CN105749908A - Photocatalyst of Au@TiO2 hollow core-shell structure and preparation method of photocatalyst of Au@TiO2 hollow core-shell structure - Google Patents
Photocatalyst of Au@TiO2 hollow core-shell structure and preparation method of photocatalyst of Au@TiO2 hollow core-shell structure Download PDFInfo
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- 239000011258 core-shell material Substances 0.000 title claims abstract description 76
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- 239000011941 photocatalyst Substances 0.000 title abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 43
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000010936 titanium Substances 0.000 claims abstract description 8
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 8
- 239000010931 gold Substances 0.000 claims description 53
- 239000003054 catalyst Substances 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 27
- 239000000084 colloidal system Substances 0.000 claims description 23
- 239000002245 particle Substances 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical group CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000013078 crystal Substances 0.000 claims description 11
- 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
- 238000006243 chemical reaction Methods 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
- 238000003756 stirring Methods 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 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
- 150000001298 alcohols Chemical class 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
- 239000002904 solvent Substances 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
- 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
- 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
- XJDNKRIXUMDJCW-UHFFFAOYSA-J titanium tetrachloride Chemical compound Cl[Ti](Cl)(Cl)Cl XJDNKRIXUMDJCW-UHFFFAOYSA-J 0.000 claims description 2
- 239000004408 titanium dioxide Substances 0.000 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 239000004065 semiconductor Substances 0.000 abstract description 10
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 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 description 19
- 229940043267 rhodamine b Drugs 0.000 description 19
- 230000015556 catabolic process Effects 0.000 description 11
- 238000006731 degradation reaction Methods 0.000 description 11
- 239000000047 product Substances 0.000 description 9
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 8
- 244000144730 Amygdalus persica Species 0.000 description 7
- 235000006040 Prunus persica var persica Nutrition 0.000 description 7
- 238000010521 absorption reaction Methods 0.000 description 7
- 238000002835 absorbance Methods 0.000 description 6
- 238000005286 illumination Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 230000003321 amplification Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 229910052681 coesite Inorganic materials 0.000 description 2
- 229910052906 cristobalite Inorganic materials 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000004005 microsphere 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
- 239000000376 reactant Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910052682 stishovite Inorganic materials 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910052905 tridymite Inorganic materials 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
- 230000001133 acceleration Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
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- 239000004020 conductor Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000007499 fusion processing Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002736 metal compounds Chemical class 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
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- 239000010970 precious metal Substances 0.000 description 1
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Classifications
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- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/396—
-
- B01J35/40—
Abstract
The invention discloses a photocatalyst of an Au@TiO2 hollow core-shell structure and a preparation method of the photocatalyst of the Au@TiO2 hollow core-shell structure and belongs to the technical field of semiconductor photocatalysts.The Au@TiO2 hollow core-shell structure takes Au nanoparticles as a core and TiO2 as a shell, and a hollow cavity is reserved between the core and the shell.The size of the Au core can be adjusted by changing the size of Au nanoparticle seeds, and shell thickness and the hollow cavity size can be adjusted by changing an adding proportion of the Au nanoparticles and a titanium source and concentration of the titanium source.The preparation method avoids that Au cores are nonuniform in size or multiple Au cores exist in one hollow cavity due to aggregation of the Au nanoparticles during titanium dioxide shell layer preparation.The photocatalyst of the Au@TiO2 hollow core-shell structure has the advantages that the size of the Au core is controllable, only one Au core exists in one hollow cavity, the core-shell structure is uniform, visible light (lambda max>420 nm) catalytic effect of the Au@TiO2 hollow core-shell structure is remarkably improved than titanium dioxide P25, and accordingly the photocatalyst of the Au@TiO2 hollow core-shell structure has a promising application prospect in the field of photocatalysis.
Description
Technical field
The invention belongs to semiconductor light-catalyst technical field, be specifically related to a kind of AuTiO2Hollow core-shell structured light Catalysts and its preparation method.
Background technology
Photocatalysis oxidation technique is considered as one of most technology having application prospect solving problem of environmental pollution.Up to now, it has been found that have the organic compound of more than 3000 kind of difficult degradation can be degraded rapidly by Photocatalytic Oxidation With Semiconductors.In the quasiconductor that photocatalysis technology is conventional, TiO2Safety non-toxic, cheap, photocatalysis performance is excellent under ultraviolet light for itself, and its physicochemical properties are stable, and reaction condition gentleness is easy to get, long service life and be widely used.But, TiO simple at present2Can only be excited by ultraviolet light, therefore the luminous energy of its absorption only about accounts for the 4% of sunlight, and the utilization ratio of solar energy is low.And semiconductor light-receiving excites produced Carrier recombination rate high, photo-quantum efficiency is low.Therefore, the conductor photocatalysis material that R and D are visible light-responded, by photoresponse range expansion to visible region, thus improving the utilization ratio of sunlight, and improve photo-quantum efficiency, advance catalysis material in the application of actual production and life, be key issue urgently to be resolved hurrily at present.
Recently, the semiconductor nano material of noble metal compound becomes the focus of research due to the ability of its raising photocatalysis efficiency.The heterojunction structure of noble metal/quasiconductor combines noble metal and the respective advantage of quasiconductor, and surface plasma body resonant vibration (SPR) effect that noble metal is strong in visible region can expand the nano material absorption to visible ray；And noble metal generally has more less fermi level than quasiconductor, promote the separation in light induced electron and hole, thus improving the photo-quantum efficiency of photocatalyst.In addition the structure regulating and controlling semi-conductor nano particles is also the important method improving its photocatalysis performance.In recent years, there is the hollow Nano microsphere of unique hollow structure of great interest because having density is low, specific surface area is high advantage.The hollow structure of quasiconductor hollow Nano microsphere uniqueness can increase light reflection in hollow structure and scattering, improves luminous energy capture rate；And its big specific surface area can increase the adsorbance to reaction substrate；Meanwhile, its internal space can hold a certain amount of reactant liquor, is conducive to the diffusion of reaction substrate and product, thus improving the catalytic efficiency of semiconductor light-catalyst from many aspects.Yin etc. pass through selective removal SiO2TiO2The kernel of core-shell nano, has synthesized TiO2Tiny balloon (crystal formation, degree of crystallinity are adjustable), compared with business-like titanium dioxide (P25), this structure has higher catalytic efficiency (Adv.Funct.Mater.2013,23,4246) in the experiment of photocatalytic degradation rhodamine B.
By analysis above, if it is expected that in combination with the advantage of precious metal nanoparticle hybrid and cavitation in a semi-conductor nano particles, can such as construct noble metal TiO2Hollow core-shell structure nano particle, will make Solar use efficiency improve further, promise to be very much a kind of New Policy strengthening semi-conductor nano particles visible light catalytic performance.Zaera etc. are by preparing AuSiO2TiO2Three-layer nuclear shell structure selectivity remove SiO2The method in intermediate layer is prepared for AuTiO2Hollow core-shell structure nano particle (Angew.Chem.Int.Ed.2011,50,10208).But the growth in this method needs strict control intermediate layer and selectivity remove process, step is comparatively laborious, and is easily generated the by-product causing environmental pollution.Chinese Academy Of Sciences Process Engineering Research Institute wangdan researcher and State Nanometer Science Center Tang Zhiyong researcher are prepared for AuTiO by accelerating Ostwald maturing process at ethanol-water system2Hollow core-shell structure nano particle (Energy.Environ.Sci.2012,5,6914).But the method is forming AuTiO2Hollow core-shell configuration process exists the gathering fusion process of the Au nanoparticle as seed, causes that in final cavity, Au nano-particles size, quantity differ, and be difficult to the size of regulation and control Au core.Therefore invention low cost and easy-operating preparation have the homogeneous AuTiO that efficient visible light absorbs2The method of hollow core-shell structure, significant as visible light catalytic.
Summary of the invention
It is an object of the invention to provide a kind of AuTiO2Hollow core-shell structured light catalyst and simple and easy to do preparation method thereof.AuTiO2Hollow core-shell structure is with Au nanoparticle for kernel, with TiO2For shell, and there is between kernel and shell cavity.Wherein the size of Au core can be regulated by the size of the Au nanoparticle seed that change adds, and the thickness of shell and the size of cavity can be adjusted by the Au nanoparticle of change addition and the ratio in titanium source and the concentration in titanium source.That reports (Energy.Environ.Sci.2012,5,6914) at present prepares AuTiO at ethanol-water system acceleration Ostwald maturing process2The method of hollow core-shell structured light catalyst, owing to directly result in the gathering of Au nanoparticle to Au nanoparticle aqueous solution adds ethanol, so that the Au core size heterogeneity finally given and occur in the situation having multiple Au core in a shell.Method provided by the invention avoids the size heterogeneity assembling the Au core that fusion causes of the Au nanoparticle prepared in titanium dioxide shell process or the appearance of multiple Au core.Hollow core-shell structure prepared by the application present invention, the size of Au core is controlled, ensures only one of which Au core in a cavity simultaneously, and nucleocapsid structure is homogeneous, is conducive to improving this AuTiO2The preparation of hollow core-shell structured light catalyst is repeatable and catalytic efficiency during as visible light catalyst and stability.
A kind of AuTiO of the present invention2The preparation method of hollow core-shell structured light catalyst, its step is as follows:
1) preparing Au nanometer particle colloid solution by the method for reduction of sodium citrate gold chloride, as primary reaction seed, the concentration range of Au nanoparticle is 1.5 × 10-11～5.0 × 10-10mol/L；
2) to 4～8mL step 1 when being stirred at room temperature) the Au nanometer particle colloid solution that obtains is sequentially added into titanium source aqueous solution 0.25～5mL, the deionized water 3.5～12mL that concentration is 0.5～5mg/mL, add alcohols solvent 5～14mL after 2～10 minutes；Mixture room temperature continues stirring 10～30 minutes, heats 2～10 hours subsequently, obtain AuTiO of the present invention at 100～180 DEG C2Hollow core-shell structured light catalyst.
The diameter of described primary reaction seed Au nanoparticle is 25～80nm.Titanium source is titanium tetrafluoride (TiF4), titanium tetrachloride, titanium sulfate, butyl titanate, isopropyl titanate or isopropyl titanate.Alcohols solvent is ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, sec-butyl alcohol or the tert-butyl alcohol.
Preparation AuTiO of the present invention2The equipment that the method for hollow core-shell structured light catalyst adopts is simple, mild condition, chemical reagent used are cheap and easy to get.The AuTiO of preparation2The diameter of hollow core-shell structure is 130～170nm, and shell thickness is the diameter of 15～20nm, core A u nanoparticle is 25～80nm, TiO2It is anatase crystal, and a TiO2Only one of which Au core (as shown in Figure 7) in shell cavity.
AuTiO prepared by the present invention2Hollow core-shell structured light catalyst presents the SPR of strong Au nanoparticle and absorbs in visible region, and Au nanoparticle can improve the separation efficiency in light induced electron and hole.In addition AuTiO2Hollow core-shell structure can effectively reduce the reflection of light, thus improving the absorption efficiency of light.Meanwhile, the specific surface area that hollow core-shell structure is big can increase the adsorbance to reaction substrate, and its internal space can also hold a certain amount of reactant liquor, is conducive to the diffusion of reaction substrate and product.Test result indicate that as semiconductor light-catalyst, AuTiO2Visible ray (the λ of hollow core-shell structured light catalystmax> 420nm) catalytic effect increases significantly than commercialization titanium dioxide P25, and its preparation method is simple, reproducible, amplification quantity can produce, have good application prospect in fields such as photocatalytic degradation environmental contaminants, solaode and solar hydrogen makings.
Accompanying drawing explanation
Fig. 1: Au nanometer particle colloid solution (curve 1) that embodiment 1 prepares and AuTiO2The uv-visible absorption spectra figure of hollow core-shell structured light catalyst colloid solution (curve 2)；
Fig. 2: the AuTiO that embodiment 1 prepares2Hollow core-shell structured light catalyst transmission electron microscope photo under different amplification, figure (b) is the partial enlarged drawing of figure (a)；
Fig. 3: the AuTiO that embodiment 1 prepares2The X-ray diffraction spectrogram of hollow core-shell structured light catalyst；
Fig. 4: the AuTiO that Application Example 1 prepares2The light degradation curve chart of hollow core-shell structured light catalyst and titanium dioxide P25 visible light photocatalytic degradation dye molecule rhodamine B；
Fig. 5: the AuTiO that embodiment 2 prepares2The transmission electron microscope photo of hollow core-shell structured light catalyst.
Fig. 6: the AuTiO that Application Example 4 prepares2The light degradation curve chart of hollow core-shell structured light catalyst and titanium dioxide P25 visible light photocatalytic degradation dye molecule rhodamine B；
Fig. 7: AuTiO of the present invention2Hollow core-shell structured light catalyst structure schematic diagram.
Detailed description of the invention
With specific embodiment, technical scheme done more detailed description below, but described example is not construed as limiting the invention.
Embodiment 1
Utilizing reduction of sodium citrate gold chloride method (NaturePhysicalScience1973,241,20-22.) to prepare concentration is 6.3 × 10-11The Au nanometer particle colloid solution (diameter of Au nanoparticle is 50nm) of mol/L.
It is sequentially added into, in 8mLAu nanometer particle colloid solution, the TiF that concentration is 5mg/mL when being stirred at room temperature4Aqueous solution 0.5mL, deionized water 8mL, add ethanol 14mL after 5 minutes.Mixture room temperature continues stirring 10 minutes, heats 6 hours subsequently, obtain peach AuTiO at 180 DEG C2Hollow core-shell structured light catalyst, product quality is 1.7mg.
Embodiment 1 performance test
Take the AuTiO that the 4mg present invention prepares2Hollow core-shell structured light catalyst adds in the aqueous solution (5ppm) of 4mL rhodamine B, is placed in dark place and within 30 minutes, makes nanoparticle dispersed and rhodamine B absorption is reached balance；Then 300W xenon source (λ is adopted under magnetic stirringmax> 420nm) irradiate (lamp and sample distance 30cm) and start timing.Separated in time samples, and takes supernatant, and measures its absorbance in rhodamine B maximum absorption wave strong point with ultraviolet-visible spectrophotometer, evaluate its Photocatalytic Degradation Property after centrifugation.Application AuTiO2Hollow core-shell structure and titanium dioxide P25 are 99.5% and 57.7% as the degradation rate after catalyst illumination rhodamine B 4 hours respectively, and the AuTiO of preparation is described2Hollow core-shell structured light catalyst has significantly superior different photocatalysis performance.
Accompanying drawing 1 is Au nanometer particle colloid solution (1) and AuTiO that obtain2The uv-visible absorption spectra figure of hollow core-shell structured light catalyst colloid solution (2).Au and AuTiO as shown in the figure2Obvious SPR absworption peak is presented respectively at 535nm and 552nm place.
Accompanying drawing 2 is the AuTiO obtained2Hollow core-shell structured light catalyst transmission electron microscope photo under different amplification.It is shown in very big scope and all presents TiO2For the uniform hollow core-shell structure that shell, Au are kernel, the diameter of nucleocapsid structure is 150nm, and shell thickness is the diameter of 15nm, core A u nanoparticle is 50nm.Figure (b) is the partial enlarged drawing of figure (a).
Accompanying drawing 3 is the AuTiO obtained2The X-ray diffraction spectrogram of hollow core-shell structured light catalyst.Anatase crystal TiO as shown in the figure2Diffraction maximum high-visible, illustrate synthesis TiO2It it is anatase crystal.
Accompanying drawing 4 is the AuTiO obtained2The light degradation curve of the Concentration-time of hollow core-shell structured light catalyst and titanium dioxide P25 visible light photocatalytic degradation dye molecule rhodamine B.According to degradation rate computing formula: η=(A0-At)/A0* 100%, (A0For the initial absorbance of rhodamine B solution before illumination；AtFor the moment absorbance of rhodamine B solution after light application time t) calculate the AuTiO that is applied2Hollow core-shell structured light catalyst and titanium dioxide P25 illumination rhodamine B degradation rate after 4 hours are 99.5% and 57.7% respectively, and the AuTiO of preparation is described2Hollow core-shell structured light catalyst has more excellent photocatalysis performance.
Embodiment 2
Utilizing reduction of sodium citrate gold chloride to prepare concentration is 6.3 × 10-11The Au nanometer particle colloid solution (diameter of Au nanoparticle is 50nm) of mol/L.It is sequentially added into, in 8mLAu nanometer particle colloid solution, the TiF that concentration is 0.5mg/mL when being stirred at room temperature4Aqueous solution 5mL, deionized water 3.5mL, add ethanol 14mL after 5 minutes.Mixture room temperature continues stirring 10 minutes, heats 6 hours subsequently, obtain peach AuTiO at 180 DEG C2Hollow core-shell structured light catalyst, product quality is 1.6mg.
Accompanying drawing 5 is the AuTiO obtained2The transmission electron microscope photo of hollow core-shell structured light catalyst.It is shown in very big scope and all presents TiO2For the uniform hollow core-shell structure that shell, Au are kernel, TiO2Shell is anatase crystal, and the diameter of nucleocapsid structure is 169nm, and shell thickness is the diameter of 23nm, core A u nanoparticle is 50nm.
Embodiment 3
Utilizing reduction of sodium citrate gold chloride to prepare concentration is 6.3 × 10-11The Au nanometer particle colloid solution (diameter of Au nanoparticle is 50nm) of mol/L.It is sequentially added into, in 4mLAu nanometer particle colloid solution, the TiF that concentration is 5mg/mL when being stirred at room temperature4Aqueous solution 0.25mL, deionized water 12mL, add ethanol 14mL after 5 minutes.Mixture room temperature continues stirring 10 minutes, heats 2 hours subsequently, obtain peach AuTiO at 180 DEG C2Hollow core-shell structured light catalyst, product quality is 1.0mg.
The photocatalyst of preparation presents TiO2For the hollow core-shell structure that shell, Au are kernel, TiO2Shell is anatase crystal, and the diameter of nucleocapsid structure is 153nm, and shell thickness is the diameter of 21nm, core A u nanoparticle is 50nm.
Embodiment 4
Utilizing reduction of sodium citrate gold chloride to prepare concentration is 6.3 × 10-11The Au nanometer particle colloid solution (diameter of Au nanoparticle is 50nm) of mol/L.It is sequentially added into, in 8mLAu nanometer particle colloid solution, the TiF that concentration is 5mg/mL when being stirred at room temperature4Aqueous solution 0.5mL, deionized water 8mL, add ethanol 14mL after 5 minutes.Mixture room temperature continues stirring 30 minutes, heats 6 hours subsequently, obtain peach AuTiO at 100 DEG C2Hollow core-shell structured light catalyst, product quality is 1.5mg.
The photocatalyst of preparation presents TiO2For the hollow core-shell structure that shell, Au are kernel, TiO2Shell is anatase crystal, and the diameter of nucleocapsid structure is 150nm, and shell thickness is the diameter of 20nm, core A u nanoparticle is 50nm.
Embodiment 4 performance test
Take the AuTiO that the 4mg present invention prepares2Hollow core-shell structured light catalyst adds in the aqueous solution (5ppm) of 4mL rhodamine B, is placed in dark place and within 30 minutes, makes nanoparticle dispersed and rhodamine B absorption is reached balance；Then 300W xenon source (λ is adopted under magnetic stirringmax> 420nm) irradiate (lamp and sample distance 30cm) and start timing.Separated in time samples, and takes supernatant, and measures its absorbance in rhodamine B maximum absorption wave strong point with ultraviolet-visible spectrophotometer, evaluate its Photocatalytic Degradation Property after centrifugation.Application AuTiO2Hollow core-shell structure and titanium dioxide P25 are 79.8% and 57.7% as the degradation rate after catalyst illumination rhodamine B 4 hours respectively, and the AuTiO of preparation is described2Hollow core-shell structured light catalyst has significantly superior different photocatalysis performance.
Accompanying drawing 6 is the AuTiO obtained2The light degradation curve of the Concentration-time of hollow core-shell structured light catalyst and titanium dioxide P25 visible light photocatalytic degradation dye molecule rhodamine B.According to degradation rate computing formula: η=(A0-At)/A0* 100%, (A0For the initial absorbance of rhodamine B solution before illumination；AtFor the moment absorbance of rhodamine B solution after light application time t) calculate the AuTiO that is applied2Hollow core-shell structured light catalyst and titanium dioxide P25 illumination rhodamine B degradation rate after 4 hours are 79.8% and 57.7% respectively, and the AuTiO of preparation is described2Hollow core-shell structured light catalyst has more excellent photocatalysis performance.
Embodiment 5
Utilizing reduction of sodium citrate gold chloride to prepare concentration is 6.3 × 10-11The Au nanometer particle colloid solution (diameter of Au nanoparticle is 50nm) of mol/L.It is sequentially added into, in 4mLAu nanometer particle colloid solution, the TiF that concentration is 5mg/mL when being stirred at room temperature4Aqueous solution 0.5mL, deionized water 12mL, add ethanol 14mL after 2 minutes.Mixture room temperature continues stirring 10 minutes, heats 10 hours subsequently, obtain peach AuTiO at 180 DEG C2Hollow core-shell structured light catalyst, product quality is 1.5mg.
The photocatalyst of preparation presents TiO2For the hollow core-shell structure that shell, Au are kernel, TiO2Shell is anatase crystal, and the diameter of nucleocapsid structure is 150nm, and shell thickness is the diameter of 15nm, core A u nanoparticle is 50nm.
Embodiment 6
Utilizing reduction of sodium citrate gold chloride to prepare concentration is 5.0 × 10-10The Au nanometer particle colloid solution (diameter of Au nanoparticle is 25nm) of mol/L.It is sequentially added into, in 4mLAu nanometer particle colloid solution, the TiF that concentration is 5mg/mL when being stirred at room temperature4Aqueous solution 0.5mL, deionized water 12mL, add ethanol 14mL after 10 minutes.Mixture room temperature continues stirring 10 minutes, heats 6 hours subsequently, obtain peach AuTiO at 180 DEG C2Hollow core-shell structured light catalyst, product quality is 1.8mg.
The photocatalyst of preparation presents TiO2For the hollow core-shell structure that shell, Au are kernel, TiO2Shell is anatase crystal, and the diameter of nucleocapsid structure is 130nm, and shell thickness is the diameter of 20nm, core A u nanoparticle is 25nm.
Embodiment 7
Utilizing reduction of sodium citrate gold chloride to prepare concentration is 1.5 × 10-11The Au nanometer particle colloid solution (diameter of Au nanoparticle is 80nm) of mol/L.It is sequentially added into, in 8mLAu nanometer particle colloid solution, the TiF that concentration is 5mg/mL when being stirred at room temperature4Aqueous solution 0.5mL, deionized water 8mL, add ethanol 5mL after 5 minutes.Mixture room temperature continues stirring 10 minutes, heats 6 hours subsequently, obtain peach AuTiO at 180 DEG C2Hollow core-shell structured light catalyst, product quality is 1.4mg.
The photocatalyst of preparation presents TiO2For the hollow core-shell structure that shell, Au are kernel, TiO2Shell is anatase crystal, and the diameter of nucleocapsid structure is 170nm, and shell thickness is the diameter of 20nm, core A u nanoparticle is 80nm.
Claims (7)
1. an AuTiO2The preparation method of hollow core-shell structured light catalyst, its step is as follows:
1) preparing Au nanometer particle colloid solution, as primary reaction seed, the concentration range of Au nanoparticle is 1.5 × 10-11～5.0 × 10-10mol/L；
2) to 4～8mL step 1 when being stirred at room temperature) the Au nanometer particle colloid solution that obtains is sequentially added into titanium source aqueous solution 0.25～5mL, the deionized water 3.5～12mL that concentration is 0.5～5mg/mL, add alcohols solvent 5～14mL after 2～10 minutes；Mixture room temperature continues stirring 10～30 minutes, heats 2～10 hours subsequently, obtain AuTiO at 100～180 DEG C2Hollow core-shell structured light catalyst.
2. a kind of AuTiO as claimed in claim 12The preparation method of hollow core-shell structured light catalyst, it is characterised in that: the diameter of described primary reaction seed Au nanoparticle is 25～80nm.
3. a kind of AuTiO as claimed in claim 12The preparation method of hollow core-shell structured light catalyst, it is characterised in that: it is that the method adopting reduction of sodium citrate gold chloride prepares Au nanometer particle colloid solution.
4. a kind of AuTiO as claimed in claim 12The preparation method of hollow core-shell structured light catalyst, it is characterised in that: the AuTiO prepared2The diameter of hollow core-shell structure is 130～170nm, and shell thickness is the diameter of 15～23nm, core A u nanoparticle is 25～80nm, TiO2It is anatase crystal, and a TiO2Only one of which Au core in shell cavity.
5. a kind of AuTiO as claimed in claim 12The preparation method of hollow core-shell structured light catalyst, it is characterised in that: titanium source is titanium tetrafluoride, titanium tetrachloride, titanium sulfate, butyl titanate, isopropyl titanate or isopropyl titanate.
6. a kind of AuTiO as claimed in claim 12The preparation method of hollow core-shell structured light catalyst, it is characterised in that: alcohols solvent is ethanol, normal propyl alcohol, isopropanol, n-butyl alcohol, isobutanol, sec-butyl alcohol or the tert-butyl alcohol.
7. an AuTiO2Hollow core-shell structured light catalyst, it is characterised in that: the method described in claim 1～6 any one prepares.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108476778A (en) * | 2018-02-10 | 2018-09-04 | 深圳万发创新进出口贸易有限公司 | A kind of energy-efficient vertical planting landscape device |
| CN108722394A (en) * | 2018-05-25 | 2018-11-02 | 东北大学 | WO with yolk-eggshell structure3-TiO2Nanocomposite and preparation method thereof |
| CN110918095A (en) * | 2019-11-12 | 2020-03-27 | 华南师范大学 | Carbon/titanium dioxide/noble metal composite material, photocatalyst and preparation method thereof |
| CN111482169A (en) * | 2020-04-14 | 2020-08-04 | 中北大学 | Noble metal-loaded nano photocatalyst and preparation method and application thereof |
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| Title |
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| JING LI ET AL.,: "Size tuning, functionalization，and reactivation of Au in TiO2 Nanoreactors", 《ANGEW.CHEM.》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108476778A (en) * | 2018-02-10 | 2018-09-04 | 深圳万发创新进出口贸易有限公司 | A kind of energy-efficient vertical planting landscape device |
| CN108722394A (en) * | 2018-05-25 | 2018-11-02 | 东北大学 | WO with yolk-eggshell structure3-TiO2Nanocomposite and preparation method thereof |
| CN110918095A (en) * | 2019-11-12 | 2020-03-27 | 华南师范大学 | Carbon/titanium dioxide/noble metal composite material, photocatalyst and preparation method thereof |
| CN111482169A (en) * | 2020-04-14 | 2020-08-04 | 中北大学 | Noble metal-loaded nano photocatalyst and preparation method and application thereof |
| CN111482169B (en) * | 2020-04-14 | 2023-04-18 | 中北大学 | Noble metal-loaded nano photocatalyst and preparation method and application thereof |
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