation condition, react 3 hours, first by the solution of reaction gained under 8000 revs/min of conditions centrifugal 5 minutes, in distilled water, disperse again washing, the centrifugal step that dispersion is washed with distilled water in triplicate, finally 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 shows that 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 in 2 θ=27.4 °, there is the weak peak of intensity in collection of illustrative plates, its corresponding to the feature diffraction of Rutile Type (110) crystal face.
Embodiment 4
1) take attapulgite 10.00g, being joined 150mL concentration is in the HCl solution of 1mol/L, 70 ℃ of magnetic agitation 2 hours, then filter the attapulgite that obtains modification, finally by the attapulgite washing of modification to neutral and dry 24 hours under 105 ℃ of conditions in baking oven;
2) take that 0.04g is dry, the attapulgite of modification joins in 32mL propyl carbinol, ultrasonic dispersion, after 5 minutes, adds 0.04g cetyl trimethylammonium bromide and 1mL distilled water successively, slowly stirs after 45 minutes and obtains attapulgite suspension;
3) with 20mL propyl carbinol dilution tetrabutyl titanate, obtain the titanium precursor solution that concentration is 0.25mol/L, by titanium precursor solution, the speed with 5mL/ hour is added drop-wise in attapulgite suspension again, stir and within 15 hours, carry out condensation reaction, after having reacted, first by the solution of reaction gained under the condition of 8000 revs/min centrifugal 5 minutes, then in straight alcohol, disperse washing, in centrifugal and straight alcohol, disperse the step of washing in triplicate, dry in a vacuum again, obtain titanium source-attapulgite mixture;
4) titanium source-attapulgite mixture is calcined in retort furnace, the temperature rise rate that stove is set is 10 ℃/min, is warming up to 950 ℃ and be incubated 3 hours, and the product after calcining is naturally cooled to room temperature, obtains TiO
2-attapulgite mixture;
5) by TiO
2-attapulgite mixture joins in the NaOH solution that concentration is 3mol/L, under 70 ℃ of water-baths and agitation condition, react 2 hours, after having reacted, first by the solution of reaction gained under 8000 revs/min of conditions centrifugal 5 minutes, in distilled water, disperse again washing, in centrifugal and distilled water, disperse the step of washing in triplicate, finally 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 shows that product is TiO
2for nanotube.
The TiO that Figure 10 is prepared for 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 be used HNO
3solution or H
2sO
4solution replaces.
Claims (5)
1. the natural mineral of take is prepared the method for titania nanotube as template, 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 by attapulgite HCl solution, the HNO that concentration is 1mol/L～5mol/L
3solution or H
2sO
4in solution, under 60 ℃～70 ℃ conditions, stir and attapulgite was carried out to modification in 2～3 hours, after filtration, obtain the attapulgite of modification, then the attapulgite of modification washed to neutrality and dry under 80 ℃～105 ℃ conditions;
2) attapulgite dry, modification is added in propyl carbinol, ultrasonic dispersion is well-dispersed in propyl carbinol attapulgite, then add cetyl trimethylammonium bromide and distilled water, 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) with propyl carbinol dilution tetrabutyl titanate, obtain the titanium precursor solution that concentration is 0.10～0.25mol/L, speed by enough titanium precursor solution with 0.8mL/ hour～5mL/ hour is added drop-wise in attapulgite suspension, stir and within 12～15 hours, carry out condensation reaction, after having reacted, to after the solution centrifugal of reaction gained, with straight alcohol, disperse washing, 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 ℃～950 ℃ conditions, then the product after calcining is cooled to room temperature, obtain TiO
2-attapulgite mixture;
5) by TiO
2-attapulgite mixture joins in the NaOH solution that enough concentration is 2mol/L～4mol/L, under 70 ℃～90 ℃ water-baths and agitation condition, react 2～3 hours, after having reacted, will after the solution centrifugal of reaction gained, with distilled water, disperse washing, finally dry in a vacuum, obtain TiO
2nanotube, wherein centrifugal rotating speed>=8000 rev/min.
2. according to claim 1ly take natural mineral and prepare the method for titania nanotube as template, it is characterized in that: step 2) in cetyl trimethylammonium bromide and distilled water addition sequence after first adding cetyl trimethylammonium bromide, add again distilled water.
3. according to claim 1ly take natural mineral and prepare the method for titania nanotube as template, it is characterized in that: in step 3), after major general reacts the solution centrifugal of gained, with straight alcohol, disperse washing to repeat twice.
4. according to claim 1ly take natural mineral and prepare the method for titania nanotube as template, it is characterized in that: step 4) in the calcining temperature of titanium source-attapulgite mixture be 550 ℃～950 ℃.
5. according to claim 1ly take natural mineral and prepare the method for titania nanotube as template, it is characterized in that: in step 5), after major general reacts the solution centrifugal of gained, with distilled water, disperse washing to repeat twice.
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| CN105236364A (en) * | 2015-08-27 | 2016-01-13 | 常州大学 | Preparation method of tubular carbon nitride |
| CN105217677A (en) * | 2015-10-27 | 2016-01-06 | 镇江纳微新材料科技有限公司 | A kind of take attapulgite clay as the method for Template preparation titanium nanotube |
| CN105854430A (en) * | 2016-05-13 | 2016-08-17 | 中环清新人工环境工程技术(北京)有限责任公司 | Method for preparing nano composite material for air purification |
| CN105920970A (en) * | 2016-05-13 | 2016-09-07 | 中环清新人工环境工程技术(北京)有限责任公司 | Air purification device for large public place |
| CN106311196A (en) * | 2016-07-19 | 2017-01-11 | 天津大学 | Tubular-structure nano titanium dioxide photocatalyst and preparation method thereof |
| 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 |
| CN109896549A (en) * | 2019-03-12 | 2019-06-18 | 淮阴工学院 | The preparation method of fibrous amorphous state di-iron trioxide |
| CN109896549B (en) * | 2019-03-12 | 2021-04-23 | 淮阴工学院 | Preparation method of fibrous amorphous ferric oxide |
| CN110882713A (en) * | 2019-11-22 | 2020-03-17 | 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 |
| 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 |
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