CN103818954A - Preparation method of anatase TiO2 hollow microspheres with exposed (001) surface - Google Patents
Preparation method of anatase TiO2 hollow microspheres with exposed (001) surface Download PDFInfo
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- CN103818954A CN103818954A CN201410055875.1A CN201410055875A CN103818954A CN 103818954 A CN103818954 A CN 103818954A CN 201410055875 A CN201410055875 A CN 201410055875A CN 103818954 A CN103818954 A CN 103818954A
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Abstract
The invention relates to a preparation method of anatase TiO2 hollow microspheres with an exposed (001) surface, and the preparation method is as follows: reacting a titanium or titanium alkoxide salt with an alkali solution to obtain a precipitate to dissolve in a hydrofluoric acid solution, then performing hydrothermal reaction at 100-200 DEG C, after the reaction, washing a product to be neutral, and then drying to obtain the anatase TiO2 hollow microspheres. The preparation method has the advantages of low cost and simple process, the prepared TiO2 crystal form is anatase, the crystal is complete, the structure is novel, and the TiO2 hollow microspheres can be widely applied in the fields of photocatalysis, dye-sensitized solar cells, lithium batteries and the like.
Description
Technical field
The invention belongs to anatase octahedrite TiO
2the preparation field of micro-sphere material, particularly one has the anatase octahedrite TiO that (001) face exposes
2the preparation method of tiny balloon.
Background technology
Titanium dioxide is a kind of very important transition metal oxide, has nontoxic, stable chemical nature, low cost and other advantages, therefore in photochemical catalysis, be widely used from fields such as peace and quiet, sensor, lithium cell, coating and makeup.
The application of titanium dioxide is not only relevant with crystalline phase and particle size, and the surface exposing to crystal is also relevant, in recent years, has the TiO of high-energy surface
2by large quantity research.From theoretical and experimental studies have found that anatase octahedrite TiO
2(001) face have higher catalytic activity than (101) mask.How to prepare the TiO with (001) face
2receive increasing concern, but, anatase octahedrite TiO
2(001) face have the higher average surface can be for 0.90J/m
2, in crystal growing process, follow surperficial energy minimization principle, (001) face can diminish very soon until disappear, and (101) mask has the lower surface can (0.44J/m
2), in the time that growing, crystal can keep Thermodynamically stable state, so the anatase octahedrite TiO making at present
2being exposed to outer great majority is low energy (101) faces, to such an extent as to more difficultly makes the TiO that very major part is (001) face
2.On the other hand, titanium dioxide nano-particle is easily reunited and is caused specific surface reduction, the compound quickening of crystal boundary, and the hollow ball of high energy (001) face exposure can overcome this shortcoming; Titanium dioxide hollow ball can be used as scattering particles, the light material of solar cell, aspect practical application and fundamental research, is having broad application prospects.Therefore, preparation has the TiO of (001) face exposure of low density, high-ratio surface and high catalytic performance
2tiny balloon has significant application value.
Many document patents disclose and have prepared the TiO with (001) face both at home and abroad
2method and performance study.The people such as Yang at [Nature.Vol.453 (2008) pp.638～642] report using titanium tetrafluoride and hydrofluoric acid as reactant, the synthetic anatase octahedrite TiO with 47% (001) face for the first time
2monocrystalline, its particle diameter is greater than 1.0 μ m.Further add after Virahol at document [Journal of the American Chemical Society.Vol.131 (2009) pp.4078～4083] report, the ratio that obtains (001) face has had large increase.Subsequently, document [Journal of the American Chemical Society.Vol.131 (2009) pp.3152～3153], [Chemistry-A European Journal.Vol.18 (2012) pp.7525～7532], [Materials Letters.Vol.66 (2012) pp.308～310], [Journal of Alloys and Compounds.Vol.548 (2013) pp.194～200], [Applied Surface Science.Vol.265 (2013) pp.438～442], [RSC Advances.Vol.3 (2013) pp.1222～1226] etc. are with titanium tetrachloride, titanium valve, titanium sulfate, titanium isopropylate, titanium tetrafluorides etc. are as titanium source, adopt different methods to prepare the anatase octahedrite TiO with (001) face
2.In patent [CN201010231407.7], disclose one and there is the anatase octahedrite TiO of (001) face area greatly
2the preparation method of monocrystalline, is take titanium valve as raw material, by hydro-thermal reaction, titanium valve is first dissolved in hydrofluoric acid solution, then the hydrofluoric acid dissolving is mixed with rare hydrogen peroxide, and hydro-thermal reaction again, thus obtain (001) face TiO
2monocrystalline.Subsequently, in patent [CN201110312094.2], a kind of titanium dioxide with high-energy surface hollow structure and preparation method thereof is disclosed, mainly using titanium valve, hydrogen fluoride and hydrogen peroxide as reactant, under hydrothermal condition, reaction can make by the platy particle of the high-energy surface hollow structure titanium dioxide forming of reuniting.
Summary of the invention
Technical problem to be solved by this invention is to provide one and has the anatase octahedrite TiO that (001) face exposes
2the preparation method of tiny balloon, this inventive method is easy and simple to handle, and equipment and process is simple, does not need tensio-active agent or inhibitor, and cost is low, does not need aftertreatment; In this invention, adopt wet TiO
2precipitation, chemically reactive is high, and in reaction, hydrofluoric acid consumption is few; The titanium dioxide crystal form that this invention prepares is anatase octahedrite, perfect crystalline, and novel structure, is widely used in fields such as photochemical catalysis, dye sensitization solar battery, lithium celies.
One of the present invention has the anatase octahedrite TiO that (001) face exposes
2the preparation method of tiny balloon, comprising:
(1) preparation of hydrofluotitanic acid solution
Titanium source is dispersed in solvent, is then added dropwise to ammoniacal liquor, stir, then add deionized water, after stirring, be heated to 60 ℃, magnetic agitation 2-4h, after completion of the reaction, is cooled to room temperature, obtains hydrous titanium oxide or titanium hydroxide, and washing, obtains moist precipitate; Wherein the volume ratio of titanium source, solvent, ammoniacal liquor, deionized water is 4:80:1:1-4:160:2:3; Moist precipitate is joined in the deionized water of 30-70ml, magnetic agitation, is then added dropwise to hydrofluoric acid, stirs, and obtains transparent or nattier blue hydrofluotitanic acid solution; Wherein F-and Ti in hydrofluotitanic acid solution
4+molar concentration rate be 6:1-10:1;
Reaction process is suc as formula shown in 1-1:
TiO
2+6HF→H
2TiF
6+2H
2O (1-1)
(2) hydrothermal treatment consists of hydrofluotitanic acid solution
Above-mentioned hydrofluotitanic acid solution is carried out to hydrothermal treatment consists, and treatment temp is 100-200 ℃, and the time is 5-20h, and then washing is dry, must have the anatase octahedrite TiO that (001) face exposes
2tiny balloon.
Reaction process is suc as formula shown in 1-2:
H
2TiF
6+2H
2O→TiO
2+6HF (1-2)
Wherein hydrothermal treatment consists is specially hydrofluotitanic acid solution is placed in teflon-lined reactor, and reactor is put into baking oven at 100-200 ℃, reaction 5-20h.
In described step (1), titanium source is titanium salt or titanium alkoxide.
Inorganic salt, tetrabutyl titanate that in described step (1), titanium source is titanium, titanium ethanolate or isopropyl titanate etc.
In described step (1), solvent is ethanol.
In described step (1), stir as first stirring 30-60min, then add after deionized water, stir 10-20min, be added dropwise to hydrofluoric acid, stir 60-120min.
In described step (1), washing is 7 for being precipitated to pH value with ethanol and deionized water wash.
In described step (1), the mass percentage concentration of hydrofluoric acid is 20.0%-40.0%.
In described step (2), washing is until the pH value of product is 7 with deionized water wash; Drying temperature is 50-110 ℃, and be 5-30h time of drying.
In described step (2), there is the anatase octahedrite TiO that (001) face exposes
2tiny balloon, wall thickness is 70-300nm, and size is 0.7-2.0 μ m, and grain-size is 30-100nm.
In the present invention, because titanium valve price is higher and reaction violent, in water-heat process, need inhibitor; Crystallization TiO
2inner particle arrangement regulation, reactive behavior is low, needs a large amount of severe corrosive solvents in reaction process; And the unformed TiO of moist precipitate
2surface and crystal in there is a large amount of defects and dislocation, easily become the deathnium of hole and electronics, can accelerate to react with hydrofluoric acid.Therefore the present invention is mainly a kind of wet TiO that adopts
2precipitation is reacted with hydrofluoric acid aqueous solution Direct Hydrothermal and is made the hollow titanium dioxide microballoon sphere with (001) face.
In the present invention, hydrofluoric acid is to having high energy (001) face TiO
2pattern have a significant impact, TiO
2(001) mask have the higher surface can, F ion can be preferentially adsorbed to high energy (001) face, slow down along the growth velocity of (001) face so, and be conducive to there is the growth compared with low surface energy (101) face, therefore F ion can be stablized (001) crystal face as crystal face directed agents in hydro-thermal reaction, form the Anatase TiO that (001) face exposes at high proportion
2; On the other hand, F ion also plays stabilizer function, suppresses TiO
2fast Growth.
beneficial effect
(1) the inventive method is easy and simple to handle, and equipment and process is simple, does not need tensio-active agent or inhibitor, and cost is low, does not need aftertreatment;
(2) in the present invention, adopt wet TiO
2precipitation, chemically reactive is high, and in reaction, hydrofluoric acid consumption is few;
(3) titanium dioxide crystal form that the present invention makes is anatase octahedrite, perfect crystalline, and novel structure, is widely used in fields such as photochemical catalysis, dye sensitization solar battery, lithium celies;
(4) titania that the present invention makes is of a size of 30～100nm, and size is 0.7～2.0 μ m, can be by controls such as hydro-thermal time and temperature.
Accompanying drawing explanation
Fig. 1 is the TiO with the exposure of (001) face that the embodiment of the present invention 1 makes
2tiny balloon X-ray diffractogram;
Fig. 2 is the TiO with the exposure of (001) face that the embodiment of the present invention 1 makes
2tiny balloon field emission scanning electron microscope figure FE-SEM; Wherein illustration is TiO
2tiny balloon section field emission scanning electron microscope (FE-SEM) photo;
Fig. 3 is the TiO with the exposure of (001) face that the embodiment of the present invention 1 makes
2tiny balloon transmission electron microscope photo TEM; Wherein a is the TiO that (001) face exposes that has making
2the low power transmission electron microscope photo of tiny balloon; The TiO that b exposes for having (001) face
2the high power transmission electron microscope photo of tiny balloon;
Fig. 4 is the TiO with the exposure of (001) face that the embodiment of the present invention 1 makes
2the N of tiny balloon
2absorption/desorption isotherm, illustration is pore size distribution curve;
Fig. 5 is the TiO with the exposure of (001) face that the embodiment of the present invention 2 makes
2tiny balloon field emission scanning electron microscope (FE-SEM) photo (a) and transmission electron microscope photo TEM(b);
Fig. 6 is the TiO with the exposure of (001) face that the embodiment of the present invention 3 makes
2tiny balloon field emission scanning electron microscope (FE-SEM) photo; (a) be low power field emission scanning electron microscope photo; (b) be high power field emission scanning electron microscope photo;
Fig. 7 is the TiO with the exposure of (001) face that the embodiment of the present invention 3 makes
2the N of tiny balloon
2absorption/desorption isotherm.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Under room temperature, take 2.0ml tetrabutyl titanate and be scattered in 100ml dehydrated alcohol, after stirring, add 1ml ammoniacal liquor, stir 60min; Then slowly add 1.5ml deionized water, stir after 20min, oil bath is heated to 60 ℃ of magnetic agitation 4h, after completion of the reaction, is cooled to room temperature, is precipitated to pH value reaches 7 with ethanol and deionized water wash.
By previous step gained moist precipitate, add 50ml deionized water, magnetic agitation 30min, adds the hydrofluoric acid of 0.7ml40.0wt%, puts in reactor, stirs after 10min, reactor is put into the baking oven of 180 ℃, reaction 15h.Reaction finish after, by reaction product with deionized water rinsing until the pH value of product is 7; Then products therefrom is placed in to the oven drying 24 hours of 100 ℃, thereby obtains described hollow TiO
2microballoon.
The powder that above-mentioned steps is made carries out analytical test.Fig. 1 is the TiO that (001) face exposes that has making in the present embodiment
2tiny balloon X-ray diffractogram, by contrasting with standard card (JCPDS No.21-1272), the known product obtaining is pure anatase octahedrite TiO
2, and (004) crystal face intensity obviously improves, and the TiO obtaining is described
2hollow ball surface is surrounded by (001) face; Fig. 2 is the TiO with the exposure of (001) face that the embodiment of the present invention makes
2tiny balloon field emission scanning electron microscope figure can know and see hollow TiO from figure
2microspherulite diameter size is 1.2 μ m, TiO
2microsphere surface is made up of the four sides cone shortening, tetrahedral length and the wide 50-100nm that is respectively, and middle hollow ball diameter is 150nm; Fig. 3 is the TiO with the exposure of (001) face that the embodiment of the present invention makes
2tiny balloon transmission electron microscope photo; Wherein Fig. 3 a is the TiO with the exposure of (001) face that the embodiment of the present invention makes
2the low power transmission electron microscope photo of tiny balloon, as we know from the figure, the TiO making
2for hollow ball, surface is made up of regular four sides cone; Fig. 3 b is the TiO with the exposure of (001) face that the embodiment of the present invention makes
2the high power transmission electron microscope photo of tiny balloon, as can be seen from the figure, has the spacing of 0.237nm, and corresponding (004) crystal face, illustrates TiO
2there is high energy (001) face on surface; Fig. 4 is the TiO with the exposure of (001) face that the embodiment of the present invention makes
2the N of tiny balloon
2absorption/desorption isotherm, illustration is pore size distribution curve, as we know from the figure, the TiO making
2the specific surface area of hollow ball is 36.1m
2g
-1, pore size distribution is at 2.0nm～100nm.
Under room temperature, take 1.5ml tetrabutyl titanate and be scattered in 80ml dehydrated alcohol, after stirring, add 0.65ml ammoniacal liquor, stir 60min; Then slowly add 1.1ml deionized water, stir after 20min, oil bath is heated to 60 ℃ of magnetic agitation 4h, after completion of the reaction, is cooled to room temperature, is precipitated to pH value reaches 7 with ethanol and deionized water wash.
By previous step gained moist precipitate, add 50ml deionized water, magnetic agitation 30min, adds the hydrofluoric acid of 0.6ml40.0wt%, puts in reactor, stirs after 10min, reactor is put into the baking oven of 200 ℃, reaction 10h.Reaction finish after, by reaction product with deionized water rinsing until the pH value of product is 7; Then products therefrom is placed in to the oven drying 24 hours of 100 ℃, thereby obtains described hollow TiO
2microballoon.
Fig. 5 is the TiO with the exposure of (001) face that the embodiment of the present invention makes
2tiny balloon field emission scanning electron microscope photo and transmission electron microscope photo; Fig. 5 a is the TiO with the exposure of (001) face that the embodiment of the present invention makes
2tiny balloon scanning electron microscope (SEM) photograph, the hollow titanium dioxide granule mean size obtaining is 1 μ m, the platy particle with high energy (001) face is evenly distributed on titanium dioxide surface; Fig. 5 b is the TiO with the exposure of (001) face that the embodiment of the present invention makes
2tiny balloon transmission electron microscope photo, from scheming, the titanium dioxide making is hollow structure.
Under room temperature, take 1.0ml tetrabutyl titanate and be scattered in 60ml dehydrated alcohol, after stirring, add 0.4ml ammoniacal liquor, stir 60min; Then slowly add 0.7ml deionized water, stir after 20min, oil bath is heated to 60 ℃ of magnetic agitation 4h, after completion of the reaction, is cooled to room temperature, is precipitated to pH value reaches 7 with ethanol and deionized water wash.
By previous step gained moist precipitate, add 50ml deionized water, magnetic agitation 30min, adds the hydrofluoric acid of 0.8ml40.0wt%, puts in reactor, stirs after 10min, reactor is put into the baking oven of 150 ℃, reaction 20h.Reaction finish after, by reaction product with deionized water rinsing until the pH value of product is 7; Then products therefrom is placed in to the oven drying 24 hours of 100 ℃, thereby obtains described hollow TiO
2microballoon.
Fig. 6 is the TiO with the exposure of (001) face that the embodiment of the present invention 3 makes
2tiny balloon scanning electron microscope (SEM) photograph, Fig. 6 a is low power field emission scanning electron microscope figure, the known titanium dioxide size uniform making is better dispersed; Fig. 6 b is high power scanning electron microscope (SEM) photograph, and known titanium dioxide surface is made up of round sheet, and platy shaped particle size homogeneous is densely distributed at titanium dioxide surface; What the embodiment of the present invention made as shown in Figure 7 has the TiO that (001) face exposes
2the specific surface area of tiny balloon is 80.8m
2g
-1.
Embodiment 4
Under room temperature, take 0.5ml tetrabutyl titanate and be scattered in 40ml dehydrated alcohol, after stirring, add 0.2ml ammoniacal liquor, stir 60min; Then slowly add 0.35ml deionized water, stir after 20min, oil bath is heated to 60 ℃ of magnetic agitation 4h, after completion of the reaction, is cooled to room temperature, is precipitated to pH value reaches 7 with ethanol and deionized water wash.
By previous step gained moist precipitate, add 50ml deionized water, magnetic agitation 30min, adds 0.5ml, and the hydrofluoric acid of 40.0wt% is put in reactor, stirs after 10min, reactor is put into the baking oven of 100 ℃, reaction 5h.Reaction finish after, by reaction product with deionized water rinsing until the pH value of product is 7; Then the product of gained is placed in to the oven drying 24h of 100 ℃, thereby obtains described hollow TiO
2microballoon.
Claims (9)
1. one kind has the anatase octahedrite TiO that (001) face exposes
2the preparation method of tiny balloon, comprising:
(1) titanium source is dispersed in solvent, then adds ammoniacal liquor to stir, then add deionized water, after stirring, be heated to 60 ℃ of magnetic agitation 2-4h, after completion of the reaction, be cooled to room temperature, washing, obtains moist precipitate; Wherein the volume ratio of titanium source, solvent, ammoniacal liquor, deionized water is 4:80:1:1-4:160:2:3; Moist precipitate is joined in deionized water, and magnetic agitation, then adds hydrofluoric acid, stirs, and obtains hydrofluotitanic acid solution; Wherein F-and Ti in hydrofluotitanic acid solution
4+molar concentration rate be 6:1-10:1;
(2) above-mentioned hydrofluotitanic acid solution is carried out to hydrothermal treatment consists, treatment temp is 100-200 ℃, and the time is 5-20h, and then washing is dry, must have the anatase octahedrite TiO that (001) face exposes
2tiny balloon.
2. one according to claim 1 has the anatase octahedrite TiO that (001) face exposes
2the preparation method of tiny balloon, is characterized in that: in described step (1), titanium source is titanium salt or titanium alkoxide.
3. one according to claim 1 has the anatase octahedrite TiO that (001) face exposes
2the preparation method of tiny balloon, is characterized in that: inorganic salt, butyl (tetra) titanate, titanium ethanolate or isopropyl titanate that in described step (1), titanium source is titanium.
4. one according to claim 1 has the anatase octahedrite TiO that (001) face exposes
2the preparation method of tiny balloon, is characterized in that: in described step (1), solvent is ethanol.
5. one according to claim 1 has the anatase octahedrite TiO that (001) face exposes
2the preparation method of tiny balloon, is characterized in that: in described step (1), stir as first stirring 30-60min, then add after deionized water, stir 10-20min, be added dropwise to hydrofluoric acid, stir 60-120min.
6. one according to claim 1 has the anatase octahedrite TiO that (001) face exposes
2the preparation method of tiny balloon, is characterized in that: in described step (1), washing is 7 for being precipitated to pH value with ethanol and deionized water wash.
7. one according to claim 1 has the anatase octahedrite TiO that (001) face exposes
2the preparation method of tiny balloon, is characterized in that: in described step (1), the mass percentage concentration of hydrofluoric acid is 20.0%-40.0%.
8. one according to claim 1 has the anatase octahedrite TiO that (001) face exposes
2the preparation method of tiny balloon, is characterized in that: in described step (2), washing is until the pH value of product is 7 with deionized water wash; Drying temperature is 50-110 ℃, and be 5-30h time of drying.
9. one according to claim 1 has the anatase octahedrite TiO that (001) face exposes
2the preparation method of tiny balloon, is characterized in that: in described step (2), have the anatase octahedrite TiO that (001) face exposes
2tiny balloon, wall thickness is 70-300nm, and size is 0.7-2.0 μ m, and grain-size is 30-100nm.
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Cited By (10)
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|---|---|---|---|---|
| CN104118907A (en) * | 2014-07-24 | 2014-10-29 | 河南科技大学 | Preparation method of surface-nanoetched titanium dioxide microspheres |
| CN104310466A (en) * | 2014-10-10 | 2015-01-28 | 常州大学 | Hollow titanium dioxide microsphere based on gel sphere precursor and preparation method of hollow titanium dioxide microsphere |
| CN104724755A (en) * | 2015-03-06 | 2015-06-24 | 华北电力大学 | Preparation method of micron-sized lamellar titanium dioxide nano material |
| CN105133013A (en) * | 2015-07-28 | 2015-12-09 | 中国人民解放军军械工程学院 | Three-dimensional hollow titanium dioxide assembled from (001) surfaces, and preparation method and application thereof |
| CN106335922A (en) * | 2016-08-23 | 2017-01-18 | 中国科学院广州地球化学研究所 | Preparation method of high(001)-crystal-facet ultrathin anatase nanosheet self-assembled microspheres |
| CN109046302A (en) * | 2018-08-27 | 2018-12-21 | 合肥工业大学 | A kind of porous petal-like anatase TiO2Nano-crystal film and preparation method thereof |
| CN109746020A (en) * | 2019-01-16 | 2019-05-14 | 浙江理工大学 | A kind of preparation method of nitrogen-doped titanium dioxide of the surface with high energy crystal face |
| CN110054222A (en) * | 2019-06-10 | 2019-07-26 | 青岛科技大学 | It is a kind of to prepare mesoporous single crystals TiO2The method of nanoparticle |
| CN110803712A (en) * | 2019-07-09 | 2020-02-18 | 华东理工大学 | Preparation method and application of ovoid carbon-coated single-crystal titanium dioxide microspheres |
| US20210039958A1 (en) * | 2018-04-12 | 2021-02-11 | Croda International Plc | Titanium dioxide particles |
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| CN104118907A (en) * | 2014-07-24 | 2014-10-29 | 河南科技大学 | Preparation method of surface-nanoetched titanium dioxide microspheres |
| CN104310466A (en) * | 2014-10-10 | 2015-01-28 | 常州大学 | Hollow titanium dioxide microsphere based on gel sphere precursor and preparation method of hollow titanium dioxide microsphere |
| CN104310466B (en) * | 2014-10-10 | 2016-03-09 | 常州大学 | A kind of hollow titanium dioxide microballoon based on gel ball presoma and preparation method thereof |
| CN104724755A (en) * | 2015-03-06 | 2015-06-24 | 华北电力大学 | Preparation method of micron-sized lamellar titanium dioxide nano material |
| CN105133013A (en) * | 2015-07-28 | 2015-12-09 | 中国人民解放军军械工程学院 | Three-dimensional hollow titanium dioxide assembled from (001) surfaces, and preparation method and application thereof |
| CN106335922B (en) * | 2016-08-23 | 2017-11-10 | 中国科学院广州地球化学研究所 | A kind of preparation method of the ultra-thin anatase nanometer sheet self-assembly microspheres in height (001) face |
| CN106335922A (en) * | 2016-08-23 | 2017-01-18 | 中国科学院广州地球化学研究所 | Preparation method of high(001)-crystal-facet ultrathin anatase nanosheet self-assembled microspheres |
| US20210039958A1 (en) * | 2018-04-12 | 2021-02-11 | Croda International Plc | Titanium dioxide particles |
| CN109046302A (en) * | 2018-08-27 | 2018-12-21 | 合肥工业大学 | A kind of porous petal-like anatase TiO2Nano-crystal film and preparation method thereof |
| CN109046302B (en) * | 2018-08-27 | 2021-12-07 | 合肥工业大学 | Porous petal-shaped anatase TiO2Nanocrystalline thin film and preparation method thereof |
| CN109746020A (en) * | 2019-01-16 | 2019-05-14 | 浙江理工大学 | A kind of preparation method of nitrogen-doped titanium dioxide of the surface with high energy crystal face |
| CN110054222A (en) * | 2019-06-10 | 2019-07-26 | 青岛科技大学 | It is a kind of to prepare mesoporous single crystals TiO2The method of nanoparticle |
| CN110803712A (en) * | 2019-07-09 | 2020-02-18 | 华东理工大学 | Preparation method and application of ovoid carbon-coated single-crystal titanium dioxide microspheres |
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