CN105749908B - A kind of Au@TiO2Hollow core-shell structure photochemical catalyst and preparation method thereof - Google Patents
A kind of Au@TiO2Hollow core-shell structure photochemical catalyst and preparation method thereof Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 82
- 239000002105 nanoparticle Substances 0.000 claims abstract description 42
- 238000000034 method Methods 0.000 claims abstract description 19
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000010936 titanium Substances 0.000 claims abstract description 9
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 9
- 239000010931 gold Substances 0.000 claims description 113
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 239000000084 colloidal system Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 21
- 239000002245 particle Substances 0.000 claims description 20
- 235000019441 ethanol Nutrition 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 10
- NMWONDKHBZEDMY-UHFFFAOYSA-H [Au](Cl)(Cl)Cl.C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+] Chemical compound [Au](Cl)(Cl)Cl.C(CC(O)(C(=O)[O-])CC(=O)[O-])(=O)[O-].[Na+].[Na+].[Na+] NMWONDKHBZEDMY-UHFFFAOYSA-H 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 230000009467 reduction Effects 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 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
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- XROWMBWRMNHXMF-UHFFFAOYSA-J titanium tetrafluoride Chemical group [F-].[F-].[F-].[F-].[Ti+4] XROWMBWRMNHXMF-UHFFFAOYSA-J 0.000 claims description 3
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000005909 ethyl alcohol group Chemical group 0.000 claims description 2
- 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 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000348 titanium sulfate Inorganic materials 0.000 claims description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims 2
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 238000007146 photocatalysis Methods 0.000 abstract description 16
- 239000004065 semiconductor Substances 0.000 abstract description 14
- 239000004408 titanium dioxide Substances 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 230000002776 aggregation Effects 0.000 abstract description 4
- 238000004220 aggregation Methods 0.000 abstract description 4
- 230000004927 fusion Effects 0.000 abstract description 2
- 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 19
- 229940043267 rhodamine b Drugs 0.000 description 17
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 10
- 239000000047 product Substances 0.000 description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000004364 calculation method Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000003321 amplification Effects 0.000 description 3
- 229910052681 coesite Inorganic materials 0.000 description 3
- 229910052906 cristobalite Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 229910052682 stishovite Inorganic materials 0.000 description 3
- 229910052905 tridymite Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
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- 238000003912 environmental pollution Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
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- 238000005070 sampling Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910010342 TiF4 Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
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- 238000000635 electron micrograph Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
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- 235000009566 rice Nutrition 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
- 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
- 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
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- 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
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
A kind of Au@TiO2Hollow core-shell structure photochemical catalyst and preparation method thereof, belongs to semiconductor light-catalyst technical field.Using Au nano-particles as kernel, with TiO2For shell, and there is cavity between kernel and shell.Wherein the size of Au cores can be adjusted by changing the size of the Au nano-particle seeds added in, and the thickness of shell and the size of cavity can be adjusted by changing the Au nano-particles added in and the ratio of titanium source and the concentration of titanium source.Method provided by the invention avoids prepare the aggregation fusion of the Au nano-particles during titanium dioxide shell caused by Au cores size is inhomogenous or a cavity in multiple Au cores appearance.Using hollow core-shell structure prepared by the present invention, the size of Au cores is controllable, while ensures that only there are one Au cores in a cavity, and nucleocapsid is uniform, visible ray (λmax>420nm) catalytic effect increases significantly than titanium dioxide P25, has good application prospect in photocatalysis field.
Description
Technical field
The invention belongs to semiconductor light-catalyst technical fields, and in particular to a kind of Au@TiO2Hollow core-shell structure light is urged
Agent and preparation method thereof.
Background technology
Photocatalysis oxidation technique is considered as one of 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 Photocatalytic Oxidation With Semiconductors.
In the common semiconductor of photocatalysis technology, TiO2Safe and non-toxic, cheap, photocatalysis performance is excellent under ultraviolet light for itself
It is good, and its physicochemical properties is stablized, reaction condition is mildly easy to get, and service life is long and is widely used.It is however, simple at present
TiO2Can only be excited by ultraviolet light, therefore its luminous energy absorbed only about accounts for the 4% of sunlight, solar energy utilizes effect
Rate is low.And Carrier recombination rate caused by semiconductor light-receiving excitation is high, and photo-quantum efficiency is low.Therefore, R and D can
See the conductor photocatalysis material of photoresponse, photoresponse range is expanded into visible region, imitated so as to improve utilizing for sunlight
Rate, and photo-quantum efficiency is improved, application of the catalysis material in actual production and life is promoted, is the key that urgently to be resolved hurrily at present
Problem.
Recently, the compound semiconductor nano material of noble metal becomes research since it improves the ability of photocatalysis efficiency
Hot spot.The advantages of heterojunction structure of noble metal/semiconductor combines noble metal and semiconductor respectively, noble metal is in visible region
Strong surface plasma body resonant vibration (SPR) effect can expand absorption of the nano material to visible ray；And noble metal generally has
There is the fermi level lower than semiconductor, promote the separation in light induced electron and hole, so as to improve the light quantum of photochemical catalyst
Efficiency.In addition the structure of regulation and control semi-conductor nano particles is also to improve the important method of its photocatalysis performance.In recent years, have only
The hollow Nano microballoon of special hollow structure is had received widespread attention when having the advantages that density is low, specific surface area is high.Partly lead
The unique hollow structure of body hollow Nano microballoon can increase reflection and scattering of the light in hollow structure, improve luminous energy capture effect
Rate；And its big specific surface area can increase the adsorbance to reaction substrate；At the same time, internal space can accommodate
A certain amount of reaction solution is conducive to the diffusion of reaction substrate and product, so as to improve urging for semiconductor light-catalyst from many aspects
Change efficiency.Yin etc. passes through selective removal SiO2@TiO2The kernel of core-shell nano, has synthesized TiO2Tiny balloon (crystal form,
Crystallinity is adjustable), compared with commercialized titanium dioxide (P25), which has in the experiment of photocatalytic degradation rhodamine B
Higher catalytic efficiency (Adv.Funct.Mater.2013,23,4246).
By analysis above, if it is expected that can be in a semi-conductor nano particles in combination with noble metal
The advantages of nano particle hybridization and cavitation, for example construct noble metal@TiO2Hollow core-shell structure nano particle will make solar energy sharp
It is further improved with efficiency, promises to be very much a kind of new strategy for enhancing semi-conductor nano particles visible light catalytic performance.
Zaera etc. is by preparing Au@SiO2@TiO2Three-layer nuclear shell structure simultaneously selectively removes SiO2The method of middle layer is prepared for Au@
TiO2Hollow core-shell structure nano particle (Angew.Chem.Int.Ed.2011,50,10208).However this method needs sternly
The growth of lattice control middle layer and selectivity remove process, and step is comparatively laborious, and is also easy to produce the by-product for causing environmental pollution
Object.Chinese Academy Of Sciences Process Engineering Research Institute wangdan researcher and State Nanometer Science Center Tang Zhiyong researcher pass through in ethyl alcohol
Aqueous systems accelerate Ostwald maturing process to be prepared for Au@TiO2Hollow core-shell structure nano particle
(Energy.Environ.Sci.2012,5,6914).But this method is forming Au@TiO2It is deposited in hollow core-shell configuration process
In the aggregation fusion process of the Au nano-particles as seed, Au nano-particles sizes, quantity in final cavity is caused to differ, and
It is difficult the size of regulation and control Au cores.Because of the invention low cost and easy-operating uniform Au of the preparation with efficient visible light absorption
TiO2The method of hollow core-shell structure, is of great significance as visible light catalytic.
Invention content
The object of the present invention is to provide a kind of Au@TiO2Hollow core-shell structure photochemical catalyst and its easy-to-use preparation side
Method.Au@TiO2Hollow core-shell structure is using Au nano-particles as kernel, with TiO2For shell, and there is sky between kernel and shell
Chamber.Wherein the size of Au cores can be adjusted by changing the size of the Au nano-particle seeds added in, the thickness and sky of shell
The size of chamber can be adjusted by changing the Au nano-particles added in and the ratio of titanium source and the concentration of titanium source.Report at present
Road (Energy.Environ.Sci.2012,5,6914) accelerates Ostwald maturing process to prepare Au@in ethanol-water system
TiO2The method of hollow core-shell structure photochemical catalyst results in Au and receives due to adding in ethyl alcohol directly into Au nano-particle aqueous solutions
The aggregation of rice corpuscles, so as to make the Au finally obtained core sizes inhomogenous and appear in the situation for having multiple Au cores in a shell.
Method provided by the invention avoids prepare the aggregation fusion of the Au nano-particles during titanium dioxide shell caused by Au cores
Size is inhomogenous or the appearance of multiple Au cores.Using hollow core-shell structure prepared by the present invention, the size of Au cores is controllable,
Ensure that only there are one Au cores in a cavity simultaneously, nucleocapsid is uniform, is conducive to improve the Au TiO2Hollow core-shell structure light
The preparation repeatability of catalyst and catalytic efficiency and stability during as visible light catalyst.
A kind of Au@TiO of the present invention2The preparation method of hollow core-shell structure photochemical catalyst, its step are as follows：
1) Au nanometer particle colloid solution is prepared with the method for reduction of sodium citrate gold chloride, as primary reaction kind
Son, the concentration range of Au nano-particles is 1.5 × 10-11~5.0 × 10-10mol/L；
2) it is sequentially added under conditions of being stirred at room temperature into the Au nanometer particle colloid solution that 4~8mL steps 1) obtain
0.25~5mL of titanium source aqueous solution of a concentration of 0.5~5mg/mL, deionized water 3.5~12mL, 2~add alcohol after ten minutes
5~14mL of class solvent；Mixture room temperature continues stirring 10~30 minutes, then heats 2~10 hours, obtains at 100~180 DEG C
To Au@TiO of the present invention2Hollow core-shell structure photochemical catalyst.
The diameter of the primary reaction seed Au nano-particles is 25~80nm.Titanium source is titanium tetrafluoride (TiF4), tetrachloro
Change titanium, titanium sulfate, butyl titanate, isopropyl titanate or isopropyl titanate.Alcohols solvent is ethyl alcohol, normal propyl alcohol, isopropanol, positive fourth
Alcohol, isobutanol, sec-butyl alcohol or the tert-butyl alcohol.
Preparation Au@TiO of the present invention2Equipment that the method for hollow core-shell structure photochemical catalyst uses is simple, condition temperature
It is cheap and easy to get with chemical reagent used.The Au@TiO of preparation2A diameter of 130~170nm of hollow core-shell structure, shell thickness
For 15~20nm, a diameter of 25~80nm, TiO of core A u nano-particles2It is anatase crystal, and a TiO2Shell cavity
Interior there are one Au cores (as shown in Figure 7).
Au@TiO prepared by the present invention2Hollow core-shell structure photochemical catalyst presents strong Au nanoparticles in visible region
The SPR of son absorbs, and Au nano-particles can improve the separative efficiency in light induced electron and hole.In addition Au@TiO2Hollow core-shell
Structure can effectively reduce the reflection of light, so as to improve the absorption efficiency of light.Meanwhile the big specific surface area of hollow core-shell structure can
To increase the adsorbance to reaction substrate, internal space can also accommodate a certain amount of reaction solution, be conducive to reaction substrate
With the diffusion of product.The experimental results showed that as semiconductor light-catalyst, Au@TiO2Hollow core-shell structure photochemical catalyst it is visible
Light (λmax>420nm) catalytic effect increases significantly, and preparation method is simple than business oxide/titanium dioxide P25, repeats
Property it is good, can amplification quantity production, have in fields such as photocatalytic degradation environmental contaminants, solar cell and solar hydrogen makings good
Application prospect.
Description of the drawings
Fig. 1：The Au nanometer particle colloids solution (curve 1) and Au@TiO that embodiment 1 is prepared2Hollow core-shell structure light
The UV-visible absorption spectrum of catalyst colloid solution (curve 2)；
Fig. 2：The Au@TiO that embodiment 1 is prepared2Hollow core-shell structure photochemical catalyst is saturating under different amplification
Electron micrograph is penetrated, figure (b) is the partial enlarged view of figure (a)；
Fig. 3：The Au@TiO that embodiment 1 is prepared2The X-ray diffraction spectrogram of hollow core-shell structure photochemical catalyst；
Fig. 4：The Au@TiO that Application Example 1 is prepared2Hollow core-shell structure photochemical catalyst and titanium dioxide P25 can
See the light degradation curve graph of photocatalytic degradation of dye molecule rhodamine B；
Fig. 5：The Au@TiO that embodiment 2 is prepared2The transmission electron microscope photo of hollow core-shell structure photochemical catalyst.
Fig. 6：The Au@TiO that Application Example 4 is prepared2Hollow core-shell structure photochemical catalyst and titanium dioxide P25 can
See the light degradation curve graph of photocatalytic degradation of dye molecule rhodamine B；
Fig. 7：Au@TiO of the present invention2Hollow core-shell structure photocatalyst structure schematic diagram.
Specific embodiment
More detailed description does technical scheme of the present invention with specific embodiment below, but the example is not formed to this
The limitation of invention.
Embodiment 1
It is made using reduction of sodium citrate gold chloride method (Nature Physical Science 1973,241,20-22.)
It is standby to obtain a concentration of 6.3 × 10-11The Au nanometer particle colloids solution (a diameter of 50nm of Au nano-particles) of mol/L.
Sequentially add a concentration of 5 mg/mL's into 8mL Au nanometer particle colloid solution under conditions of being stirred at room temperature
TiF4Aqueous solution 0.5mL, deionized water 8mL add ethyl alcohol 14mL after five minutes.Mixture room temperature continues stirring 10 minutes, with
It is heated 6 hours at 180 DEG C afterwards, obtains the Au@TiO of pink2Hollow core-shell structure photochemical catalyst, product quality are 1.7mg.
1 performance test of embodiment
Take 4mg Au@TiO produced by the present invention2Hollow core-shell structure photochemical catalyst adds in the aqueous solution of 4mL rhodamine Bs
In (5ppm), being placed in dark place uniformly disperses 30 minutes nano-particle and reaches balance to rhodamine B absorption；Then it is stirred in magnetic force
It mixes lower using 300W xenon sources (λmax>It 420nm) irradiates (lamp and sample distance 30cm) and starts timing.Separated in time
Sampling, takes supernatant, and measure it in rhodamine B maximum absorption wave strong point with ultraviolet-visible spectrophotometer after centrifugation
Absorbance, evaluate its Photocatalytic Degradation Property.Using Au@TiO2Hollow core-shell structure and titanium dioxide P25 are as catalyst
Degradation rate of the illumination rhodamine B after 4 hours is 99.5% and 57.7% respectively, illustrates the Au@TiO prepared2Hollow core-shell structure
Photochemical catalyst has significantly superior different photocatalysis performance.
The Au nanometer particle colloids solution (1) and Au@TiO that attached drawing 1 is2Hollow core-shell structure light catalyst colloid is molten
The UV-visible absorption spectrum of liquid (2).Au and Au@TiO as shown in the figure2It is presented at 535 nm and 552nm respectively apparent
SPR absorption peaks.
The Au@TiO that attached drawing 2 is2Transmitted electron of the hollow core-shell structure photochemical catalyst under different amplification is shown
Micro mirror photo.It is shown in very big range and all presents TiO2For the uniform hollow core-shell structure that shell, Au are kernel,
A diameter of 150nm of nucleocapsid, shell thickness 15nm, a diameter of 50nm of core A u nano-particles.It is figure (a) to scheme (b)
Partial enlarged view.
The Au@TiO that attached drawing 3 is2The X-ray diffraction spectrogram of hollow core-shell structure photochemical catalyst.Rutile titania as shown in the figure
Ore deposit crystal form TiO2Diffraction maximum it is high-visible, illustrate synthesis TiO2It is anatase crystal.
The Au@TiO that attached drawing 4 is2Hollow core-shell structure photochemical catalyst and titanium dioxide P25 visible light photocatalytic degradations dye
Expect the light degradation curve of the Concentration-time of molecule rhodamine B.According to degradation rate calculation formula：η=(A0-At)/A0* 100%,
(A0Initial absorbance for rhodamine B solution before illumination；AtFor absorbance at the time of rhodamine B solution after light application time t) meter
Calculation is applied Au@TiO2The degradation rate of hollow core-shell structure photochemical catalyst and titanium dioxide P25 illumination rhodamine B after 4 hours
It is 99.5% and 57.7% respectively, illustrates the Au@TiO prepared2Hollow core-shell structure photochemical catalyst has superior photocatalysis
Performance.
Embodiment 2
A concentration of 6.3 × 10 are prepared using reduction of sodium citrate gold chloride-11The Au nanometer particle colloids of mol/L are molten
Liquid (a diameter of 50nm of Au nano-particles).Add successively into 8mL Au nanometer particle colloid solution under conditions of being stirred at room temperature
Enter the TiF of a concentration of 0.5mg/mL4Aqueous solution 5mL, deionized water 3.5mL add ethyl alcohol 14mL after five minutes.Mixture room
Temperature continues stirring 10 minutes, is then heated 6 hours at 180 DEG C, obtains the Au@TiO of pink2Hollow core-shell structure photocatalysis
Agent, product quality are 1.6mg.
The Au@TiO that attached drawing 5 is2The transmission electron microscope photo of hollow core-shell structure photochemical catalyst.As shown in the figure
TiO is all presented in very big range2For the uniform hollow core-shell structure that shell, Au are kernel, TiO2Shell is anatase
Crystal form, a diameter of 169nm of nucleocapsid, shell thickness 23nm, a diameter of 50nm of core A u nano-particles.
Embodiment 3
A concentration of 6.3 × 10 are prepared using reduction of sodium citrate gold chloride-11The Au nanometer particle colloids of mol/L are molten
Liquid (a diameter of 50nm of Au nano-particles).Add successively into 4mL Au nanometer particle colloid solution under conditions of being stirred at room temperature
Enter the TiF of a concentration of 5mg/mL4Aqueous solution 0.25mL, deionized water 12mL add ethyl alcohol 14mL after five minutes.Mixture room
Temperature continues stirring 10 minutes, is then heated 2 hours at 180 DEG C, obtains the Au@TiO of pink2Hollow core-shell structure photocatalysis
Agent, product quality are 1.0mg.
The photochemical catalyst of preparation presents TiO2For the hollow core-shell structure that shell, Au are kernel, TiO2Shell is anatase
Crystal form, a diameter of 153nm of nucleocapsid, shell thickness 21nm, a diameter of 50nm of core A u nano-particles.
Embodiment 4
A concentration of 6.3 × 10 are prepared using reduction of sodium citrate gold chloride-11The Au nanometer particle colloids of mol/L are molten
Liquid (a diameter of 50nm of Au nano-particles).Add successively into 8mL Au nanometer particle colloid solution under conditions of being stirred at room temperature
Enter the TiF of a concentration of 5mg/mL4Aqueous solution 0.5mL, deionized water 8mL add ethyl alcohol 14mL after five minutes.Mixture room temperature
Continue stirring 30 minutes, then heated 6 hours at 100 DEG C, obtain the Au@TiO of pink2Hollow core-shell structure photocatalysis
Agent, product quality are 1.5mg.
The photochemical catalyst of preparation presents TiO2For the hollow core-shell structure that shell, Au are kernel, TiO2Shell is anatase
Crystal form, a diameter of 150nm of nucleocapsid, shell thickness 20nm, a diameter of 50nm of core A u nano-particles.
4 performance test of embodiment
Take 4mg Au@TiO produced by the present invention2Hollow core-shell structure photochemical catalyst adds in the aqueous solution of 4mL rhodamine Bs
In (5ppm), being placed in dark place uniformly disperses 30 minutes nano-particle and reaches balance to rhodamine B absorption；Then it is stirred in magnetic force
It mixes lower using 300W xenon sources (λmax>It 420nm) irradiates (lamp and sample distance 30cm) and starts timing.Separated in time
Sampling, takes supernatant, and measure it in rhodamine B maximum absorption wave strong point with ultraviolet-visible spectrophotometer after centrifugation
Absorbance, evaluate its Photocatalytic Degradation Property.Using Au@TiO2Hollow core-shell structure and titanium dioxide P25 are as catalyst
Degradation rate of the illumination rhodamine B after 4 hours is 79.8% and 57.7% respectively, illustrates the Au@TiO prepared2Hollow core-shell structure
Photochemical catalyst has significantly superior different photocatalysis performance.
The Au@TiO that attached drawing 6 is2Hollow core-shell structure photochemical catalyst and titanium dioxide P25 visible light photocatalytic degradations dye
Expect the light degradation curve of the Concentration-time of molecule rhodamine B.According to degradation rate calculation formula：η=(A0-At)/A0* 100%,
(A0Initial absorbance for rhodamine B solution before illumination；AtFor absorbance at the time of rhodamine B solution after light application time t) meter
Calculation is applied Au@TiO2The degradation rate of hollow core-shell structure photochemical catalyst and titanium dioxide P25 illumination rhodamine B after 4 hours
It is 79.8% and 57.7% respectively, illustrates the Au@TiO prepared2Hollow core-shell structure photochemical catalyst has superior photocatalysis
Performance.
Embodiment 5
A concentration of 6.3 × 10 are prepared using reduction of sodium citrate gold chloride-11The Au nanometer particle colloids of mol/L are molten
Liquid (a diameter of 50nm of Au nano-particles).Add successively into 4mL Au nanometer particle colloid solution under conditions of being stirred at room temperature
Enter the TiF of a concentration of 5mg/mL4Aqueous solution 0.5mL, deionized water 12mL, adds ethyl alcohol 14mL after 2 minutes.Mixture room
Temperature continues stirring 10 minutes, is then heated 10 hours at 180 DEG C, obtains the Au@TiO of pink2Hollow core-shell structure light is urged
Agent, product quality are 1.5mg.
The photochemical catalyst of preparation presents TiO2For the hollow core-shell structure that shell, Au are kernel, TiO2Shell is anatase
Crystal form, a diameter of 150nm of nucleocapsid, shell thickness 15nm, a diameter of 50nm of core A u nano-particles.
Embodiment 6
A concentration of 5.0 × 10 are prepared using reduction of sodium citrate gold chloride-10The Au nanometer particle colloids of mol/L are molten
Liquid (a diameter of 25nm of Au nano-particles).Add successively into 4mL Au nanometer particle colloid solution under conditions of being stirred at room temperature
Enter the TiF of a concentration of 5mg/mL4Aqueous solution 0.5mL, deionized water 12mL add ethyl alcohol 14mL after ten minutes.Mixture room
Temperature continues stirring 10 minutes, is then heated 6 hours at 180 DEG C, obtains the Au@TiO of pink2Hollow core-shell structure photocatalysis
Agent, product quality are 1.8mg.
The photochemical catalyst of preparation presents TiO2For the hollow core-shell structure that shell, Au are kernel, TiO2Shell is anatase
Crystal form, a diameter of 130nm of nucleocapsid, shell thickness 20nm, a diameter of 25nm of core A u nano-particles.
Embodiment 7
A concentration of 1.5 × 10 are prepared using reduction of sodium citrate gold chloride-11The Au nanometer particle colloids of mol/L are molten
Liquid (a diameter of 80nm of Au nano-particles).Add successively into 8mL Au nanometer particle colloid solution under conditions of being stirred at room temperature
Enter the TiF of a concentration of 5mg/mL4Aqueous solution 0.5mL, deionized water 8mL add ethyl alcohol 5mL after five minutes.Mixture room temperature
Continue stirring 10 minutes, then heated 6 hours at 180 DEG C, obtain the Au@TiO of pink2Hollow core-shell structure photocatalysis
Agent, product quality are 1.4mg.
The photochemical catalyst of preparation presents TiO2For the hollow core-shell structure that shell, Au are kernel, TiO2Shell is anatase
Crystal form, a diameter of 170nm of nucleocapsid, shell thickness 20nm, a diameter of 80nm of core A u nano-particles.
Claims (5)
1. a kind of Au@TiO2The preparation method of hollow core-shell structure photochemical catalyst, its step are as follows：
1) Au nanometer particle colloid solution is prepared using the method for reduction of sodium citrate gold chloride, as primary reaction kind
Son, the concentration range of Au nano-particles is 1.5 × 10-11~5.0 × 10-10The diameter of mol/L, Au nano-particle is 25~
80nm；
2) under conditions of being stirred at room temperature concentration is sequentially added into the Au nanometer particle colloid solution that 4~8mL steps 1) obtain
0.25~5mL of titanium source aqueous solution for 0.5~5mg/mL, deionized water 3.5~12mL, 2~to add alcohols after ten minutes molten
5~14mL of agent；Mixture room temperature continues stirring 10~30 minutes, then heats 2~10 hours, obtains at 100~180 DEG C
Au@TiO2Hollow core-shell structure photochemical catalyst.
2. a kind of Au@TiO as described in claim 12The preparation method of hollow core-shell structure photochemical catalyst, it is characterised in that：System
Standby obtained Au@TiO2A diameter of 130~170nm of hollow core-shell structure, shell thickness be 15~23nm, core A u nanoparticles
A diameter of 25~the 80nm, TiO of son2It is anatase crystal, and a TiO2Only there are one Au cores in shell cavity.
3. a kind of Au@TiO as described in claim 12The preparation method of hollow core-shell structure photochemical catalyst, it is characterised in that：Titanium
Source is titanium tetrafluoride, titanium tetrachloride, titanium sulfate, butyl titanate, isopropyl titanate or isopropyl titanate.
4. a kind of Au@TiO as described in claim 12The preparation method of hollow core-shell structure photochemical catalyst, it is characterised in that：Alcohol
Class solvent is ethyl alcohol, normal propyl alcohol, isopropanol, n-butanol, isobutanol, sec-butyl alcohol or the tert-butyl alcohol.
5. a kind of Au@TiO2Hollow core-shell structure photochemical catalyst, it is characterised in that：As described in Claims 1 to 4 any one
Method is prepared.
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