CN104843786A - Hierarchical titanium dioxide microspheres based on surface oriented growth nano-rods and preparation method thereof - Google Patents
Hierarchical titanium dioxide microspheres based on surface oriented growth nano-rods and preparation method thereof Download PDFInfo
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Abstract
The invention relates to hierarchical titanium dioxide microspheres based on surface oriented growth nano-rods and a preparation method thereof. The hierarchical titanium dioxide microspheres are three-dimensional microspheres formed by a cluster of one-dimensional nano-rods which own a common core and grow uniformly and outwards in a radiation manner along the core. The preparation method comprises the following main steps of: adding a titanium precursor in a polycondensation reaction process of resorcinol-formaldehyde, then preparing organic gel in a sol-gel process, and finally carrying out high-temperature carbonization to obtain the titanium dioxide nano-rod microspheres with hierarchical structures. The hierarchical titanium dioxide microspheres based on the surface oriented growth nano-rods, prepared by the method, have a good adsorption performance and a good pollutant photocatalytic degradation performance; and after being used, the hierarchical titanium dioxide microspheres based on the surface oriented growth nano-rods are separated from water simply and conveniently, thus easily realizing the recycling and reusing of photocatalytic materials. In addition, the preparation method is simple in technology, the mass production is easily realized by adopting the preparation method, the appearance and size of the products are controllable, and the products are high in crystalline of degree and conform to practical production application requirements.
Description
Technical field
The invention belongs to technical field of nano material, relate to a kind of graduation titanium dioxide microballoon sphere based on surface orientation growing nano-rod and preparation method thereof.
Background technology
In recent years, environmental pollution has become and has threatened the serious problems of human survival, and photocatalysis oxidation technique without the selectively nearly all organic pollutant of mineralising, can kill rapidly most of pathogenic microorganism because of it, and non-secondary pollution, be subject to the extensive attention of academia and industry member.In numerous photocatalyst material, titanium dioxide, because of its excellent photocatalytic activity, stability and lower-price characteristic, is most widely used photocatalyst always, and it is all widely used in fields such as water treatment, purifying air, antibacterial, deodorizing.But consider from practical application angle, photocatalytic activity still needs further raising.In addition, the titanium dioxide of current practical application mostly is nano powder final states, use rear difficult separation and recycling, and nanometer powder is more easily reunited, and causes photocatalytic activity in use procedure to reduce further.
1-dimention nano titanium dioxide crystal degree is high, and carrier localization is less, and transmission speed is fast, and recombination rate is low, and has large specific surface area, high adsorption capacity, and reaction active site is many, and its photocatalytic activity is far above nano powder final states titanium dioxide.Micro-scale titanium dioxide is comparatively large because of its size, by self standing sedimentation, can be separated with water fast, or by simple membrane filtration, titanic oxide material can be reclaimed completely, and serious film blocking can not be caused, titanium dioxide can be solved well and reclaim problem.There is the titanic oxide material of micro-nano secondary graded structure, merged the reactive behavior of nano material efficient and the good recyclability of micro materials, get the attention in pollutant removal, solar fuel cell and gas sensor are prepared etc.But often degree of crystallization is not high for the graduation titanic oxide material of current bibliographical information, and yield poorly, reproducibility is poor, is not suitable for scale operation.Therefore, find a kind of efficient preparation method easily, for the synthesis of the graduation titanium dioxide microballoon sphere with highlight catalytic active and good recovery performance, there is important practical application meaning.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of graduation titanium dioxide microballoon sphere based on surface orientation growing nano-rod and preparation method thereof.This titanium dioxide microballoon sphere has very high photocatalytic pollutant degradation ability, and is separated easy with water with rear, is easy to the recycling realizing photocatalyst material.Preparation method's technique of this titanium dioxide microballoon sphere is simple, is easy to realize scale operation, realistic production application demand.
Technical scheme of the present invention is as follows:
Based on a graduation titanium dioxide microballoon sphere for surface orientation growing nano-rod, this microballoon is had common core monodimension nano stick by cluster grows along the outside homogeneous radiation of core the three dimensional micron ball formed.
According to the present invention, preferably, the diameter of described monodimension nano stick is 30-50nm, and length is 400-700nm.
According to the present invention, preferably, described three dimensional micron spherical diameter is 0.8-1.4 μm.
According to the present invention, preferably, the BET specific surface area of described graduation titanium dioxide microballoon sphere is 20.4-46.3m
3/ g.
According to the present invention, the preparation method of the above-mentioned graduation titanium dioxide microballoon sphere based on surface orientation growing nano-rod, comprises step as follows:
(1) under room temperature, by Resorcinol and formaldehyde in molar ratio example be 1:(1-8) be dissolved in the water successively, make Resorcinol mass concentration be 1.5%-15%, obtain mixing solutions;
(2) under agitation, in step (1) gained mixing solutions, dropwise add Titanium Trichloride Solution, make titanous chloride and Resorcinol molar ratio be 1:(1-8), obtain reaction solution;
(3) by step (2) gained reaction solution in 50-90 DEG C of confined reaction 2-6 hour, obtain gel;
(4) by step (3) gained gel in 70-105 DEG C of dry 6-24 hour, then in 300-800 DEG C calcining 2-6 hour, naturally cooling, obtains the graduation titanium dioxide microballoon sphere based on surface orientation growing nano-rod.
According to the present invention, preferably, the formalin of to be mass concentration the be 5-35% of the formaldehyde described in step (1), the mol ratio of Resorcinol and formaldehyde is 1:(4-8).
According to the present invention, preferably, the Titanium Trichloride Solution described in step (2) is be dissolved in the Titanium Trichloride Solution in 3wt% hydrochloric acid soln, and titanous chloride concentration is 0.05-1.5mol/L; Described titanous chloride and Resorcinol molar ratio are 1:(6-8); The speed of described stirring is 500-2000 rev/min.
According to the present invention, preferably, in step (3), confined reaction carries out in the water bath with thermostatic control of 70-90 DEG C.Temperature of reaction is to the photocatalysis performance important of obtained graduation titanium dioxide microballoon sphere, and bath temperature is too low, and not exclusively, be unfavorable for the formation of micro-sphere structure, the photocatalytic activity of products therefrom is poor for Resorcinol and formaldehyde reaction.
According to the present invention, preferably, in step (4), calcining temperature is 400-500 DEG C.Calcining temperature is also to the photocatalysis performance important of obtained graduation titanium dioxide microballoon sphere, and when calcining temperature is too low, in products therefrom, organic substance residues is too much, and titanium dioxide effective content is lower, and titanium dioxide crystal degree is lower, and its lytic activity is poor; When calcining temperature is too high, in products therefrom there is sintering adhesion in nanometer rod, and specific surface area declines, and its lytic activity is also poor.
According to the present invention, preferably, the ultrapure water of the water that preparation process is used to be specific conductivity be 18.2M Ω.
The present invention is by adding titanium precursors in the polycondensation process of resorcinol-formaldehyde, organogel is prepared through sol-gel process, the titanium dioxide microballoon sphere with graded structure is obtained again through high temperature carbonization, the primary structure of this titanium dioxide microballoon sphere is titanium dioxide nano-rod, and secondary structure is the three dimensional micron ball be made up of titanium dioxide nano-rod.For the nano TiO 2 powder material of single structure, this graduation titanium dioxide microballoon sphere, to Organic Pollutants In Water, as acidic bright red paint, shows the Photocatalytic Degradation Property of enhancing, and have good in settling property, easy by the Separation and Recovery of rear material.This material can be applicable to the fields such as feedwater, wastewater treatment, purifying air, solar fuel cell, gas sensor, daily-use chemical industry, is with a wide range of applications.
Compared with prior art, tool of the present invention has the following advantages:
1. graduation titanium dioxide microballoon sphere of the present invention has unique three-dimensional graded structure, and primary structure is the monodimension nano stick of diameter 30-50nm, length 400-700nm, and secondary structure is the three dimensional micron ball of diameter 0.8-1.4 μm.This microballoon is the Rutile Type mesoporous material of stable performance, and have larger specific surface area and good scattering of light, receptivity, photocatalysis degradation organic contaminant performance is better than Degussa P25.
2. graduation titanium dioxide microballoon sphere of the present invention is obviously better than nano powder final states titanium dioxide (as DegussaP25) from settling property, with after be easy to be separated with water, be convenient to the recycling realizing material.
3. graduation titanium dioxide microballoon sphere preparation method of the present invention is without the need to tensio-active agent and hard template, and operational path is simple, is easy to realize scale operation, and product morphology size is controlled, crystallization degree is high, and realistic production application demand, has great industrialization potential.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the titanium dioxide microballoon sphere that the embodiment of the present invention 1 obtains;
Fig. 2 is the X-ray diffractogram of the titanium dioxide microballoon sphere that the embodiment of the present invention 1 obtains;
Fig. 3 is the isothermal nitrogen suction-desorption curve of the titanium dioxide microballoon sphere that the embodiment of the present invention 1 obtains;
Fig. 4 is the pore size distribution curve of the titanium dioxide microballoon sphere that the embodiment of the present invention 1 obtains;
Fig. 5 is that the obtained titanium dioxide microballoon sphere of the embodiment of the present invention 1 and Degussa P25 are to the absorption of acidic bright red paint and Photocatalytic Degradation Property correlation curve;
Fig. 6 is that the obtained titanium dioxide microballoon sphere of the embodiment of the present invention 1 and Degussa P25 are to the photochemical catalysis removal efficiency correlation curve of acidic bright red paint;
Fig. 7 is the scanning electron microscope (SEM) photograph of the titanium dioxide microballoon sphere that the embodiment of the present invention 4 obtains;
Fig. 8 is the X-ray diffractogram of the titanium dioxide microballoon sphere that the embodiment of the present invention 4 obtains;
Fig. 9 is the photocatalytic degradation acid scarlet performance curve of the titanium dioxide that comparative example 1 of the present invention obtains;
Figure 10 is the X-ray diffractogram of the titanium dioxide that comparative example 2 of the present invention obtains;
Figure 11 is the photocatalytic degradation acid scarlet performance curve of the titanium dioxide that comparative example 2 of the present invention obtains.
Embodiment
Also come by reference to the accompanying drawings to explain the present invention further below by way of specific embodiment.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various change or amendment to the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
Raw materials usedly in embodiment be convenient source, commercial products, equipment used is conventional equipment.
The ultrapure water of water used in embodiment to be specific conductivity be 18.2M Ω.
Embodiment 1
Based on a preparation method for the graduation titanium dioxide microballoon sphere of surface orientation growing nano-rod, comprise step as follows:
(1), in room temperature and constantly under agitation condition, the speed of stirring is 2000 revs/min, by Resorcinol and formaldehyde in molar ratio example be dissolved in the water successively for 1:8, the control water yield, makes Resorcinol mass concentration be 1.5%, obtains mixing solutions;
(2) in gained mixing solutions, dropwise add Titanium Trichloride Solution, be 1:8 to titanous chloride and Resorcinol molar ratio, obtain reaction solution; Described Titanium Trichloride Solution is be dissolved in the Titanium Trichloride Solution in 3wt% hydrochloric acid soln, and titanous chloride concentration is 1.5mol/L;
(3) gained reaction solution is moved in encloses container, and be placed in 90 DEG C of water bath with thermostatic control reactions 2 hours, generate garnet gel;
(4) at gained gel being placed in 105 DEG C, drying 6 hours, calcines 2 hours, naturally cooling, i.e. scoring rank titanium dioxide microballoon sphere afterwards at 500 DEG C.
The product obtained to the present embodiment carries out electron-microscope scanning, and as shown in Figure 1, as shown in Figure 1, this titanium dioxide microballoon sphere is had common core monodimension nano stick by cluster grows along the outside homogeneous radiation of core the three dimensional micron ball formed to scanning electron microscope (SEM) photograph.Microsphere diameter is 0.8-1.4 μm, and nanorod diameter is 30-50nm, and length is 400-700nm.
The product obtained to the present embodiment carries out X-ray diffraction scanning, X-ray diffractogram as shown in Figure 2, as shown in Figure 2, the each diffraction peak of this product is all corresponding with standard red schorl phase titanium dioxide (JCPDS No.:21-1276) peak position, and exist without dephasign peak, illustrate that product is pure red schorl phase titanium dioxide.
Measure isothermal nitrogen suction-desorption curve and pore size distribution curve that the present embodiment obtains product, as shown in Figure 3,4, from Fig. 3,4, this titanium dioxide microballoon sphere known is mesoporous material to result, and BET specific surface area is 40.8m
3/ g, this is conducive to the absorption on the material of the organic macromolecules such as dyestuff.
The product obtained using the present embodiment and commercial Degussa P25 are as photocatalyst, and to absorption and the Photocatalytic Degradation Property test comparison of acidic bright red paint, step is as follows:
Light-catalyzed reaction is at cylindrical glass container (transverse section 30cm
2, high 25cm) carry out under interior normal temperature and pressure, adopt light source immersion to react, light source is the low pressure mercury lamp (13W) of predominant wavelength 254nm, carrys out the photocatalytic activity of assess sample using acidic bright red paint as simulating pollution thing.Get 0.5g photocatalyst to be scattered in 500ml acid scarlet solution (50mg/L).Before light-catalyzed reaction, stir 30 minutes at lucifuge condition lower magnetic force, make acid scarlet reach adsorption equilibrium in photocatalyst surface.After logical light, every 5 minutes sampling 5ml, after syringe filters is filtered, utilize ultraviolet-visible pectrophotometer to measure the absorbancy of filtrate, calculate the bright red concentration of remaining acid with this.The photocatalysis performance of the titanium dioxide microballoon sphere prepared by the present embodiment and commercial Degussa P25 all adopts same experimental conditions to measure.Test result as shown in Figure 5,6, from Fig. 5,6, titanium dioxide microballoon sphere prepared by the present embodiment is all better than commercial Degussa P25 to the absorption of acid scarlet and Photocatalytic Degradation Property, and microballoon is functional from sedimentation, just can be separated with reaction solution through natural subsidence, reach recycling object.
Embodiment 2
Based on a preparation method for the graduation titanium dioxide microballoon sphere of surface orientation growing nano-rod, comprise step as follows:
(1), in room temperature and constantly under agitation condition, the speed of stirring is 500 revs/min, by Resorcinol and formaldehyde in molar ratio example be dissolved in the water successively for 1:2, the control water yield, makes Resorcinol mass concentration be 3%, obtains mixing solutions;
(2) in gained mixing solutions, dropwise add Titanium Trichloride Solution, be 1:2 to titanous chloride and Resorcinol molar ratio, obtain reaction solution; Described Titanium Trichloride Solution is be dissolved in the Titanium Trichloride Solution in 3wt% hydrochloric acid soln, and titanous chloride concentration is 0.1mol/L;
(3) gained reaction solution is moved in encloses container, and be placed in 70 DEG C of water bath with thermostatic control reactions 4 hours, generate garnet gel;
(4) at gained gel being placed in 105 DEG C, drying 6 hours, calcines 2 hours, naturally cooling, i.e. scoring rank titanium dioxide microballoon sphere afterwards at 500 DEG C.
Embodiment 3
Based on a preparation method for the graduation titanium dioxide microballoon sphere of surface orientation growing nano-rod, comprise step as follows:
(1), in room temperature and constantly under agitation condition, the speed of stirring is 1000 revs/min, by Resorcinol and formaldehyde in molar ratio example be dissolved in the water successively for 1:2, the control water yield, makes Resorcinol mass concentration be 3%, obtains mixing solutions;
(2) in gained mixing solutions, dropwise add Titanium Trichloride Solution, be 1:2 to titanous chloride and Resorcinol molar ratio, obtain reaction solution; Described Titanium Trichloride Solution is be dissolved in the Titanium Trichloride Solution in 3wt% hydrochloric acid soln, and titanous chloride concentration is 0.5mol/L;
(3) gained reaction solution is moved in encloses container, and be placed in 50 DEG C of water bath with thermostatic control reactions 6 hours, generate garnet gel;
(4) at gained gel being placed in 70 DEG C, drying 24 hours, calcines 6 hours, naturally cooling, i.e. scoring rank titanium dioxide microballoon sphere afterwards at 300 DEG C.
Embodiment 4
Based on a preparation method for the graduation titanium dioxide microballoon sphere of surface orientation growing nano-rod, comprise step as follows:
(1), in room temperature and constantly under agitation condition, the speed of stirring is 1500 revs/min, by Resorcinol and formaldehyde in molar ratio example be dissolved in the water successively for 1:1, the control water yield, makes Resorcinol mass concentration be 15%, obtains mixing solutions;
(2) in gained mixing solutions, dropwise add Titanium Trichloride Solution, be 1:1 to titanous chloride and Resorcinol molar ratio, obtain reaction solution; Described Titanium Trichloride Solution is be dissolved in the Titanium Trichloride Solution in 3wt% hydrochloric acid soln, and titanous chloride concentration is 1.5mol/L;
(3) gained reaction solution is moved in encloses container, and be placed in 50 DEG C of water bath with thermostatic control reactions 6 hours, generate garnet gel;
(4) at gained gel being placed in 70 DEG C, drying 24 hours, calcines 2 hours, naturally cooling, i.e. scoring rank titanium dioxide microballoon sphere afterwards at 700 DEG C.
The product obtained to the present embodiment carries out electron-microscope scanning, and as shown in Figure 7, as shown in Figure 7, titanium dioxide microballoon sphere is had common core monodimension nano stick by cluster grows along the outside homogeneous radiation of core the three dimensional micron ball formed to scanning electron microscope (SEM) photograph.Microsphere diameter is 0.8-1.2 μm, and nanorod diameter is 30-50nm, and length is 400-600nm.Be with the difference of the titanium dioxide microballoon sphere prepared by embodiment 1, in the present embodiment, titanium dioxide nano-rod growth is more tight, and diameter and length are more homogeneous.
The product obtained to the present embodiment carries out X-ray diffraction scanning, and as shown in Figure 8, as shown in Figure 8, prepared titanium dioxide microballoon sphere is pure red schorl phase titanium dioxide to X-ray diffractogram.
Comparative example 1
As described in Example 1, be 25 DEG C unlike water bath with thermostatic control temperature in step (3), other steps are with embodiment 1.
Carry out Photocatalytic Degradation Property test to this comparative example products therefrom, test result as shown in Figure 9.As seen from Figure 9, compared to embodiment 1, water-bath temperature is the photocatalytic activity of 25 DEG C of products therefrom titanium dioxide is 90 DEG C of products therefroms far below water-bath temperature, this mainly due to water-bath temperature too low time, Resorcinol and formaldehyde reaction incomplete, be unfavorable for the formation of micro-sphere structure, therefore products therefrom activity is lower.
Comparative example 2
As described in Example 1, be 200 DEG C unlike calcining temperature in step (4), other steps are with embodiment 1.
The product titanium dioxide obtained to the present embodiment carries out X-ray diffraction scanning, and as shown in Figure 10, as shown in Figure 10, product is rutile crystal type to X-ray diffractogram, but compared to embodiment 1 products therefrom, this comparative example products therefrom crystallization degree is low.
Carry out Photocatalytic Degradation Property test to this comparative example products therefrom, test result as shown in figure 11.As seen from Figure 11, compared to embodiment 1, the photocatalysis performance of calcining temperature to be the photocatalytic activity of 200 DEG C of products therefrom titanium dioxide far below calcining temperature be 500 DEG C of products therefroms.When calcining temperature is too low, on the one hand, in products therefrom, organic substance residues is too much, and titanium dioxide effective content is lower; On the other hand, in products therefrom, titanium dioxide crystal degree is low, and therefore product photocatalytic activity is poor.
Claims (10)
1. based on a graduation titanium dioxide microballoon sphere for surface orientation growing nano-rod, it is characterized in that, this microballoon is had common core monodimension nano stick by cluster grows along the outside homogeneous radiation of core the three dimensional micron ball formed.
2. titanium dioxide microballoon sphere according to claim 1, is characterized in that, the diameter of described monodimension nano stick is 30-50nm, and length is 400-700nm.
3. titanium dioxide microballoon sphere according to claim 1, is characterized in that, described three dimensional micron spherical diameter is 0.8-1.4 μm.
4. titanium dioxide microballoon sphere according to claim 1, is characterized in that, the BET specific surface area of described graduation titanium dioxide microballoon sphere is 20.4-46.3m
3/ g.
5. a preparation method for the graduation titanium dioxide microballoon sphere based on surface orientation growing nano-rod described in any one of claim 1-4, comprises step as follows:
(1) under room temperature, by Resorcinol and formaldehyde in molar ratio example be 1:(1-8) be dissolved in the water successively, make Resorcinol mass concentration be 1.5%-15%, obtain mixing solutions;
(2) under agitation, in step (1) gained mixing solutions, dropwise add Titanium Trichloride Solution, make titanous chloride and Resorcinol molar ratio be 1:(1-8), obtain reaction solution;
(3) by step (2) gained reaction solution in 50-90 DEG C of confined reaction 2-6 hour, obtain gel;
(4) by step (3) gained gel in 70-105 DEG C of dry 6-24 hour, then in 300-800 DEG C calcining 2-6 hour, naturally cooling, obtains the graduation titanium dioxide microballoon sphere based on surface orientation growing nano-rod.
6. preparation method according to claim 5, is characterized in that, the formalin of to be mass concentration the be 5-35% of the formaldehyde described in step (1), and the mol ratio of Resorcinol and formaldehyde is 1:(4-8).
7. preparation method according to claim 5, is characterized in that, the Titanium Trichloride Solution described in step (2) is be dissolved in the Titanium Trichloride Solution in 3wt% hydrochloric acid soln, and titanous chloride concentration is 0.05-1.5mol/L.
8. preparation method according to claim 5, is characterized in that, step (2) described titanous chloride and Resorcinol molar ratio are 1:(6-8).
9. preparation method according to claim 5, is characterized in that, in step (3), confined reaction carries out in the water bath with thermostatic control of 70-90 DEG C.
10. preparation method according to claim 5, is characterized in that, in step (4), calcining temperature is 400-500 DEG C.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540827A (en) * | 2015-12-17 | 2016-05-04 | 山东大学 | Method for preparing graded titanium dioxide microsphere filler of surface-directional-growth-based nanorod |
| WO2017085493A1 (en) * | 2015-11-20 | 2017-05-26 | Huntsman P&A Uk Limited | Coatings |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09202620A (en) * | 1996-01-22 | 1997-08-05 | Titan Kogyo Kk | Rutile-type titanium dioxide particle and its production |
| US20090291044A1 (en) * | 2008-05-26 | 2009-11-26 | Korea Research Institute Of Chemical Technology | ANATASE TYPE TiO2 NANORODS AND ITS PREPARATION METHOD |
| CN101891248A (en) * | 2010-07-12 | 2010-11-24 | 山东大学 | Titania nanotube/nanorod microspheres with hierarchical structure and preparation method thereof |
| CN102786085A (en) * | 2012-08-06 | 2012-11-21 | 东华大学 | Method for preparing rutile type titanium dioxide nanorod microsphere |
| CN103058275A (en) * | 2013-01-07 | 2013-04-24 | 中国科学院合肥物质科学研究院 | Rutile crystal form titanium oxide having hierarchical structure, and preparation method and use thereof |
-
2015
- 2015-06-01 CN CN201510293039.1A patent/CN104843786A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09202620A (en) * | 1996-01-22 | 1997-08-05 | Titan Kogyo Kk | Rutile-type titanium dioxide particle and its production |
| US20090291044A1 (en) * | 2008-05-26 | 2009-11-26 | Korea Research Institute Of Chemical Technology | ANATASE TYPE TiO2 NANORODS AND ITS PREPARATION METHOD |
| CN101891248A (en) * | 2010-07-12 | 2010-11-24 | 山东大学 | Titania nanotube/nanorod microspheres with hierarchical structure and preparation method thereof |
| CN102786085A (en) * | 2012-08-06 | 2012-11-21 | 东华大学 | Method for preparing rutile type titanium dioxide nanorod microsphere |
| CN103058275A (en) * | 2013-01-07 | 2013-04-24 | 中国科学院合肥物质科学研究院 | Rutile crystal form titanium oxide having hierarchical structure, and preparation method and use thereof |
Non-Patent Citations (3)
| Title |
|---|
| HONGWEI BAI等: "Facile preparation of monodisperse, carbon doped single crystal rutile TiO2 nanorod spheres with a large percentage of reactive (110) facet exposure for highly efficient H2 generation", 《JOURNAL OF MATERIALS CHEMISTRY》, vol. 22, no. 36, 28 September 2012 (2012-09-28), pages 18801 - 18807 * |
| HONGWEI BAI等: "Large-Sc ale Production of Hierarch ical TiO2 Nanorod Spheres for Photocatalytic Elimination of Contaminants and Killing Bacteria", 《CHEMISTRY EUROPEAN JOURNAL》, vol. 19, 31 December 2013 (2013-12-31), pages 3061 - 3070 * |
| SHAHEEN A.AL-MUHTASEB等: "Preparation and Properties of Resorcinol-Formaldehyde Organic and Carbon Gels", 《ADBANCED MATERIALS》 * |
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| WO2017085493A1 (en) * | 2015-11-20 | 2017-05-26 | Huntsman P&A Uk Limited | Coatings |
| CN108884339A (en) * | 2015-11-20 | 2018-11-23 | 维纳特材料英国有限公司 | coating |
| JP2019501271A (en) * | 2015-11-20 | 2019-01-17 | ベナトール マテリアルズ ユーケー リミテッド | Coating material |
| US10406505B1 (en) | 2015-11-20 | 2019-09-10 | Venator Materials Uk Limited | Coatings |
| TWI726005B (en) * | 2015-11-20 | 2021-05-01 | 英商英國漢士門Ｐ＆Ａ股份有限公司 | Coatings |
| AU2016355108B2 (en) * | 2015-11-20 | 2021-06-24 | Venator Materials Uk Limited | Coatings |
| CN108884339B (en) * | 2015-11-20 | 2021-10-15 | 维纳特材料英国有限公司 | Coating layer |
| CN105540827A (en) * | 2015-12-17 | 2016-05-04 | 山东大学 | Method for preparing graded titanium dioxide microsphere filler of surface-directional-growth-based nanorod |
| CN105540827B (en) * | 2015-12-17 | 2018-01-05 | 山东大学 | A kind of preparation method of the graduation titanium dioxide microballoon sphere filler based on surface orientation growing nano-rod |
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Application publication date: 20150819 |