CN108704634A - A kind of TiO2TiO is loaded on nano wire2The preparation method of the photochemical catalyst of nano particle - Google Patents
A kind of TiO2TiO is loaded on nano wire2The preparation method of the photochemical catalyst of nano particle Download PDFInfo
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- CN108704634A CN108704634A CN201810446590.9A CN201810446590A CN108704634A CN 108704634 A CN108704634 A CN 108704634A CN 201810446590 A CN201810446590 A CN 201810446590A CN 108704634 A CN108704634 A CN 108704634A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 13
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 63
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002070 nanowire Substances 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000000034 method Methods 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 229910010062 TiCl3 Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 238000005342 ion exchange Methods 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 230000015556 catabolic process Effects 0.000 abstract description 4
- 150000001875 compounds Chemical class 0.000 abstract description 4
- 238000006731 degradation reaction Methods 0.000 abstract description 4
- 238000005286 illumination Methods 0.000 abstract description 3
- 230000002045 lasting effect Effects 0.000 abstract description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 239000004408 titanium dioxide Substances 0.000 abstract 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 abstract 1
- 239000000908 ammonium hydroxide Substances 0.000 abstract 1
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 abstract 1
- 238000007146 photocatalysis Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 150000002431 hydrogen Chemical class 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 3
- 229940043267 rhodamine b Drugs 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000008450 motivation Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000004224 protection Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/30—Ion-exchange
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to a kind of TiO2Nanowire supported TiO2The preparation method of the photochemical catalyst of nano particle passes through P first25Titanium dioxide nano thread is prepared with NaOH, then by the way that the titanium dioxide nano thread prepared is added to titanium trichloride (TiCl3) and ammonium hydroxide NH3·H2O in), by hydro-thermal method, compound TiO is prepared2NPs@TiO2NWs.A kind of cheap and efficient photochemical catalyst has been prepared by 400 DEG C in temperature in the present invention.Compound TiO of the present invention2NPs@TiO2NWs photochemical catalysts have extraordinary Photocatalytic Degradation Property, under room temperature, normal pressure and illumination, energy fast degradation, and there is lasting photocatalytic activity.
Description
Technical field
The present invention relates to a kind of TiO2TiO is loaded on nano wire2The preparation method of the photochemical catalyst of nano particle, belongs to light
Catalyst technical field.
Background technology
As a kind of green catalyst, photochemical catalyst achieves huge progress in recent years.Push light-catalyzed reaction research
Strong request and photochemical catalyst itself of the enormous motivation from the clean sources the Sheng Chan ﹑ Neng Wei Ji ﹑ environmental protections of Qing are potentially explored
Value and application potential.
One-dimensional TiO2The efficient catalytic degradation capability of hetero-junctions catalyst can allow overwhelming majority pollution to turn materially harmless object
Matter contributes for water conservation, can solve the problems, such as country and enterprise's sewage effluent together.It is anti-by simple hydro-thermal
TiO should be prepared2Then nano wire loads TiO as carrier using the nano wire prepared in water-heat process2Nano particle, to make
For at one-dimensional TiO2Nano-heterogeneous structure, then by regulating and controlling TiO2The ratio of nano particle prepares the best product of performance.Entirely
It tests simple and practicable and environment friendly and pollution-free.By by TiO2Nano particle is supported on TiO2On nano wire, not only product is made to remain
Respective performance, and the specific surface area of material is largely increased, heterojunction boundary also largely promotes light
The separation rate of raw charge and photohole, these new properties are all essential for the catalytic activity for improving catalyst.
Invention content
The object of the present invention is to provide a kind of TiO2TiO is loaded on nano wire2The preparation side of the photochemical catalyst of nano particle
Method.
The present invention uses following technical scheme：
A kind of TiO2TiO is loaded on nano wire2Photochemical catalyst (the abbreviation TiO of nano particle2NPs@TiO2NWs preparation)
Method, preparation process are as follows：
(1)TiO2Nano wire monolithic catalyst (abbreviation TiO2NWs preparation)：(referred to as by P25 types nano-titanium dioxide
P25) be dissolved in NaOH solution, 24~48h of hydro-thermal reaction is carried out at 170~190 DEG C filters to obtain solid matter after cooling,
Solid matter is added in HCl solution and carries out ion exchange, refilters to obtain solid matter, 5h is then calcined at 400 DEG C, is made
Obtain TiO2NWs；
(2)TiO2NPs@TiO2The preparation of NWs：By TiCl3It is dissolved in the water, then by TiO made from step (1)2NWs adds
Enter into this solution, adds NH3·H2O turns to carry out hydro-thermal reaction 12h at 180 DEG C after being sufficiently mixed, after cooling down, centrifuges solid
Then state substance calcines 2h at 400 DEG C, TiO is made2NPs@TiO2NWs。
Preferably, in step (1) HCl solution a concentration of 0.1M.
Preferably, calcining carries out in Muffle furnace in step (1), and heating rate is 5 DEG C/min.
Preferably, NH in step (2)3·H2The mass fraction of O is 28wt%.
This method passes through P25TiO is prepared with NaOH2NWs, by the TiO to prepare2NWs additions contain TiCl3And NH3·
H2In the clear solution of O, TiO is made with hydro-thermal method2NPs@TiO2NWs.The TiO of the present invention2NPs@TiO2NWs is a kind of compound
There is photochemical catalyst extraordinary photocatalysis performance can quickly be produced by photocatalysis water under room temperature, normal pressure and illumination
Hydrogen, and there is lasting photocatalytic activity.
Advantages of the present invention：
1、TiO2NPs@TiO2NWs has very strong photocatalysis performance, very high to the utilization rate of sunlight, can be ultraviolet
It can fast degradation rhodamine B (RhB) under the conditions of light.TiO2NPs nanostructures show excellent photocatalytic activity；This may
Them are attributed to due to the intrinsic open channel in lattice and the single facet of preferential exposure height crystallization.In addition, when illumination, point
Not in TiO2Photoinduced Electron (e is generated in the conduction band and valence band of NPs-) and hole (H+)；It can efficiently separate and move to
TiO2The surfaces NWs.Therefore, TiO2NPs@TiO2NWs shows excellent photocatalytic activity.To TiO2NPs@TiO2NWs photocatalysis
The catalyzed conversion repeatedly of the RhB of agent shows it with chemical inertness and good stability.
2, the TiO prepared by hydro-thermal method2NPs@TiO2NWs not will produce new pollution for user and environment, and
The catalyzing manufacturing of hydrogen energy recycled for multiple times of the compound is a kind of photochemical catalyst of Cheap highly effective.
3, the TiO prepared by this hydro-thermal method2NPs@TiO2NWs, before the application proposition prepared by nobody.
Description of the drawings
Fig. 1 is TiO of the present invention2The electron microscopic picture of NWs.
Fig. 2 is TiO of the present invention2The electron microscopic picture of NPs.
Fig. 3 is TiO of the present invention2NPs@TiO2The electron microscopic picture of the photochemical catalyst of NWs.
Fig. 4 is TiO of the present invention2NWs、TiO2NPs and TiO2NPs@TiO2The photocatalysis performance figure of NWs.
Specific implementation mode
(1)TiO2The preparation of NWs monolithic catalysts
By 1.5g P25It being dissolved in 30mL NaOH solutions, solution continuously stirs 10min, is sealed in 50mL reaction kettles,
Reaction kettle is put into 180 DEG C of modulation in electric drying oven with forced convection to be heated for 24 hours, it is multi-purpose true with circulating water type after natural cooling
Sky pump is filtered, and neutrality is washed with deionized, and product is added in the HCl solution of 500mL0.1M and is stirred for 24 hours,
It allows product to carry out ion exchange, product after acidification is filtered and be washed with deionized neutrality, product is in vacuum drying chamber 80
It is dry at DEG C, it is ground after dry and is put into 400 DEG C of calcining 5h of Muffle furnace, heating rate is 5 DEG C/min, and sample TiO is made2NWs。
(2)TiO2Nano particle monolithic catalyst (abbreviation TiO2NPs preparation)
0.12g TiCl are weighed with electronic balance3(300mg of 20wt.%TiCl3Solution) it is added to 60mL water
In, add 200uL NH3·H2O (28wt%) makes solution be sufficiently mixed, is then transferred into 100mL with glass bar uniform stirring
Reaction kettle in, 180 DEG C carry out heating 12h, after natural cooling, solution are poured into centrifuge tube, centrifuge washing, product is at 60 DEG C
Lower drying is put into 400 DEG C of calcining 2h of Muffle furnace, obtains sample TiO after dry2NPs。
(3)TiO2NPs@TiO2The preparation of the photochemical catalyst of NWs
0.12g TiCl are weighed with electronic balance3(300mg of 20wt.%TiCl3Solution) it is added to 60mL water
In, then by 0.1866g TiO obtained in above-mentioned (1)2NWs is added in this solution, adds 200uL NH3·H2O
(28wt%) makes solution be sufficiently mixed, is then transferred into the reaction kettle of 100mL with glass bar uniform stirring, and 180 DEG C are added
Hot 12h after natural cooling, solution is poured into centrifuge tube, centrifuge washing, and product is dry at 60 DEG C, and Muffle is put into after dry
400 DEG C of calcining 2h of stove, are made sample TiO2NPs@TiO2NWs。
Photocatalysis CO2Reduction.Other than photocatalysis liberation of hydrogen, it is based on TiO2NPs@TiO2The light-catalysed carbon dioxide light of NWs
It is reduced into organic-fuel source and shows huge potential application in terms of reducing greenhouse effects and solving energy crisis.Although
TiO2NPs@TiO2NWs based composites are widely used to photocatalytic degradation and liberation of hydrogen, only a small number of report concern photocatalysis
Former CO2.This is because CO2Reduction is a kind of multielectron transfer and multi-step process.Moreover, the CO of report2Reduction activation still compared with
It is low；This needs further improvement and optimization.
As seen from Figure 1, TiO2NWs has thread-like morphology.TiO2The heating of NWs will not cause the bright of nanometer line morphology
Aobvious variation.Average diameter is about 60-90nm, and length is several microns.
As seen from Figure 2, the water-heat process middle grade TiO since central seed grain2The formation of nanostructure.Three
The form of dimension layering nanostructure originates from the growth of the radially-arranged thin slice of dozens of, and each nano thickness leads to the big of optimization
Surface area.
As seen from Figure 3, prepared TiO2NPs@TiO2NWs composite materials are by diameter 200nm, length some tens of pm
Nano wire composition.Transmission electron microscope (TEM) image shows, prepared TiO2NPs@TiO2NWs is core-shell structure copolymer nano junction
Structure, each of which by a diameter of 60-90nm TiO2NWs and ultra-thin TiO for winding2NWs。
As seen from Figure 4, about TiO2NPs@TiO2NWs composite materials are for H2The periodic performance of production also carries out
Test, to assess its stability.As shown in figure 4, in being recycled at first, H2Yield can reach about 3200 μ at 4 hours
molg-1.Even if after 20 cycles within 80 hours, TiO2NPs@TiO2NWs still shows H2Generate about 3020 μm of olg-1,
94% keeps initil output, without any significant degradation.
Claims (6)
1. a kind of TiO2TiO is loaded on nano wire2The preparation method of the photochemical catalyst of nano particle, preparation process are as follows：
(1) P25 type nano-titanium dioxides are dissolved in NaOH solution, 24~48h of hydro-thermal reaction are carried out at 170~190 DEG C,
After cooling, solid matter is filtered to obtain, solid matter is added in HCl solution and carries out ion exchange, refilters to obtain solid matter,
Then 5h is calcined at 400 DEG C, TiO is made2Nano wire monolithic catalyst；
(2) by TiCl3It is dissolved in the water, then by TiO made from step (1)2Nano wire monolithic catalyst is added in this solution,
Add NH3·H2O turns to carry out hydro-thermal reaction 12h at 180 DEG C after being sufficiently mixed, after cooling down, centrifuges to obtain solid matter, then exist
2h is calcined at 400 DEG C, TiO is made2TiO is loaded on nano wire2The photochemical catalyst of nano particle.
2. according to the method described in claim 1, it is characterized in that：In step (1), a concentration of 0.1M of HCl solution.
3. according to the method described in claim 1, it is characterized in that：In step (1), calcining carries out in Muffle furnace, heating speed
Rate is 5 DEG C/min.
4. according to the method described in claim 1, it is characterized in that：In step (2), NH3·H2The mass fraction of O is 28wt%.
5. the TiO that the method according to Claims 1 to 4 any claim is prepared2TiO is loaded on nano wire2Nanometer
The photochemical catalyst of particle.
6. TiO according to claim 52TiO is loaded on nano wire2The purposes of the photochemical catalyst of nano particle, feature exist
In：For hydrogen making.
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|---|---|---|---|
| CN201810446590.9A CN108704634A (en) | 2018-05-11 | 2018-05-11 | A kind of TiO2TiO is loaded on nano wire2The preparation method of the photochemical catalyst of nano particle |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102760581A (en) * | 2011-04-25 | 2012-10-31 | 北京大学 | Titanium dioxide photoelectrode and preparation method thereof |
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| CN104628262A (en) * | 2014-11-14 | 2015-05-20 | 湖北文理学院 | Method for preparing matchstick-shaped TiO2 nanoparticle and nanorod composite array |
| CN104941618A (en) * | 2015-06-23 | 2015-09-30 | 南昌航空大学 | Titanium dioxide nano-particles repairing nanowires heterojunction composite material |
| CN106582592A (en) * | 2016-12-13 | 2017-04-26 | 湖北工业大学 | Spherical core-shell type TiO2/TiO2 material and preparation method thereof |
-
2018
- 2018-05-11 CN CN201810446590.9A patent/CN108704634A/en active Pending
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|---|---|---|---|---|
| CN102760581A (en) * | 2011-04-25 | 2012-10-31 | 北京大学 | Titanium dioxide photoelectrode and preparation method thereof |
| CN103265006A (en) * | 2013-05-13 | 2013-08-28 | 浙江理工大学 | Preparation method of titanium dioxide evenly-loaded carbon nanorod |
| CN104628262A (en) * | 2014-11-14 | 2015-05-20 | 湖北文理学院 | Method for preparing matchstick-shaped TiO2 nanoparticle and nanorod composite array |
| CN104941618A (en) * | 2015-06-23 | 2015-09-30 | 南昌航空大学 | Titanium dioxide nano-particles repairing nanowires heterojunction composite material |
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Application publication date: 20181026 |