CN104692457A - Litchi-shaped micro-nano hierarchical-structure TiO2 crystal and synthesis method thereof - Google Patents

Litchi-shaped micro-nano hierarchical-structure TiO2 crystal and synthesis method thereof Download PDF

Info

Publication number
CN104692457A
CN104692457A CN201510035292.7A CN201510035292A CN104692457A CN 104692457 A CN104692457 A CN 104692457A CN 201510035292 A CN201510035292 A CN 201510035292A CN 104692457 A CN104692457 A CN 104692457A
Authority
CN
China
Prior art keywords
crystal
tio
micro
nano hierarchy
spherical
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510035292.7A
Other languages
Chinese (zh)
Other versions
CN104692457B (en
Inventor
赵巍
王红杏
冯香宁
殷建
赵丹
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tianjin Chengjian University
Original Assignee
Tianjin Chengjian University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tianjin Chengjian University filed Critical Tianjin Chengjian University
Priority to CN201510035292.7A priority Critical patent/CN104692457B/en
Publication of CN104692457A publication Critical patent/CN104692457A/en
Application granted granted Critical
Publication of CN104692457B publication Critical patent/CN104692457B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G23/00—Compounds of titanium
    • C01G23/04—Oxides; Hydroxides
    • C01G23/047—Titanium dioxide
    • C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
    • C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/03—Particle morphology depicted by an image obtained by SEM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/30—Particle morphology extending in three dimensions
    • C01P2004/32—Spheres
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/60—Particles characterised by their size
    • C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)

Abstract

The invention relates to a litchi-shaped micro-nano hierarchical-structure TiO2 crystal and a synthesis method thereof. The synthesis method comprises the following steps: preparing a uniformly dispersed spherical amorphous precursor TiO2, and crystallizing the precursor TiO2 and a solvent in a hydrothermal environment to obtain a TiO2 crystal with a litchi-shaped micro-nano hierarchical structure. The prepared TiO2 crystal is spherical and has a diameter of 500-700nm, and spherical bulges with diameters of 10-20nm are uniformly distributed on the spherical surface. With an anatase structure, the TiO2 crystal has important application to solar cells, photocatalysis, self-cleaning and the like. Meanwhile, the method provides a new idea for the surface grading decoration of other particles.

Description

The micro-nano hierarchy TiO of a kind of lichee shape 2crystal and synthetic method thereof
Technical field
The present invention relates to a kind of TiO 2micro Nano material, the micro-nano hierarchy TiO of especially a kind of lichee shape 2crystal and synthetic method thereof
Technical background
Titanium dioxide (TiO 2) there is excellent photoelectric properties and physical property, have a wide range of applications in fields such as chromatographic separation, lithium ion battery, dye sensitization solar battery, gas sensor, catalysis, its with low cost and environment friendly also receives the favor of investigator, is therefore the study hotspot of information and power and environmentally conscious materials always.
Pile up because spherical morphology has uniform close, the characteristic that surface curvature, mobility etc. are adjustable, monodisperse spherical TiO 2material has demonstrated many real and emerging application.Utilize liquid phase method, synthesize the TiO of different morphologies 2powder granule, as adopted sol-gel traditional technology mating surface promoting agent synthesizing spherical TiO 2particle, utilizes polystyrene spheres, SiO 2the synthesizing porous TiO of prefab-form such as ball, C ball, PMMA ball 2ball.But above-mentioned preparation technology mostly is the single dispersing TiO of synthesizing micron-grade 2ball, still there is pattern and dispersed uncontrollable, the shortcoming such as technique is more complicated in the monodisperse sphere for Nano grade.
The microtexture of material and the arrangement mode in space thereof produce material impact by the performance of material, the nanostructure field that the is prepared in dominate of low-dimensional nano structure material, and the compound with secondary nanostructure makes it may will have more novel character in optical, electrical, magnetic etc. because of the structure of its novelty and unique chemical physical property and pattern and the extreme influence of size to character.Therefore, to TiO 2the research of the secondary structure of granule-morphology is also more and more extensive, and its Application Areas is also provided with more wide prospect.
The present invention is based on the principle of process simplification, by first synthesizing micron-grade single dispersing persursor material, then in the liquid phase environment of gentleness the secondary microtexture of decorative material, synthesized the TiO with new meaning pattern 2powder granule, expects to be more widely used.
Summary of the invention
The invention provides the micro-nano hierarchy TiO of a kind of lichee shape 2crystal and synthetic method thereof, is characterized in that, the micro-nano hierarchy TiO of described lichee shape 2crystal is spherical, and spherical surface is distributed with the ball bumps of small particle size, and crystal formation is Detitanium-ore-type;
The micro-nano hierarchy TiO of described lichee shape 2spherical diameter is 500-700nm, and the diameter of described ball bumps is 10-20nm.
Preferably, the micro-nano hierarchy TiO of lichee shape 2crystal preparation step is as follows:
(1), under room temperature condition, be that the PVP of 1.5-2:25:75, water and n-propyl alcohol make mixed liquor A, by Ti (SO by W/V/V 4) 2solution is slowly poured in mixed liquor A, and after stirring, 70 DEG C of heating in water bath 3h-6h obtain mixed liquid B, after mixed liquid B is cooled to room temperature, centrifugal, washing, be 60 DEG C of ageing 12h in 1-2mol/L KOH solution in volumetric molar concentration, centrifugal, washing, dry after obtain presoma TiO 2powder C;
(2) mixed by precursor powder C and solvent D, precursor powder C and solvent D mass volume ratio W/V is 0.4:20, inserts water heating kettle and heat 2h at 180 DEG C, centrifugal, washing, dry after obtain the micro-nano hierarchy TiO of lichee shape 2crystal powder.
Preferably, in described step (1), Ti (SO 4) 2solution volumetric molar concentration is 0.8mol/L, Ti (SO 4) 2described in solution and this step, mixed solution A volume ratio V/V is 1:2.
Preferably, in described step (2), solvent D is ethylene glycol, the 0.01g/mL cetyl trimethylammonium bromide aqueous solution or volume ratio V/V are one in the DMF/ aqueous solution of 1:1.
Major advantage of the present invention is as follows:
(1) the obtained micro-nano hierarchy TiO of lichee shape 2the spherical diameter of crystal is 500-700nm, belongs to micro/nano level, and large particle diameter makes TiO 2crystal is easy to when being used as catalyzer reclaim.
(2) lichee shape hierarchy is that final product remains the pattern of presoma by obtaining the finishing of presoma, and defines secondary microtexture, is conducive to the specific surface area improving material, improves its photocatalysis characteristic further.
Accompanying drawing explanation
Fig. 1 is presoma TiO in embodiment 1 2scanning electron microscope diagram;
Fig. 2 is the micro-nano hierarchy TiO of lichee shape in embodiment 1 2the scanning electron microscope diagram of crystal;
Fig. 3 is presoma TiO in embodiment 1 2and the micro-nano hierarchy TiO of lichee shape 2xRD figure;
Fig. 4 is the micro-nano hierarchy TiO of lichee shape in embodiment 2 2the scanning electron microscope diagram of crystal;
Fig. 5 is the micro-nano hierarchy TiO of lichee shape in embodiment 3 2the scanning electron microscope diagram of crystal;
Fig. 6 is presoma TiO in embodiment 5 2scanning electron microscope diagram;
Fig. 7 is presoma TiO in embodiment 6 2scanning electron microscope diagram;
Fig. 8 is the test result of degradation of methylene blue in embodiment 7.
Embodiment
Embodiment 1
(1) 2gPVP, 25mL water and 75mL n-propyl alcohol are mixed with mixed liquor A, by the Ti (SO of 50mL 0.8mol/L 4) 2the aqueous solution is slowly poured in mixed liquor A, and after stirring, 70 DEG C of heating in water bath 3h-6h obtain mixed liquid B, after mixed liquid B is cooled to room temperature, centrifugal, washing, 60 DEG C of ageing 12h in 1mol/L KOH solution, centrifugal, washing, dry after obtain TiO 2precursor powder C;
(2) 0.4g precursor powder C being joined 20mL volume ratio is mix in the DMF/ aqueous solution of 1:1, and the water heating kettle pouring 25mL into heats 2h at 180 DEG C, centrifugal, washing, dry after obtain the micro-nano hierarchy TiO of lichee shape 2crystal powder.
Fig. 1 is presoma TiO in the present embodiment 2the scanning electron microscope diagram of powder, can find out presoma TiO 2for equally distributed spherical, diameter is about 700nm.
Fig. 2 is the micro-nano hierarchy TiO of lichee shape that the present embodiment obtains 2the scanning electron microscope diagram of crystal, can find out, this TiO 2crystal entirety is spherical, and diameter is about 700nm, and spherical surface is evenly distributed with the ball bumps that diameter is about 20nm.
Fig. 3 is the present embodiment presoma TiO 2and the micro-nano hierarchy TiO of lichee shape 2the XRD figure of crystal, can find out, presoma TiO 2xRD spectra substantially do not go out peak, presoma TiO is described 2do not form crystallization, belong to unformed shape.The micro-nano hierarchy TiO of lichee shape 2crystal is Detitanium-ore-type, does not have dephasign, and show that crystalline structure is complete, peak shape is broadening slightly, shows have nanostructure to generate.
Embodiment 2
(1) 2.0gPVP, 25mL water and 75mL n-propyl alcohol are mixed with mixed liquor A, by the Ti (SO of 50mL 0.8mol/L 4) 2the aqueous solution is slowly poured in mixed liquor A, and after stirring, 70 DEG C of heating in water bath 3h-6h obtain mixed liquid B, after mixed liquid B is cooled to room temperature, centrifugal, washing, 60 DEG C of ageing 12h in 1.0mol/L KOH solution, centrifugal, washing, dry after obtain TiO 2precursor powder C;
(2) 4g precursor powder C being joined 20mL volume is mix in the ethylene glycol solution of 20mL, and the water heating kettle pouring 25mL into heats 2h at 180 DEG C, centrifugal, washing, dry after obtain the micro-nano hierarchy TiO of lichee shape 2crystal powder.
The micro-nano hierarchy TiO of the lichee shape obtained 2the scanning electron microscope diagram of crystal as shown in Figure 4.Can find out, this TiO 2crystal entirety is spherical, and diameter is about 500nm, and spherical surface is evenly distributed with the ball bumps that diameter is about 10nm.
Embodiment 3
(1) 2gPVP, 25mL water and 75mL n-propyl alcohol are mixed with mixed liquor A, by the Ti (SO of 50mL 0.8mol/L 4) 2the aqueous solution is slowly poured in mixed liquor A, and after stirring, 70 DEG C of heating in water bath 3h-6h obtain mixed liquid B, after mixed liquid B is cooled to room temperature, centrifugal, washing, 60 DEG C of ageing 12h in 1mol/LKOH solution, centrifugal, washing, dry after obtain TiO 2precursor powder C;
(2) joined in the 20mL 0.01g/mL cetyl trimethylammonium bromide aqueous solution by 0.4g precursor powder C and mix, the water heating kettle pouring 25mL into heats 2h at 180 DEG C, centrifugal, washing, dry after obtain the micro-nano hierarchy TiO of lichee shape 2crystal powder.
The micro-nano hierarchy TiO of the lichee shape obtained 2the scanning electron microscope diagram of crystal as shown in Figure 5.Can find out, this TiO 2crystal entirety is spherical, and diameter is about 600nm, and spherical surface is evenly distributed with the ball bumps that diameter is about 10nm.
Embodiment 4
(1) 200gPVP, 2500mL water and 7500mL n-propyl alcohol are mixed with mixed liquor A, by the Ti (SO of 5000mL 0.8mol/L 4) 2the aqueous solution is slowly poured in mixed liquor A, and after stirring, 70 DEG C of heating in water bath 3h-6h obtain mixed liquid B, after mixed liquid B is cooled to room temperature, centrifugal, washing, 60 DEG C of ageing 12h in 1mol/L KOH solution, centrifugal, washing, dry after obtain TiO 2precursor powder C;
(2) 40g precursor powder C being joined 2000mL volume ratio is mix in the DMF/ aqueous solution of 1:1, and the water heating kettle pouring 2500mL into heats 2h at 180 DEG C, centrifugal, washing, dry after obtain the micro-nano hierarchy TiO of lichee shape 2crystal powder.
The presoma TiO that the present embodiment obtains 2the micro-nano hierarchy TiO of the scanning electron microscope diagram of powder, lichee shape 2the scanning electron microscope diagram of crystal and presoma TiO 2and the micro-nano hierarchy TiO of lichee shape 2the XRD figure of crystal is with Fig. 1-Fig. 3 in embodiment 1.
Embodiment 5
The present embodiment is embodiment as a comparison, detects PVP addition to the micro-nano hierarchy TiO of lichee shape 2the impact of crystal, PVP add-on is 1.5g, all the other conditions with embodiment 1, the presoma TiO obtained 2scanning electron microscope diagram as shown in Figure 6, can find out, this presoma TiO 2there is agglomeration, reason is that surfactant concentration is not high, sterically hindered DeGrain.
Embodiment 6
The present embodiment is embodiment as a comparison, and during detection ageing, in step (1), KOH adds concentration to the micro-nano hierarchy TiO of lichee shape during ageing 2the impact of crystal, it is 2mol/L that KOH adds concentration, and all the other conditions are with embodiment 1.The presoma TiO obtained 2scanning electron microscope diagram as shown in Figure 7, can find out, this presoma TiO 2pattern is uneven, spheroid has small-particle or pit exist.Reason is that KOH concentration is excessive, has corrosive nature to presoma.
Embodiment 7
Embodiment 1-3 is carried out degradation of methylene blue experiment: the methylene blue solution of 50mg composite photocatalyst for degrading 30mL, 20mg/L, take ultraviolet lamp as light source irradiation, sampling in every 15 minutes once, centrifugal rear survey absorbancy (first stirs 30min sampling under dark condition, using the solution absorbance after adsorbing in the dark as blank), sample 6 times altogether.As shown in Figure 8,3 embodiment samples all can be degradable by methylene blue solution in 60min, and degradation effect, it is preferred that embodiment 1, is namely degraded at 45min completely for result.
Embodiment group 1-3 has the efficiency of good photocatalytic degradation methylene blue, and reason is that the adsorptivity of embodiment 1-3 sample is very large, and in light-catalyzed reaction, surface adsorption ability has a great impact catalytic activity, the TiO of stronger adsorptive power 2light-catalyzed reaction speed can be increased, and the micro-nano hierarchy TiO of lichee shape 2crystal surface structure then adds surface-area, improves photocatalytic speed.

Claims (4)

1. the micro-nano hierarchy TiO of lichee shape 2crystal and synthetic method thereof, is characterized in that, the micro-nano hierarchy TiO of described lichee shape 2crystal is spherical, and spherical surface is distributed with the ball bumps of small particle size, and crystal formation is Detitanium-ore-type;
The micro-nano hierarchy TiO of described lichee shape 2spherical diameter is 500-700nm, and the diameter of described ball bumps is 10-20nm.
2. the micro-nano hierarchy TiO of a kind of lichee shape as claimed in claim 1 2crystal and synthetic method thereof, is characterized in that, preparation process is as follows:
(1) under room temperature condition, PVP, water and n-propyl alcohol are made mixed liquor A, PVP, water and n-propyl alcohol quality volume volume ratio W/V/V are 1.6-2:25:75, by Ti (SO 4) 2solution is slowly poured in mixed liquor A, and after stirring, 70 DEG C of heating in water bath 3h-6h obtain mixed liquid B, after mixed liquid B is cooled to room temperature, centrifugal, washing, be 60 DEG C of ageing 12h in 1-1.8mol/L KOH solution in volumetric molar concentration, centrifugal, washing, dry after obtain presoma TiO 2powder C;
(2) mixed by precursor powder C and solvent D, precursor powder C and solvent D mass volume ratio W/V is 0.4:20, inserts water heating kettle and heat 2h at 180 DEG C, centrifugal, washing, dry after obtain the micro-nano hierarchy TiO of lichee shape 2crystal powder.
3. the micro-nano hierarchy TiO of a kind of lichee shape as claimed in claim 2 2crystal and synthetic method thereof, is characterized in that: in described step (1), Ti (SO 4) 2solution volumetric molar concentration is 0.8mol/L, Ti (SO 4) 2solution and described mixed liquor A volume ratio V/V are 1:2.
4. the micro-nano hierarchy TiO of a kind of lichee shape as claimed in claim 2 2crystal and synthetic method thereof, is characterized in that: in described step (2), and solvent D is ethylene glycol, the 0.01g/mL cetyl trimethylammonium bromide aqueous solution or volume ratio are one in the DMF/ aqueous solution of 1:1.
CN201510035292.7A 2015-01-23 2015-01-23 The micro-nano hierarchy TiO of a kind of lichee shape 2crystal and synthetic method thereof Expired - Fee Related CN104692457B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510035292.7A CN104692457B (en) 2015-01-23 2015-01-23 The micro-nano hierarchy TiO of a kind of lichee shape 2crystal and synthetic method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201510035292.7A CN104692457B (en) 2015-01-23 2015-01-23 The micro-nano hierarchy TiO of a kind of lichee shape 2crystal and synthetic method thereof

Publications (2)

Publication Number Publication Date
CN104692457A true CN104692457A (en) 2015-06-10
CN104692457B CN104692457B (en) 2016-04-06

Family

ID=53340076

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201510035292.7A Expired - Fee Related CN104692457B (en) 2015-01-23 2015-01-23 The micro-nano hierarchy TiO of a kind of lichee shape 2crystal and synthetic method thereof

Country Status (1)

Country Link
CN (1) CN104692457B (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105600822A (en) * 2016-03-31 2016-05-25 天津城建大学 Preparation method of litchi-like hierarchical-structure {001}-surface-exposed TiO2 powder
CN107445201A (en) * 2017-09-11 2017-12-08 广东工业大学 A kind of preparation method of rear-earth-doped anatase titanium dioxide micro-nano-sphere
CN109794290A (en) * 2019-01-31 2019-05-24 天津城建大学 A kind of screw type titanium oxyoxalate salt photochemical catalyst and preparation method thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102795664A (en) * 2012-08-10 2012-11-28 东华大学 Preparation method of mesoporous titanium dioxide microballoons with controllable particle size
CN103739013A (en) * 2014-01-07 2014-04-23 天津大学 Porous spherical titanium dioxide with controllable diameter and preparation and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102795664A (en) * 2012-08-10 2012-11-28 东华大学 Preparation method of mesoporous titanium dioxide microballoons with controllable particle size
CN103739013A (en) * 2014-01-07 2014-04-23 天津大学 Porous spherical titanium dioxide with controllable diameter and preparation and application thereof

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
扈玫珑等: "粒径可控球形TiO2的制备", 《物理化学学报》 *
王鸿雁等: "《有色金属冶金技术问答》", 30 June 2013, 化学工业出版社 *

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105600822A (en) * 2016-03-31 2016-05-25 天津城建大学 Preparation method of litchi-like hierarchical-structure {001}-surface-exposed TiO2 powder
CN107445201A (en) * 2017-09-11 2017-12-08 广东工业大学 A kind of preparation method of rear-earth-doped anatase titanium dioxide micro-nano-sphere
CN107445201B (en) * 2017-09-11 2019-01-08 广东工业大学 A kind of preparation method of rear-earth-doped anatase titanium dioxide micro-nano-sphere
CN109794290A (en) * 2019-01-31 2019-05-24 天津城建大学 A kind of screw type titanium oxyoxalate salt photochemical catalyst and preparation method thereof
CN109794290B (en) * 2019-01-31 2021-08-27 天津城建大学 Spiral titanyl oxalate photocatalyst and preparation method thereof

Also Published As

Publication number Publication date
CN104692457B (en) 2016-04-06

Similar Documents

Publication Publication Date Title
CN104525266B (en) Preparation method of metal-organic framework material photocatalyst and application
CN105056929A (en) Graphene/titanium dioxide composite adopting hollow microspherical structure and preparation method of composite
CN103730259B (en) A kind of nanocrystalline titanium dioxide film of two-specification pore structure and manufacturing method of nanocrystalline titanium dioxide film and preparation method thereof
CN104707542A (en) Photocatalyst/SiO2 composite aerogel material and preparation method thereof
CN105502342A (en) Method for preparing nanometer hollow carbon spheres with dopamine serving as carbon source
CN101817548A (en) Method for preparing zinc oxide hollow spheres
CN107915234A (en) A kind of preparation method of 1 nano zeolite aggregation molecular sieves of multi-stage porous TS
CN104692457B (en) The micro-nano hierarchy TiO of a kind of lichee shape 2crystal and synthetic method thereof
CN103007912B (en) One-dimensional nanometer titania photocatalyst with mica serving as support and preparation method thereof
CN103949274B (en) A kind of Co0.85Se catalyst material and preparation method
CN102389788B (en) Preparation method for porous titanium dioxide-carbon combined nano hollow microsphere
CN102887548B (en) Sea-urchin-shaped hiberarchy cobaltosic oxide nanosphere and preparing method thereof
CN107452512A (en) A kind of preparation method of hollow cobalt acid nickel for electrode material for super capacitor
CN109576986A (en) A kind of multilayer that bombax cotton/manganese dioxide is constructed is from driving tubulose micro-nano motor and preparation method thereof
CN104787800B (en) A kind of flowered-spherical titanium dioxide and preparation method thereof
CN103803634A (en) Preparation method of mesoporous zinc oxide microsphere photocatalyst
CN103611550B (en) A kind of preparation method of molybdenum bisuphide-silver metavanadate composite Nano photochemical catalyst
CN105289457B (en) A kind of hollow structure TiO2The preparation method and applications of nano material
CN105056927A (en) TiO2 nanotube composite SiO2 aerogel-based photocatalytic material and preparation method thereof
CN104310466A (en) Hollow titanium dioxide microsphere based on gel sphere precursor and preparation method of hollow titanium dioxide microsphere
CN108640149B (en) Titanium dioxide nano hollow ball and preparation method thereof
CN106914231A (en) Individual layer nano-TiO2The self assembling process of synthesizing of@yeast carbon balls and its application
CN103626226B (en) Method for preparing hollow nano titanium dioxide without template
CN110803710B (en) Method for preparing zinc oxide material based on surfactant-free microemulsion
CN112354559A (en) Two-dimensional receptor molecule/hierarchical pore TiO2Composite photocatalyst, preparation method and photocatalytic application thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20160406

Termination date: 20200123

CF01 Termination of patent right due to non-payment of annual fee