CN106179337B - A kind of TiO2/ Au nanometer rods sea urchin shape heterojunction structure photochemical catalysts and preparation method thereof - Google Patents
A kind of TiO2/ Au nanometer rods sea urchin shape heterojunction structure photochemical catalysts and preparation method thereof Download PDFInfo
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- CN106179337B CN106179337B CN201610505542.3A CN201610505542A CN106179337B CN 106179337 B CN106179337 B CN 106179337B CN 201610505542 A CN201610505542 A CN 201610505542A CN 106179337 B CN106179337 B CN 106179337B
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 241000257465 Echinoidea Species 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 241001104043 Syringa Species 0.000 claims abstract description 9
- 235000004338 Syringa vulgaris Nutrition 0.000 claims abstract description 9
- 238000005119 centrifugation Methods 0.000 claims abstract description 6
- 150000003608 titanium Chemical class 0.000 claims abstract description 3
- 239000004094 surface-active agent Substances 0.000 claims description 11
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical group [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000010936 titanium Substances 0.000 claims description 4
- 229910052719 titanium Inorganic materials 0.000 claims description 4
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 4
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 3
- XWXLRBOUSFMWNC-UHFFFAOYSA-N CCCCCCCCCCCCCCCC(CC1=CC=CC=C1)Cl.N Chemical group CCCCCCCCCCCCCCCC(CC1=CC=CC=C1)Cl.N XWXLRBOUSFMWNC-UHFFFAOYSA-N 0.000 claims description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- YONPGGFAJWQGJC-UHFFFAOYSA-K titanium(iii) chloride Chemical compound Cl[Ti](Cl)Cl YONPGGFAJWQGJC-UHFFFAOYSA-K 0.000 claims description 2
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims 2
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims 1
- PCHPORCSPXIHLZ-UHFFFAOYSA-N diphenhydramine hydrochloride Chemical compound [Cl-].C=1C=CC=CC=1C(OCC[NH+](C)C)C1=CC=CC=C1 PCHPORCSPXIHLZ-UHFFFAOYSA-N 0.000 claims 1
- DCKVFVYPWDKYDN-UHFFFAOYSA-L oxygen(2-);titanium(4+);sulfate Chemical compound [O-2].[Ti+4].[O-]S([O-])(=O)=O DCKVFVYPWDKYDN-UHFFFAOYSA-L 0.000 claims 1
- 229910000348 titanium sulfate Inorganic materials 0.000 claims 1
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 claims 1
- 239000004065 semiconductor Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000010931 gold Substances 0.000 description 42
- 229910052737 gold Inorganic materials 0.000 description 10
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 8
- 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 8
- 239000012141 concentrate Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 230000001699 photocatalysis Effects 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 7
- 230000009102 absorption Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 229940043267 rhodamine b Drugs 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- 230000003321 amplification Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 3
- 238000005286 illumination Methods 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 239000002077 nanosphere Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 230000008033 biological extinction Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 230000035040 seed growth Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- 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—
-
- B01J35/60—
Abstract
A kind of TiO2/ Au nanometer rods sea urchin shape heterojunction structure photochemical catalysts and preparation method thereof, belong to semiconductor light-catalyst technical field.8~16mL, the Au nanometer rods colloidal solution that Au nanometer rods quality is 0.78~1.56mg are concentrated by the method for centrifugation, it is concentrated to the 2~3% of original volume, then 10~30mL of deionized water is added into lower layer's enriched product, after 10~20min is stirred at room temperature, add 0.5~1mL of titanium salt aqueous solution of 5~10mg/mL, mixture room temperature continues 30~50min of stirring, is then heated 2~6 hours at 100~130 DEG C, obtains lilac TiO2/ Au nanometer rods sea urchin shape heterojunction structure photochemical catalysts.TiO prepared by the present invention2The SPR that/AuNR sea urchins shape heterojunction structure photochemical catalyst presents strong Au nanometer rods in visible region absorbs, and excellent antireflection characteristic, more sunlights can be captured, AuNR can improve the separative efficiency in light induced electron and hole simultaneously, in addition there is sea urchin shape structure big specific surface area, these characteristics to be all conducive to improve the catalytic efficiency of the photochemical catalyst.
Description
Technical field
The invention belongs to semiconductor light-catalyst technical fields, and in particular to a kind of TiO2/ Au nanometer rods sea urchin shapes are heterogeneous
Structure photochemical catalyst and preparation method thereof.
Background technology
Photocatalysis oxidation technique is considered as one of the technology for most having application prospect for solving problem of environmental pollution.It is so far
Only, it has been found that have more than 3000 kinds of organic compound difficult to degrade that can rapidly degrade by photochemical catalytic oxidation.In photocatalysis
In the common semiconductor of technology, TiO2Manufacturing cost relative moderate, have reaction condition is mild, chemical stability is high, safety
It has no toxic side effect, the advantages that service life is long, and causes people and more and more pay close attention to.Currently, simple TiO2Catalyst
There is also two urgent problems to be solved in practical applications：First, the utilization ratio of solar energy is low, TiO2To the absorption master of light
The luminous energy for accounting for solar spectrum range 4% can only be utilized in a bit of of ultra-violet (UV) band；Second, semiconductor carriers recombination rate is high,
Photo-quantum efficiency is low.Therefore, the visible light-responded catalysis material of R and D, and photo-quantum efficiency is improved, to improve
The utilization ratio of sunlight promotes the application of catalysis material, is current critical issue urgently to be resolved hurrily.
Recently, the compound TiO of emerging noble metal2Base heterojunction structure nano material has obtained scientist and has widely paid close attention to.
In noble metal/semiconductor heterostructure, noble metal can be in the strong surface plasma body resonant vibration of visible region (SPR) effect
Expand visible absorption；And noble metal generally has fermi level more lower than semiconductor, can promote light induced electron and hole
Separation, to improve the photo-quantum efficiency of photochemical catalyst, thus as the hot spot of research.The surface plasma of gold nanoparticle
The shape of resonance body (SPR) strong depend-ence particle, spherical particle shows as single SPR spectral peaks, and rod-shaped particle then has laterally
With longitudinal SPR spectral peaks, and longitudinal direction SPR spectral peaks peak position and intensity depend on the horizontal ratio of diameter of rod-shaped particle, in visible light to near-infrared
Light area is continuously adjustable.Therefore, the spectral response range of noble metal nano stick/semiconductor hybrid nano-particle is wider, will show more
Add excellent photocatalysis performance.
Researcher designs the noble metal/TiO for having synthesized a variety of different structures2Dissimilar materials improves its photocatalysis efficiency.
Na Zhou etc. report TiO2The hybrid material for coating Au nanometer rods (AuNR), with high visible light catalysis activity
(Nanoscale 2013,5,4236).Ang Li et al. utilizes removal intermediate sacrificial layer using gold chloride and butyl titanate as raw material
Method synthesized using AuNR as core, with TiO2For the hollow core-shell structure photochemical catalyst of shell, improves and degrade under visible light
The efficiency (Small 2015,16,1892) of benzaldehyde.Hybrid material in these researchs is the TiO using AuNR as core2For shell
Layer.Compared with this structure, Au Nanoparticle Modifieds are in TiO2The heterojunction structure hybrid material of outer surface, can preferably utilize
Au nano-particles absorb visible light, to show more excellent photocatalysis performance.Such as Tatiana C.Damato
Et al. describe it is a kind of in the TiO prepared2Nanosphere surface in situ restores the gold nanosphere of gold chloride preparation uniform particle sizes
Method (Langmuir 2013,29,1642).But this method hardly results in other shapes of gold nanoparticle.Do not have also at present
There is solution phase noble metal nano stick to modify TiO on the outside2The report of heterojunction structure.Because of the invention low cost and easy-operating preparation
The TiO absorbed with efficient visible light2The method of/AuNR heterojunction structures, is of great significance as visible light catalytic.
Invention content
The object of the present invention is to provide a kind of easy-to-use preparation TiO2/ Au nanometer rods (AuNR) sea urchin shape heterojunction structure
The method of photochemical catalyst, and TiO in heterojunction structure2The ratio of the AuNR and titanium source that can be added by change with the ratio of Au
To be adjusted.
TiO of the present invention2The preparation method of/Au nanometer rods sea urchin shape heterojunction structure photochemical catalysts, its step are as follows：
1) using surfactant be prepared Au nanometer rods (AuNR) colloidal solution (Chem.Mater.2003,15,
1957), as primary reaction seed；
2) 8~16mL for obtaining step 1), the Au nanometer rods that Au nanometer rods (AuNR) quality is 0.78~1.56mg
(AuNR) colloidal solution is concentrated by the method for centrifugation, is concentrated to the 2~3% of original volume, is then concentrated to lower layer
10~30mL of deionized water is added in product, after 10~20min is stirred at room temperature, adds the titanium salt aqueous solution of 5~10mg/mL
0.5~1mL, mixture room temperature continue 30~50min of stirring, then heat 2~6 hours, obtain pale purple at 100~130 DEG C
The TiO of color2/ Au nanometer rods (AuNR) sea urchin shape heterojunction structure photochemical catalyst.
The diameter of the Au nanometer rods (AuNR) of the primary reaction seed is 10~18nm, and length is 40~47nm.Centrifugation
The rotating speed of separation is 6000~8000rpm, and the time is 8~10 minutes.Titanium source is titanium tetrafluoride, titanium tetrachloride, titanium trichloride, sulphur
Sour titanium, butyl titanate, tetraisopropoxy titanium or triethanolamine isopropyl titanate.Surfactant is benzyl cetyl chloride
Ammonium, polyvinylpyrrolidone, lauryl sodium sulfate, cetyl trimethylammonium bromide or cetyl trimethyl chlorination
Ammonium.
A kind of TiO2/ Au nanometer rods sea urchin shape heterojunction structure photochemical catalysts, are prepared by the above method.
Synthesis TiO of the present invention2What the method of/Au nanometer rods (AuNR) sea urchin shape heterojunction structure photochemical catalyst used sets
Standby simple, mild condition, chemical reagent used are cheap and easy to get.The TiO of preparation2/ Au nanometer rods (AuNR) sea urchin shape heterojunction structure
A diameter of 175~250nm of photochemical catalyst, wherein AuNR are uniformly modified in TiO2Surface, the diameter of Au nanometer rods (AuNR)
For 10~18nm, length is 40~47nm, TiO2It is Detitanium-ore-type structure.TiO prepared by the present invention2/ AuNR sea urchin shape hetero-junctions
Structure photochemical catalyst presents the SPR absorptions of strong Au nanometer rods (AuNR) and excellent antireflection characteristic in visible region, can
To capture more sunlights；AuNR can improve the separative efficiency in light induced electron and hole simultaneously, and sea urchin shape structure has in addition
Big specific surface area.The experimental results showed that as semiconductor light-catalyst, visible light (λmax>420nm) catalytic effect is than business
The TiO of change2(P25) it increases significantly.
The present invention is for the first time that seed growth obtains Au nanometer rods (AuNR) with Au nanometer rods (AuNR) in water solution system
Modification is in TiO2The sea urchin shape heterojunction structure photochemical catalyst of outer surface.The TiO of preparation2/ Au nanometer rods (AuNR) sea urchin shape hetero-junctions
Structure photocatalyst material can effectively absorb visible light, present the visible light catalytic performance of stability and high efficiency, preparation method letter
List, favorable repeatability, can amplification quantity production, in necks such as photocatalytic degradation environmental contaminants, solar cell and solar hydrogen makings
There is good application prospect in domain.
Description of the drawings
Fig. 1：Au nanometer rods (AuNR) colloidal solution (1) and TiO that embodiment 1 is prepared2/ Au nanometer rods (AuNR)
The UV-visible absorption spectrum of sea urchin shape heterojunction structure photochemical catalyst colloidal solution (2)；
Fig. 2：The TiO that embodiment 1 is prepared2/ Au nanometer rods (AuNR) sea urchin shape heterojunction structure photochemical catalyst is in difference
Transmission electron microscope photo under amplification factor, figure (b) are the partial enlarged views of figure (a)；
Fig. 3：The TiO that embodiment 1 is prepared2The X-ray of/Au nanometer rods (AuNR) sea urchin shape heterojunction structure photochemical catalyst
Diffraction spectrogram；
Fig. 4：The TiO that Application Example 1 is prepared2/ Au nanometer rods (AuNR) sea urchin shape heterojunction structure photochemical catalyst and
The light degradation curve of P25 visible light photocatalytic degradation dye molecule rhodamine Bs；
Fig. 5：The TiO that embodiment 2 is prepared2The transmission of/Au nanometer rods (AuNR) sea urchin shape heterojunction structure photochemical catalyst
Electron micrograph.
Specific implementation mode
More detailed description is done to technical scheme of the present invention with specific embodiment below, but the example is not constituted to this
The limitation of invention.
Embodiment 1
Au nanometer rods (AuNR) colloidal solution is prepared using CTAB as surfactant, and (AuNR's is a diameter of
10nm, a concentration of 0.492mM of length 44nm, Au atom).It is in rotating speed by Au nanometer rods (AuNR) colloidal solution of 8mL
After being centrifuged 8 minutes under conditions of 7000rpm, removing a layer concentrate, (volume is 0.2mL, wherein the matter of nanometer rods containing Au (AuNR)
Amount is 0.78mg), deionized water 30mL is then added, after 10min is stirred at room temperature, the titanium tetrafluoride for adding 5mg/mL is water-soluble
Liquid 0.5mL.Mixture room temperature continues to stir 30min, is then heated 6 hours at 100 DEG C, obtains lilac TiO2/AuNR
Sea urchin shape heterojunction structure photochemical catalyst, product quality is 1.1mg.
1 performance test of embodiment
Take 4mg TiO produced by the present invention24mL Luo Dan are added in/Au nanometer rods (AuNR) sea urchin shape heterojunction structure photochemical catalyst
In the aqueous solution (5ppm) of bright B, standing 30min at room temperature makes nano-particle reach balance to rhodamine B absorption；Then in magnetic
Power stirring is lower to use 300W xenon sources (λmax>It 420nm) irradiates (lamp and sample distance 30cm) and starts timing.Interval is certain
Time sampling takes supernatant after centrifugation, and ultraviolet-uisible spectrophotometer is used in combination to measure it in rhodamine B maximum absorption wavelength
The absorbance at place evaluates its Photocatalytic Degradation Property.Using TiO2/ AuNR sea urchin shape heterojunction structures and titanium dioxide P25 conducts
Degradation rate after catalyst illumination rhodamine B 90min is 90.6% and 25.6% respectively, illustrates the TiO prepared2/ AuNR sea urchins
Shape heterojunction structure photochemical catalyst has significantly superior different photocatalysis performance.
The AuNR colloidal solution (1) and TiO that attached drawing 1 is2/ AuNR sea urchin shape heterojunction structure photochemical catalyst colloidal solution
(2) UV-visible absorption spectrum.Au and TiO as shown in the figure2/ AuNR respectively 513nm, 850nm and 513nm,
Apparent lateral resonance and longitudinal resonance absorption peak are presented at 814.5nm.
The TiO that attached drawing 2 is2The transmission electricity of/AuNR sea urchin shape heterojunction structure photochemical catalysts under different amplification
Sub- microscope photo.As shown in the figure uniform sea urchin shape structure, average diameter 250nm are all presented in prodigious range；Its
Middle AuNR is uniformly modified in TiO2Surface, AuNR a diameter of 10nm, length 44nm.Figure (b) is the partial enlargement of figure (a)
Figure.
The TiO that attached drawing 3 is2The X-ray diffraction spectrogram of/AuNR sea urchin shape heterojunction structure photochemical catalysts.As shown in the figure
The TiO of anatase crystal2Diffraction maximum it is high-visible, illustrate synthesis TiO2It is anatase crystal.
The TiO that attached drawing 4 is2/ AuNR sea urchins shape heterojunction structure photochemical catalyst and titanium dioxide P25 visible light catalytics drop
Solve the light degradation curve of the Concentration-time of dye molecule rhodamine B.According to degradation rate calculation formula：η=(A0-At)/A0`
100%, (A0For the initial absorbance of rhodamine B solution before illumination；AtFor extinction at the time of rhodamine B solution after light application time t
Degree) it is calculated using TiO2/ AuNR sea urchins shape heterojunction structure photochemical catalyst and titanium dioxide P25 illumination rhodamine Bs 90min
Degradation rate afterwards is 90.6% and 25.6% respectively, illustrates the TiO prepared2/ AuNR sea urchin shape heterojunction structure photochemical catalysts have
Superior photocatalysis performance.
Embodiment 2
AuNR colloidal solution is prepared using CTAB as surfactant, and (a diameter of 16nm of AuNR, length are
A concentration of 0.492mM of 40nm, Au atom).The AuNR colloidal solution of 8mL is centrifuged 10 under conditions of rotating speed is 8000rpm
After minute, a layer concentrate (volume is 0.2mL, wherein the quality containing AuNR is 0.78mg) is removed, deionized water is then added
30mL after 10min is stirred at room temperature, adds the titanium tetrafluoride aqueous solution 0.5mL of 5mg/mL.Mixture room temperature continues to stir
30min then heats 6 hours at 100 DEG C, obtains lilac TiO2/ AuNR sea urchin shape heterojunction structure photochemical catalysts, production
Amount of substance is 1.1mg.
The TiO that attached drawing 5 is2The transmission electron microscope photo of/AuNR sea urchin shape heterojunction structure photochemical catalysts.Such as figure
It is shown all to present uniform sea urchin shape structure, average diameter 200nm in prodigious range；Wherein AuNR is uniformly modified
In TiO2Surface, a diameter of 16nm of AuNR, length 40nm.
Embodiment 3
AuNR colloidal solution is prepared using CTAB as surfactant, and (a diameter of 18nm of AuNR, length are
A concentration of 0.492mM of 47nm, Au atom).The AuNR colloidal solution of 8mL is centrifuged 8 under conditions of rotating speed is 6000rpm
After minute, a layer concentrate (volume is 0.2mL, wherein the quality containing AuNR is 0.78mg) is removed, deionized water is then added
30mL after 10min is stirred at room temperature, adds the titanium tetrafluoride aqueous solution 0.5mL of 5mg/mL.Mixture room temperature continues to stir
30min then heats 6 hours at 100 DEG C, obtains lilac TiO2/ AuNR sea urchin shape heterojunction structure photochemical catalysts, production
Amount of substance is 1.1mg.
TiO2The average diameter of/AuNR sea urchin shape heterojunction structure photochemical catalysts is 200nm；Uniformly modification exists wherein AuNR
TiO2Surface, a diameter of 18nm of AuNR, length 47nm.
Embodiment 4
AuNR colloidal solution is prepared using CTAB as surfactant, and (a diameter of 10nm of AuNR, length are
A concentration of 0.492mM of 42nm, Au atom).The AuNR colloidal solution of 8mL is centrifuged 10 under conditions of rotating speed is 8000rpm
After minute, a layer concentrate (volume is 0.2mL, wherein the quality containing AuNR is 0.78mg) is removed, deionized water is then added
30mL after 10min is stirred at room temperature, adds the titanium tetrafluoride aqueous solution 0.5mL of 5mg/mL.Mixture room temperature continues to stir
30min then heats 6 hours at 100 DEG C, obtains lilac TiO2/ AuNR sea urchin shape heterojunction structure photochemical catalysts, production
Amount of substance is 1.1mg.
TiO2The average diameter of/AuNR sea urchin shape heterojunction structure photochemical catalysts is 200nm；Uniformly modification exists wherein AuNR
TiO2Surface, a diameter of 10nm of AuNR, length 42nm.
Embodiment 5
AuNR colloidal solution is prepared using CTAB as surfactant, and (a diameter of 16nm of AuNR, length are
A concentration of 0.492mM of 40nm, Au atom).The AuNR colloidal solution of 16mL is centrifuged 10 under conditions of rotating speed is 8000rpm
After minute, a layer concentrate (volume is 0.4mL, wherein the quality containing AuNR is 1.55mg) is removed, deionized water is then added
29.5mL after 20min is stirred at room temperature, adds the titanium tetrafluoride aqueous solution 1mL of 10 mg/mL.Mixture room temperature continues to stir
50min then heats 6 hours at 100 DEG C, obtains lilac TiO2/ AuNR sea urchin shape heterojunction structure photochemical catalysts, product
Quality is 2.8mg.
TiO2The average diameter of/AuNR sea urchin shape heterojunction structure photochemical catalysts is 230nm；Uniformly modification exists wherein AuNR
TiO2Surface, a diameter of 16nm of AuNR, length 40nm.
Embodiment 6
AuNR colloidal solution is prepared using CTAB as surfactant, and (a diameter of 16nm of AuNR, length are
A concentration of 0.492mM of 40nm, Au atom).The AuNR colloidal solution of 8mL is centrifuged 10 under conditions of rotating speed is 8000rpm
After minute, a layer concentrate (volume is 0.2mL, wherein the quality containing AuNR is 0.78mg) is removed, deionized water is then added
10mL after 10min is stirred at room temperature, adds the titanium tetrafluoride aqueous solution 0.5mL of 5mg/mL.Mixture room temperature continues to stir
30min then heats 6 hours at 100 DEG C, obtains lilac TiO2/ AuNR sea urchin shape heterojunction structure photochemical catalysts, production
Amount of substance is 1.1mg.
TiO2The average diameter of/AuNR sea urchin shape heterojunction structure photochemical catalysts is 175nm；Uniformly modification exists wherein AuNR
TiO2Surface, a diameter of 16nm of AuNR, length 40nm.
Embodiment 7
AuNR colloidal solution is prepared using CTAB as surfactant, and (a diameter of 44nm of AuNR, length are
A concentration of 0.492mM of 10nm, Au atom).The AuNR colloidal solution of 8mL is centrifuged 10 under conditions of rotating speed is 8000rpm
After minute, a layer concentrate (volume is 0.2mL, wherein the quality containing AuNR is 0.78mg) is removed, deionized water is then added
30mL after 10min is stirred at room temperature, adds the titanium tetrafluoride aqueous solution 0.5mL of 5mg/mL.Mixture room temperature continues to stir
30min then heats 2 hours at 130 DEG C, obtains lilac TiO2/ AuNR sea urchin shape heterojunction structure photochemical catalysts, production
Amount of substance is 1.1mg.
TiO2The average diameter of/AuNR sea urchin shape heterojunction structure photochemical catalysts is 210nm；Uniformly modification exists wherein AuNR
TiO2Surface, a diameter of 10nm of AuNR, length 44nm.
Claims (5)
1. a kind of TiO2The preparation method of/Au nanometer rods sea urchin shape heterojunction structure photochemical catalysts, its step are as follows：
1) Au nanometer rods colloidal solution is prepared using surfactant, as primary reaction seed, the diameter of Au nanometer rods
It is 10~18nm, length is 40~47nm；
2) 8~16mL that step 1) obtains, the Au nanometer rods colloidal solution that Au nanometer rods quality is 0.78~1.56mg are passed through
The method of centrifugation is concentrated, and the 2~3% of original volume are concentrated to, and deionized water then is added into lower layer's enriched product
10~30mL after 10~20min is stirred at room temperature, adds titanium salt 0.5~1mL of aqueous solution of 5~10mg/mL, mixture room temperature
Continue 30~50min of stirring, is then heated 2~6 hours at 100~130 DEG C, obtain lilac TiO2/ Au nanometer rods sea
Courage shape heterojunction structure photochemical catalyst.
2. a kind of TiO as described in claim 12The preparation method of/Au nanometer rods sea urchin shape heterojunction structure photochemical catalysts, it is special
Sign is：The rotating speed of centrifugation is 6000~8000rpm, and the time is 8~10 minutes.
3. a kind of TiO as described in claim 12The preparation method of/Au nanometer rods sea urchin shape heterojunction structure photochemical catalysts, it is special
Sign is：Titanium source is titanium tetrafluoride, titanium tetrachloride, titanium trichloride, titanium sulfate, butyl titanate, tetraisopropoxy titanium or three second
Hydramine isopropyl titanate.
4. a kind of TiO as described in claim 12The preparation method of/Au nanometer rods sea urchin shape heterojunction structure photochemical catalysts, it is special
Sign is：Surfactant is benzyl cetyl chloride ammonium, polyvinylpyrrolidone, lauryl sodium sulfate, hexadecane
Base trimethylammonium bromide or hexadecyltrimethylammonium chloride.
5. a kind of TiO2/ Au nanometer rods sea urchin shape heterojunction structure photochemical catalysts, it is characterised in that：It is any by Claims 1 to 4
One method is prepared.
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