CN106238097A - The TiO that a kind of butoxy is modified2single crystal hollow four directions nanocone materials, preparation method and applications - Google Patents
The TiO that a kind of butoxy is modified2single crystal hollow four directions nanocone materials, preparation method and applications Download PDFInfo
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- CN106238097A CN106238097A CN201610604763.6A CN201610604763A CN106238097A CN 106238097 A CN106238097 A CN 106238097A CN 201610604763 A CN201610604763 A CN 201610604763A CN 106238097 A CN106238097 A CN 106238097A
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- tio
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- butoxy
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- 239000013078 crystal Substances 0.000 title claims abstract description 78
- 239000002110 nanocone Substances 0.000 title claims abstract description 77
- 239000000463 material Substances 0.000 title claims abstract description 74
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 64
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 230000005693 optoelectronics Effects 0.000 claims abstract description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- NAQMVNRVTILPCV-UHFFFAOYSA-N hexane-1,6-diamine Chemical compound NCCCCCCN NAQMVNRVTILPCV-UHFFFAOYSA-N 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000000725 suspension Substances 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims 1
- 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 abstract description 14
- 229940043267 rhodamine b Drugs 0.000 abstract description 14
- 239000000975 dye Substances 0.000 abstract description 9
- 230000009466 transformation Effects 0.000 abstract description 4
- 239000007791 liquid phase Substances 0.000 abstract description 3
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 238000010189 synthetic method Methods 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 230000003287 optical effect Effects 0.000 description 7
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 3
- 230000005518 electrochemistry Effects 0.000 description 3
- 150000002118 epoxides Chemical class 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000008878 coupling Effects 0.000 description 2
- 238000010168 coupling process Methods 0.000 description 2
- 238000005859 coupling reaction Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 239000002270 dispersing agent Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000001052 transient effect Effects 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 239000007832 Na2SO4 Substances 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- 229910003077 Ti−O Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000002800 charge carrier Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000002186 photoelectron spectrum Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical compound FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0201—Oxygen-containing compounds
- B01J31/0211—Oxygen-containing compounds with a metal-oxygen link
- B01J31/0212—Alkoxylates
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
- C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- 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
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
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Abstract
The invention provides the TiO that a kind of butoxy is modified2Single crystal hollow four directions nanocone materials, preparation method and applications.Preparation method is: by single crystal hollow TiO2Four directions nanocone materials is scattered in ethylene glycol, adds dropwise butyl titanate, stirs, obtains dispersion liquid；Reacting by heating, product washs, and is dried, and obtains the TiO that butoxy is modified2Single crystal hollow four directions nanocone materials.Compared with prior art, the present invention utilizes low temperature liquid phase synthetic method, and butoxy is modified single crystal hollow TiO2On nanocone materials surface, four directions, method is simple, low cost；The active height of photocatalyst, good stability for organic dyestuff rhodamine B visible light photocatalytic degradation；The material for opto-electronic conversion is provided to have photoelectric transformation efficiency height.
Description
Technical field
The present invention relates to preparation method of nano material and Environmental Chemistry and Optical Electro-Chemistry cross-application field, be specifically related to one
Plant the TiO that butoxy is modified2Single crystal hollow four directions nanocone materials, preparation method and applications.
Background technology
In trade effluent, environment is caused serious pollution by the residual of organic dyestuff, and the use energy of semiconductor light-catalyst
The organic dyestuff of residual in enough effectively degraded sewage.TiO in semiconductor light-catalyst2It is a kind of materials of furtheing investigate of people
Material, has the advantages such as nontoxic, low cost, photocatalytic activity height, good stability, is widely used to various photocatalysis field, as
Photocatalyzed Hydrogen Production, carbonaceous solar energy fuel, environment remediation and biomedical applications.
But TiO2It is wide bandgap semiconductor materials (3.0 3.2eV), ultraviolet light can only be absorbed, be little to absorption visible
Light, and the visible ray arriving earth surface constitutes about the 43% of total solar spectrum, ultraviolet light only accounts for the 4% of total solar spectrum, from
And greatly limit TiO2Potential as sunlight photocatalysis agent.
Therefore, people are to TiO2Functionalization extends its absorption region to sunlight so that it is photocatalytic activity arrives can
See light region.Such as: the coupling of nonmetal doping, transition metal, narrow gap semiconductor coupling, noble metal decorated, carbon modification and table
Face adsorbent (or coordination compound) sensitization etc..TiO2The photogenerated charge transfer row of the material extreme influence interface zone that surface is modified
For, thus affect photocatalytic activity.
Summary of the invention
It is an object of the invention to, it is provided that the TiO that a kind of butoxy is modified2Single crystal hollow four directions nanocone materials and system thereof
Preparation Method, utilizes low temperature liquid phase synthetic method, butoxy is modified TiO2Nanocone materials surface, single crystal hollow four directions, method letter
Single, low cost.
Present invention also offers the TiO that a kind of butoxy is modified2The application of single crystal hollow four directions nanocone materials, including can
See photocatalytically degradating organic dye and the application of visible ray opto-electronic conversion.
The TiO that a kind of butoxy that the present invention provides is modified2The preparation method of single crystal hollow four directions nanocone materials, including
Following steps:
(1) by TiO2Single crystal hollow four directions nanocone materials is scattered in alcoholic solvent, adds dropwise butyl titanate, stirs
Mix uniformly, obtain dispersion liquid；
(2) step (1) gained dispersion liquid reacting by heating, is cooled to room temperature, centrifugation, and product washs, and is dried, obtains fourth
The TiO that epoxide is modified2Single crystal hollow four directions nanocone materials.
TiO in step (1)2The preparation method of single crystal hollow four directions nanocone materials is:
A, by 1, after 6-hexamethylene diamine mixes with hexamethylene, add Ti (OC4H9)4；It is subsequently adding deionized water stirring mixing,
Obtain suspension；
B, step A gained suspension heated sealed are reacted, and cool down, centrifugal, washing of precipitate, are dried, and obtain TiO2Monocrystalline is empty
Heart four directions nanocone materials.
Further, in step A 1,6-hexamethylene diamine, hexamethylene, Ti (OC4H9)4It is 3-8 with the volume ratio of deionized water:
15-40:0.5-2:0.5-3；Stirring incorporation time is 8-15min.
Further, in step B, reacting by heating condition is: react 8-24h at 160-200 DEG C；Described reacting by heating is poly-
The stainless steel cauldron of tetrafluoroethene liner is carried out；Described washing is: be first washed with deionized 3-5 time, then uses anhydrous second
Alcohol washs 3-5 time；Described be dried in 55-60 DEG C of vacuum drying oven be dried 6-12h；
TiO in step (1)2Single crystal hollow four directions nanocone materials and butyl titanate amount ratio are 0.1-0.4:1g/mL.
Further, TiO in step (1)2Single crystal hollow four directions nanocone materials is 0.5-2 with the amount ratio of alcoholic solvent:
1mg/mL；Described alcoholic solvent is selected from dehydrated alcohol or ethylene glycol.
Described in step (2), reacting by heating condition is temperature 50-80 DEG C, response time 10-40min.
Further, described in step (2), washing is: is first washed with deionized 3-5 time, then uses absolute ethanol washing 3-
5 times；Described being dried is: be dried 6-12h in 55-60 DEG C of vacuum drying oven.
The TiO that a kind of butoxy that the present invention provides is modified2Single crystal hollow four directions nanocone materials, uses above method system
Standby, form, for boring long average out to 200nm, the hollow quadratic poppet surface of cone mouth diameter average out to 100nm is modified mass content
2.2%-3.1% butoxy radicals.
The TiO that a kind of butoxy that the present invention provides is modified2Single crystal hollow four directions nanocone materials is as visible light catalytic
Degraded application, specially organic dyestuff visible light photocatalytic degradation application；Especially the visible light catalytic of rhodamine B (RhB) is dropped
Solve.
Present invention also offers the TiO that a kind of butoxy is modified2Single crystal hollow four directions nanocone materials visible ray photoelectricity turns
Change application.
The described visible light photocatalytic degradation as organic dyestuff rhodamine B (RhB) apply particularly as follows:
The TiO that the 10mg butoxy present invention prepared is modified2It is dense that single crystal hollow four directions nanocone materials joins 100mL
Degree, in 0.01mmol/L RhB solution, after ultrasonic 1-2min, is placed in dark at and stirs 1h, make catalyst surface reach to adsorb-
Desorption balances.Afterwards, 300W xenon lamp (adding optical filter λ > 420nm) is used to irradiate.3mL sample is taken every 20min centrifuge tube,
After centrifugal (10000rpm, 2min), take supernatant, use ultraviolet-visible spectrophotometer to measure the absorption spectrum of solution.Pass through
Characteristic absorption peak at 554nm determines the concentration of RhB.
The application of described visible ray opto-electronic conversion is particularly as follows: the TiO that modifies of the butoxy the present invention prepared2Single crystal hollow four
Side's nanocone materials 5mg ultrasonic disperse is in 1mL deionized water, and taking 0.01mL dispersant liquid drop at area is 0.28cm2FTO glass
On glass.Afterwards, this FTO glass is put in drying baker, at a temperature of 80 DEG C, be dried 30min.Optical Electro-Chemistry test use standard
Three-electrode system, be loaded with catalyst FTO glass as working electrode, platinum filament and Ag/AgCl electrode be respectively auxiliary electrode and
Reference electrode.Na with concentration as 0.2mol/L2SO4With 10-5The RhB mixed solution of mol/L is electrolyte.Opto-electronic conversion is passed through
Electrochemical workstation (CHI660B) is tested, and uses 300W xenon lamp (adding optical filter λ > 420nm) as light source.Scanning voltage model
Enclose :-0.1～+0.8V, sweep speed: 50mV s-1。
Compared with prior art, the present invention first passes through liquid interface chemical synthesis, at non-polar solven hexamethylene and
The water of trace and 1, in 6-hexamethylene diamine mixed liquor, utilizes Ti (OC4H9)4Slowly hydrolysis obtains TiO2Single crystal hollow four directions nanometer
Cone material structure.Ti (OC is added after 1,6-hexamethylene diamine, hexamethylene mixing4H9)4, add deionized water, otherwise Ti afterwards
(OC4H9)4Fast hydrolyzing, it is impossible to obtain specific pattern.Ti(OC4H9) slow on the interface that a small amount of water and a large amount of hexamethylene are formed
Slow hydrolysis, 1,6-hexamethylene diamine is at TiO2{ preferred orientation on 101} family of crystal planes forms the TiO that a large amount of (101) face exposes2Single crystal hollow
Four directions nanocone structures.Then heated sealed reaction, under specified temp pressure, regulates and controls physical-chemical reaction, generates target and produces
Thing.The anatase TiO of preparation2Single crystal hollow four directions nanocone materials, has { 101} face and the big specific surface of a large amount of exposure
Long-pending；Then the present invention is by simple cryochemistry liquid phase method, at TiO2Fourth is modified on nanocone materials surface, single crystal hollow four directions
Epoxide, it is thus achieved that the TiO that butoxy is modified2Single crystal hollow four directions nanocone materials.By controlling temperature and time, it is thus achieved that product is
Good pattern and yield, preparation technology has environmental friendliness and technique preparation is simple, the advantage of low cost.The fourth oxygen prepared
The TiO that base is modified2Single crystal hollow four directions nanocone materials is for the photocatalyst of organic dyestuff rhodamine B visible light photocatalytic degradation
Active height, good stability；It is high that material for opto-electronic conversion has photoelectric transformation efficiency.
Accompanying drawing explanation
Fig. 1 is the TiO of the butoxy modification of embodiment 1 preparation2The X-ray powder of single crystal hollow four directions nanocone materials
Diffraction (XRD) figure；
Fig. 2 is the TiO of the butoxy modification of embodiment 1 preparation2The scanning electron of single crystal hollow four directions nanocone materials shows
Micro mirror (SEM) figure；
Fig. 3 is the TiO of the butoxy modification of embodiment 1 preparation2The Fourier transformation of single crystal hollow four directions nanocone materials
Infrared spectrum (FTIR) figure；
Fig. 4 is the TiO of the butoxy modification of embodiment 1 preparation2The O1s high-resolution of single crystal hollow four directions nanocone materials
XPS spectrum figure, provides pure TiO simultaneously2The result of single crystal hollow four directions nanocone materials is so that comparing；
Fig. 5 is the TiO that embodiment 2 butoxy is modified2The ultraviolet of single crystal hollow four directions nanocone materials Visible Light Induced Photocatalytic RhB
Abosrption spectrogram；
Fig. 6 is the TiO that embodiment 2 butoxy is modified2Single crystal hollow four directions nanocone materials visible light photocatalytic degradation RhB's
Concentration changes with time curve, provides pure TiO simultaneously2Single crystal hollow four directions nanocone materials, P25 (business TiO2) and blank
The result of experiment (not adding catalyst) is so that comparing；
Fig. 7 is the TiO that embodiment 3 butoxy is modified2Single crystal hollow four directions nanocone materials visible ray lower linear scanning volt
Peace curve, provides pure TiO simultaneously2Single crystal hollow four directions nanocone materials and P25 (business TiO2) result so that comparing；
Fig. 8 is the TiO that embodiment 3 butoxy is modified2Initial potential under the nanocone materials visible ray of single crystal hollow four directions
During 0.3V, transient current density over time, provides pure TiO simultaneously2Single crystal hollow four directions nanocone materials and P25
(business TiO2) result so that comparing.
Detailed description of the invention
Embodiment 1
The TiO that a kind of butoxy is modified2The preparation method of single crystal hollow four directions nanocone materials, comprises the following steps:
(1) the pure TiO of 40mg is taken2Single crystal hollow four directions nanocone materials adds in 30mL ethylene glycol, and ultrasonic 10min disperses
Uniformly, drip 0.2mL butyl titanate, stir, obtain dispersion liquid.
(2) by above-mentioned dispersion liquid reacting by heating, temperature 60 C, response time 30min, reaction naturally cools to room after terminating
Temperature.Product is centrifugal to be collected, and is first washed with deionized 3-5 time, then with absolute ethanol washing 3-5 time, is finally placed in 60 DEG C of vacuum
Drying baker is dried 6-12h.
Described TiO2The preparation method of single crystal hollow four directions nanocone materials is:
(1) by 5mL1,6-hexamethylene diamine adds in 25mL hexamethylene, is subsequently added 1mL Ti (OC4H9)4, add 1mL and go
Ionized water, continuously stirred 10min, it is thus achieved that white suspension；
(2) the most above-mentioned white suspension is transferred in 50mL teflon-lined stainless steel cauldron, by high pressure
Still is sealed at 180 DEG C reaction 12h, after reaction terminates, naturally cools to room temperature, and the precipitate of white is centrifugal to be collected and with first using
Deionized water wash 3-5 time, then with absolute ethanol washing 3-5 time, be placed in 60 DEG C of vacuum drying ovens and be dried 6-12h, obtain TiO2
Single crystal hollow four directions nanocone materials.
The structure of product and morphology characterization:
With X-ray powder diffractometer, embodiment 1 products therefrom being carried out Discriminating materials, result is as shown in Figure 1.All of
Diffraction maximum and Tetragonal anatase TiO2Fit like a glove (JCPDS standard card number: 71-1166), shows that butoxy modification does not has
Change product anatase Tetragonal TiO2Thing phase.
TiO butoxy modified by scanning electron microscope2Single crystal hollow four directions nanocone carries out morphology analysis, result
As shown in Figure 2.Show sized by prepared sample uniformly, to bore long average out to 200nm, the sky of cone mouth diameter average out to 100nm
Heart four directions nanocone structures.Being analyzed product with Fourier transform infrared spectroscopy, result (is given as shown in Figure 3 simultaneously
Pure TiO2The infrared spectrum of single crystal hollow four directions nanocone is to compare).At 1454cm-1And 1380cm-1Place absworption peak with
CH3CH2CH2CH2The bending vibration of-middle C H key is relevant；At 1120cm-1And 1040cm-1The peak of wave band is flexible with C O group
Vibrate relevant.Therefore, Fourier transform infrared spectroscopy confirms at TiO2There is butoxy in single crystal hollow tetragonal pyramid surface.Penetrate with X
Product is analyzed by photoelectron spectra, and the XPS spectrum result of O1s (provides pure TiO as shown in Figure 4 simultaneously2Monocrystalline is empty
The result of heart four directions nanocone is to compare).Having three to combine energy at 529.3,531.8 and 533.0eV, the first two peak is respectively
Corresponding lattice O2-, hydroxyl, last peak can belong to the oxygen in C-O key, the oxygen of chemisorbed or the water of residual.In fourth
The TiO that epoxide is modified2In the nanocone spectrogram of single crystal hollow four directions, last peak is more prominent, and auxiliary confirms at TiO2Single crystal hollow
The existence of nanocone surface, four directions butoxy.TiO butoxy modified by burning element analytic process2Single crystal hollow four directions nanometer
Cone is analyzed, and result shows that product contains C 1.71% and H 0.43%, and calculating butoxy content by C element is 2.6%.
TiO is proved from another angle2There is butoxy in nanocone surface, single crystal hollow four directions.
Embodiment 2
The TiO that a kind of butoxy is modified2Answering of single crystal hollow four directions nanocone materials visible light photocatalytic degradation organic dyestuff
With.
The TiO that the butoxy of above-mentioned preparation is modified2Single crystal hollow four directions nanocone takes 10mg addition 100mL concentration
In 0.01mmol/LRhB solution, after ultrasonic 1-2min, it is placed in stirring 1h at dark, makes catalyst surface reach absorption-desorption attached
Balance.Afterwards, 300W xenon lamp (add optical filter and make λ > 420nm) is used to irradiate.3mL sample is taken every 5min centrifuge tube, centrifugal
Afterwards (10000rpm, 2min), take supernatant, use ultraviolet-visible spectrophotometer (Shimadzu UV-2550) to measure solution
Absorption spectrum.The concentration of RhB is determined by the characteristic absorption peak at 554nm.The uv absorption of photocatalytic degradation RhB result
Spectrogram is as it is shown in figure 5, degradation process concentration versus time curve (provides pure TiO as shown in Figure 6 simultaneously2Single crystal hollow
Four directions nanocone materials and P25 (business TiO2) photocatalysis result to compare).After visible ray shines 2h, sieve in solution
Red bright B degradation rate reaches 84.5%.
Embodiment 3
The TiO that a kind of butoxy is modified2The nanocone visible ray opto-electronic conversion application of single crystal hollow four directions.
The TiO that the butoxy present invention prepared is modified2Single crystal hollow four directions nanocone materials 5mg ultrasonic disperse is at 1mL
In deionized water, taking 0.01mL dispersant liquid drop at area is 0.28cm2FTO glass on.Afterwards, this FTO glass is put into dry
In dry case, at a temperature of 80 DEG C, it is dried 30min.The three-electrode system of Optical Electro-Chemistry test use standard, to be loaded with the FTO of catalyst
Glass is working electrode, and platinum filament and Ag/AgCl electrode are respectively auxiliary electrode and reference electrode.With concentration as 0.2mol/L
Na2SO4With 10-5The RhB mixed solution of mol/L is electrolyte.Opto-electronic conversion is tested by electrochemical workstation (CHI660B),
Use 300W xenon lamp (adding optical filter λ > 420nm) as light source.Scanning voltage scope :-0.1～+0.8V, sweeps speed: 50mV s-1。
Visible ray lower linear scanning volt-ampere curve, result (provides pure TiO as shown in Figure 7 simultaneously2Single crystal hollow four directions nanocone materials
And P25 (business TiO2) result to make comparisons).The TiO that butoxy is modified2Prepared by single crystal hollow four directions nanocone materials
Electrode creates significant photoelectric current.During initial potential 0.3V, it is seen that under light, transient current density is over time, and result is such as
(provide pure TiO shown in Fig. 8 simultaneously2Single crystal hollow four directions nanocone materials and P25 (business TiO2) result with make compare
Relatively).The TiO that butoxy is modified2Visible light exposure is presented powerful by electrode prepared by single crystal hollow four directions nanocone materials
Instantaneous photocurrent response.Obviously, TiO2The electronic structure of its uniqueness of butoxy of single crystal hollow four directions nanocone surface adsorption carries
The high surface Ti-O group ability from the colored dyes capture photo-excited electron excited, reduces the compound of charge carrier, increases
Enter visible light photocatalysis active and photoelectric transformation efficiency.
Claims (10)
1. the TiO that a butoxy is modified2The preparation method of single crystal hollow four directions nanocone materials, it is characterised in that described preparation
Method comprises the following steps:
(1) by single crystal hollow TiO2Four directions nanocone materials is scattered in alcoholic solvent, adds dropwise butyl titanate, and stirring is all
Even, obtain dispersion liquid；
(2) step (1) gained dispersion liquid reacting by heating, is cooled to room temperature, centrifugation, and product washs, and is dried, obtains butoxy
The TiO modified2Single crystal hollow four directions nanocone materials.
The TiO that butoxy the most according to claim 1 is modified2The preparation method of single crystal hollow four directions nanocone materials, it is special
Levy and be, TiO in step (1)2The preparation method of single crystal hollow four directions nanocone materials is:
A, by 1, after 6-hexamethylene diamine mixes with hexamethylene, add Ti (OC4H9)4；It is subsequently adding deionized water stirring mixing, it is thus achieved that
Suspension；
B, step A gained suspension heated sealed are reacted, and cool down, centrifugal, washing of precipitate, are dried, and obtain TiO2Single crystal hollow four directions
Nanocone materials.
The TiO that butoxy the most according to claim 2 is modified2The preparation method of single crystal hollow four directions nanocone materials, it is special
Levy and be, in step A 1,6-hexamethylene diamine, hexamethylene, Ti (OC4H9)4It is 3-8:15-40:0.5-2 with the volume ratio of deionized water:
0.5-3。
4. the TiO modified according to the butoxy described in Claims 2 or 32The preparation method of single crystal hollow four directions nanocone materials,
It is characterized in that, in step B, reacting by heating condition is: react 8-24h at 160-200 DEG C.
The TiO that butoxy the most according to claim 1 is modified2The preparation method of single crystal hollow four directions nanocone materials, it is special
Levy and be, TiO in step (1)2Single crystal hollow four directions nanocone materials and butyl titanate amount ratio are 0.1-0.4:1g/mL.
The TiO that the most according to claim 1 or 5, butoxy is modified2The preparation method of single crystal hollow four directions nanocone materials,
It is characterized in that, TiO in step (1)2Single crystal hollow four directions nanocone materials is 0.5-2:1mg/mL with the amount ratio of alcohol；Described
Alcoholic solvent is selected from dehydrated alcohol or ethylene glycol.
The TiO that the most according to claim 1 or 5, butoxy is modified2The preparation method of single crystal hollow four directions nanocone materials,
It is characterized in that, described in step (2), reacting by heating condition is temperature 50-80 DEG C, response time 10-40min.
8. the TiO that a butoxy is modified2Single crystal hollow four directions nanocone materials, it is characterised in that use claim 1-7 to appoint
Prepared by one described method, the TiO that described butoxy is modified2Single crystal hollow four directions nanocone materials form is for boring long average out to
200nm, the hollow quadratic poppet surface of cone mouth diameter average out to 100nm is modified 2.2%-3.1% butoxy radicals.
9. the TiO that a butoxy is modified2The nanocone materials visible light photocatalytic degradation Organic substance application of single crystal hollow four directions.
10. the single crystal hollow TiO that a butoxy is modified2Four directions nanocone materials visible ray opto-electronic conversion application.
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| EP1411033A1 (en) * | 2002-10-02 | 2004-04-21 | Sumitomo Chemical Company, Limited | Method for producing titanium oxide |
| CN101209413A (en) * | 2006-12-31 | 2008-07-02 | 明道管理学院 | Titanium dioxide photo-catalytic and manufacturing method thereof |
| US20100316561A1 (en) * | 2008-02-11 | 2010-12-16 | Daunia Solar Cell S.R.L. | Process for the preparation of titanium dioxide with nanometric dimensions and controlled shape |
| CN102181929A (en) * | 2011-04-20 | 2011-09-14 | 上海师范大学 | Process for synthesizing TiO2 mesoporous single crystals |
| 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 |
| CN104843779A (en) * | 2015-04-29 | 2015-08-19 | 浙江大学 | Hollow spherical rutile titanium dioxide mesocrystal and preparation method thereof |
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| EP1411033A1 (en) * | 2002-10-02 | 2004-04-21 | Sumitomo Chemical Company, Limited | Method for producing titanium oxide |
| CN101209413A (en) * | 2006-12-31 | 2008-07-02 | 明道管理学院 | Titanium dioxide photo-catalytic and manufacturing method thereof |
| US20100316561A1 (en) * | 2008-02-11 | 2010-12-16 | Daunia Solar Cell S.R.L. | Process for the preparation of titanium dioxide with nanometric dimensions and controlled shape |
| CN102181929A (en) * | 2011-04-20 | 2011-09-14 | 上海师范大学 | Process for synthesizing TiO2 mesoporous single crystals |
| 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 |
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