CN107126958A - A kind of Au nanometer rods/ZnO plate-like heterojunction photocatalysts and preparation method thereof - Google Patents
A kind of Au nanometer rods/ZnO plate-like heterojunction photocatalysts and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000002245 particle Substances 0.000 claims abstract description 13
- 241000549556 Nanos Species 0.000 claims abstract description 9
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims abstract description 7
- 238000005119 centrifugation Methods 0.000 claims abstract description 6
- 239000011701 zinc Substances 0.000 claims abstract description 6
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims abstract 2
- 229910021641 deionized water Inorganic materials 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 26
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 16
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- 238000012986 modification Methods 0.000 claims description 3
- 230000004048 modification Effects 0.000 claims description 3
- 229910052984 zinc sulfide Inorganic materials 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 2
- WHMDKBIGKVEYHS-IYEMJOQQSA-L Zinc gluconate Chemical compound [Zn+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O WHMDKBIGKVEYHS-IYEMJOQQSA-L 0.000 claims description 2
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- WGIWBXUNRXCYRA-UHFFFAOYSA-H trizinc;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Zn+2].[Zn+2].[Zn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O WGIWBXUNRXCYRA-UHFFFAOYSA-H 0.000 claims description 2
- 150000003751 zinc Chemical class 0.000 claims description 2
- 239000004246 zinc acetate Substances 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- 229960001939 zinc chloride Drugs 0.000 claims description 2
- 239000011746 zinc citrate Substances 0.000 claims description 2
- 235000006076 zinc citrate Nutrition 0.000 claims description 2
- 229940068475 zinc citrate Drugs 0.000 claims description 2
- 239000011670 zinc gluconate Substances 0.000 claims description 2
- 235000011478 zinc gluconate Nutrition 0.000 claims description 2
- 229960000306 zinc gluconate Drugs 0.000 claims description 2
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 2
- 229960001763 zinc sulfate Drugs 0.000 claims description 2
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 2
- MFXMOUUKFMDYLM-UHFFFAOYSA-L zinc;dihydrogen phosphate Chemical compound [Zn+2].OP(O)([O-])=O.OP(O)([O-])=O MFXMOUUKFMDYLM-UHFFFAOYSA-L 0.000 claims description 2
- CANRESZKMUPMAE-UHFFFAOYSA-L Zinc lactate Chemical compound [Zn+2].CC(O)C([O-])=O.CC(O)C([O-])=O CANRESZKMUPMAE-UHFFFAOYSA-L 0.000 claims 1
- 150000001412 amines Chemical class 0.000 claims 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims 1
- 239000000920 calcium hydroxide Substances 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- 239000011576 zinc lactate Substances 0.000 claims 1
- 235000000193 zinc lactate Nutrition 0.000 claims 1
- 229940050168 zinc lactate Drugs 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 11
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 239000004065 semiconductor Substances 0.000 abstract description 9
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 3
- 239000001257 hydrogen Substances 0.000 abstract description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 3
- 238000012360 testing method Methods 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 9
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 7
- 229910000510 noble metal Inorganic materials 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 229910052737 gold Inorganic materials 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 230000009102 absorption Effects 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 230000003321 amplification Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001000 micrograph 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
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 239000002073 nanorod Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 241000165940 Houjia Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000035040 seed growth Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000006228 supernatant Substances 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
- 235000016804 zinc Nutrition 0.000 description 1
Classifications
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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
- 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
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/66—Silver or 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
-
- 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
-
- 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
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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
- B01J35/391—Physical properties of the active metal ingredient
- B01J35/393—Metal or metal oxide crystallite size
-
- 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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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
A kind of Au nanometer rods/ZnO plate-like heterojunction photocatalysts and preparation method thereof, belong to semiconductor light-catalyst preparing technical field.It is to prepare Au nanometer rods colloidal solution using surfactant, then by 25~50mL, the solution is concentrated to the 10~20% of original volume by the method for centrifugation, 2.5~25mL of zinc solution that 2.5~25mL of aqueous slkali, concentration that 120~240mL of deionized water, concentration are 10~50mM are 10~50mM is separately added into enriched product again, then heated 2~3 hours at 80~95 DEG C, so as to obtain Au nanometer rods/ZnO plate-like heterojunction photocatalysts.The SPR that photochemical catalyst prepared by the present invention presents strong Au nano-particles in visible region absorbs, and Au rod-like nanos particle can improve the separative efficiency in light induced electron and hole.Test result indicates that as semiconductor light-catalyst, its photocatalysis effect is excellent, there is good application prospect in fields such as photocatalytic degradation environmental contaminants, solar cell and solar hydrogen makings.
Description
Technical field
The invention belongs to semiconductor light-catalyst preparing technical field, and in particular to a kind of Au nanometer rods/ZnO plate-likes are heterogeneous
Tie photochemical catalyst and preparation method thereof.
Background technology
Photocatalysis oxidation technique is considered as to solve problem of environmental pollution most to have one of technology of application prospect.It is so far
Only, it has been found that the organic compound for having more than 3000 kinds of difficult degradation can rapidly be degraded by photochemical catalytic oxidation.In photocatalysis
In the conventional semiconductor of technology, ZnO's prepares relative inexpensiveness, and with relatively low growth and crystallization temperature, easily prepared
Various pattern and structure, and cause people and more and more pay close attention to.At present, simple ZnO catalyst is gone back in actual applications
In the presence of two urgent problems to be solved：First, the utilization ratio of solar energy is low, and absorptions of the ZnO to light is main the one of ultra-violet (UV) band
Segment, can only utilize the luminous energy for accounting for solar spectrum scope 4%；Second, semiconductor carriers recombination rate is high, and photo-quantum efficiency is low.
Therefore, the visible light-responded catalysis material of R and D, and photo-quantum efficiency is improved, imitated so as to improve utilizing for sunshine
Rate, promotes the application of catalysis material, is key issue urgently to be resolved hurrily at present.
Recently, the zno-based heterojunction structure nano material that emerging noble metal is combined has obtained scientist and widely paid close attention to.
In noble metal/semiconductor heterostructure, noble metal can be expanded in the strong surface plasma body resonant vibration of visible region (SPR) effect
Visible absorption；And noble metal typically has the fermi level lower than semiconductor, light induced electron and point in hole can be promoted
From, so that the photo-quantum efficiency of photochemical catalyst is improved, thus as the focus of research.The SPR strong depend-ences grain of golden nanometer particle
The shape of son, spheroidal particle shows as single SPR spectral peaks, and rod-shaped particle then has horizontal and vertical SPR spectral peaks, and longitudinal direction
SPR spectral peaks peak position and intensity depend on the horizontal ratio in footpath of rod-shaped particle, in visible ray to near-infrared region continuously adjustabe.Therefore, it is expensive
The spectral response range of metal nano-rod/semiconductor hybrid nano-particle is wider, will show more excellent photocatalysis performance.
Current researcher's design is prepared for noble metal/ZnO nano dissimilar materials of a variety of different structures, to improve its light
Catalytic efficiency, but majority is all spherical noble metal/ZnO nano hetero-junctions.Chen etc. reports the Au nanometer rods nucleocapsids of ZnO claddings
Hetero-junctions catalyst (Journal of the American Chemical Society, 2013,135,9099-9110).With
This structure is compared, and Au nanometer rods modify the heterojunction structure hybrid material in ZnO outer surfaces, preferably can be inhaled using Au nanometer rods
Visible ray is received, so that more excellent photocatalysis performance will likely be showed.There is presently no solution noble metal nano rod outside
The report of ZnO heterojunction structure is modified in side.Therefore the inexpensive and easy-operating Au absorbed with efficient visible light for preparing is invented to receive
The method of rice rod/ZnO heterojunction structure, it is significant as visible light catalytic.
The content of the invention
It is an object of the invention to provide a kind of easy-to-use Au nanometer rods/ZnO plate-likes heterojunction photocatalyst and its system
ZnO and Au ratio can be adjusted by changing the ratio of the Au nanometer rods added and zinc source in Preparation Method, and hetero-junctions
Section.
The preparation method of Au nanometer rods of the present invention/ZnO plate-like heterojunction photocatalysts, its step is as follows：
(1) Au nanometer rods colloidal solution (Chem.Mater.2003,15,1957) is prepared using surfactant to make
For primary reaction seed, the concentration of Au atoms is 0.492mM；
(2) step (1) is obtained 25~50mL Au nanometer rods colloidal solution (Au nanometer rods quality be 2.43~
4.87mg) be concentrated to the 10~20% of original volume by the method for centrifugation, be then separately added into enriched product from
The zinc solution 2.5 that 2.5~25mL of aqueous slkali that sub- 120~240mL of water, concentration are 10~50mM, concentration are 10~50mM~
25mL, is then heated 2~3 hours at 80~95 DEG C, so as to obtain Au nanometer rods/ZnO plate-like heterojunction photocatalysts.
The diameter of the primary reaction seed Au nanometer rods is 8~18nm, and length is 40~47nm.The rotating speed of centrifugation
Scope is 2000~14000rpm, and the time is 3~20 minutes.Zinc salt is zinc acetate, zinc sulfate, zinc nitrate, zinc dihydrogen phosphate, breast
One kind in sour zinc, zinc gluconate, zinc citrate or zinc chloride.Aqueous slkali is ammoniacal liquor, sodium carbonate, sodium acid carbonate, hydroxide
In calcium, sodium hydroxide, potassium hydroxide, hexamethylenetetramine, triethylamine, the aqueous solution of triethylene diamine or tetramethylethylenediamine
It is a kind of.
Equipment that the method for the present invention for preparing Au nanometer rods/ZnO plate-like heterojunction photocatalysts is used is simple, condition
Gently, chemical reagent used is cheap and easy to get.The ZnO disks of the Au nanometer rods of preparation/ZnO plate-like heterojunction photocatalysts are averagely straight
Footpath be 3~4 μm, average thickness be 1.5~2.7 μm, the wherein modification of Au rod-like nanos uniform particle on the surface of ZnO disks,
The diameter of Au nanometer rods is 8~18nm, and length is 40~47nm, and ZnO is wurtzite.Au nanometers prepared by the present invention
The SPR that rod/ZnO plate-likes heterojunction photocatalyst presents strong Au nano-particles in visible region absorbs, and Au rod-like nanos
Particle can improve the separative efficiency in light induced electron and hole.Test result indicates that being used as semiconductor light-catalyst, its photocatalysis
Excellent effect, there is good application prospect in fields such as photocatalytic degradation environmental contaminants, solar cell and solar hydrogen makings.
The present invention obtains Au nanometer rods/ZnO plate-likes by seed growth of Au rod-like nanos particle in water solution system first
Heterojunction photocatalyst.The Au nanometer rods of preparation/ZnO plate-like heterojunction photocatalyst materials can effectively absorb visible ray,
Present the visible light catalytic performance of stability and high efficiency, preparation method is simple, favorable repeatability, can amplification quantity production, in photocatalysis
There is good application prospect in the fields such as degraded environmental contaminants, solar cell and solar hydrogen making.
Brief description of the drawings
Fig. 1：The Au nanometer rods colloidal solution (1) and Au nanometer rods that embodiment 1 is prepared/ZnO plate-like hetero-junctions light are urged
The UV-visible absorption spectrum of agent colloidal solution (2)；
Fig. 2：Au nanometer rods/ZnO plate-likes heterojunction photocatalyst that embodiment 1 is prepared is under different amplification
Electron scanning micrograph, figure (b) is the partial enlarged drawing of figure (a)；
Fig. 3：The X-ray diffraction spectrogram of the Au nanometer rods that embodiment 1 is prepared/ZnO plate-like heterojunction photocatalysts；
Fig. 4：The Au nanometer rods that Application Example 1 is prepared/ZnO plate-like heterojunction photocatalyst catalytic degradations dyestuff point
The autosensibilization light degradation curve of sub- rhodamine B and rhodamine B；
Fig. 5：The SEM of the Au nanometer rods that embodiment 2 is prepared/ZnO plate-like heterojunction photocatalysts is shone
Piece, figure (b) is the partial enlarged drawing of figure (a)；
Embodiment
More detailed description is done to technical scheme with specific embodiment below, but the example is not constituted to this
The limitation of invention.
Embodiment 1
Au nanometer rods colloidal solution (AuNR is prepared by the use of CTAB (cetyl trimethylammonium bromide) as surfactant
A diameter of 8nm, length is 44nm, and the concentration of Au atoms is 0.492mM).By 50mL Au nanometer rods colloidal solution (wherein Au
Nanometer rods quality is 4.87mg) centrifuged 10 minutes under conditions of rotating speed is 10000rpm, volume is concentrated to for 10mL, Ran Houjia
Enter 240mL deionized waters to stir at room temperature 5 minutes, next sequentially add the zinc nitrate aqueous solution 5mL that concentration is 50mM, concentration
For 50mM hexamethylenetetramine aqueous solution 5mL, subsequent 95 DEG C are heated 2.5 hours, obtain Au nanometer rods/ZnO plate-like hetero-junctions
Photochemical catalyst, product quality is 15mg.
The performance test of embodiment 1
25mg Au nanometer rods produced by the present invention/ZnO plate-likes heterojunction photocatalyst is taken to add the water-soluble of 25mL rhodamine Bs
In liquid (5ppm), 30min is stirred in the dark to be made nano-particle dispersed and reaches balance to rhodamine B absorption；Then in magnetic
Power stirring is lower using 300W xenon sources (λ>200nm) irradiate (lamp is with sample apart from 30cm) and start timing.The timing of interval one
Between sample, supernatant is taken after centrifugation, and it is determined in rhodamine B maximum absorption wavelength with ultraviolet-uisible spectrophotometer
(λmax=554nm) place absorbance, evaluate its Photocatalytic Degradation Property.Using Au nanometer rods/ZnO plate-like heterojunction photocatalysis
Degradation rate after agent and rhodamine B autosensibilization 4h is 88% and 58% respectively, illustrates that the Au nanometer rods/ZnO plate-likes prepared are heterogeneous
Knot photochemical catalyst has excellent photocatalysis performance.
Accompanying drawing 1 is obtained Au nanometer rods colloidal solution (1) and Au nanometer rods/ZnO plate-like heterojunction photocatalyst colloids
The UV-visible absorption spectrum of solution (2).Au nanometer rods and Au nanometer rods/ZnO plate-like hetero-junctions exist respectively as shown in the figure
Obvious lateral resonance and longitudinal resonance SPR absworption peaks are presented at 517nm, 702nm and 517nm, 660nm.
Accompanying drawing 2 is obtained Au nanometer rods/scanning electron of the ZnO plate-likes heterojunction photocatalyst under different amplification
Microphotograph.It is shown in very big scope and all presents uniform disk-like structure, disk average diameter is 4 μm, average
Thickness is 2.7 μm, and wherein Au nanometer rods are uniformly modified in ZnO disc surfaces, a diameter of 8nm of Au nanometer rods, and length is
44nm.Figure (b) is the partial enlarged drawing of figure (a).
Accompanying drawing 3 is the X-ray diffraction spectrogram of obtained Au nanometer rods/ZnO plate-like heterojunction photocatalysts.It is fine as shown in the figure
The ZnO of zinc ore crystal formation diffraction maximum is high-visible, illustrates that the ZnO prepared is wurtzite phase.
Accompanying drawing 4 is obtained Au nanometer rods/ZnO plate-like heterojunction photocatalyst catalytic degradation dye molecule rhodamine Bs
The light degradation curve of Concentration-time.According to degradation rate calculation formula：η=(A0-At)/A0* 100%, (A0For rhodamine before illumination
The initial absorbance of B solution；AtFor absorbance at the time of rhodamine B solution after light application time t) calculate and be applied Au nanometers
Degradation rate after rod/ZnO plate-likes heterojunction photocatalyst and rhodamine B autosensibilization 4h is 88% and 58% respectively, illustrates to prepare
Au nanometer rods/ZnO plate-like heterojunction photocatalysts there is excellent photocatalysis performance.
Embodiment 2
Preparing Au nanometer rods colloidal solution by the use of CTAB as surfactant, (AuNR a diameter of 18nm, length is
The concentration of 40nm, Au atom is 0.492mM).By 50mL Au nanometer rods colloidal solution rotating speed be 7000rpm under conditions of from
The heart 8 minutes, is concentrated to volume for 10mL, then sequentially adds 240mL deionized waters, and concentration is 50mM zinc nitrate aqueous solution
5mL, concentration is 50mM hexamethylenetetramine aqueous solution 5mL, and subsequent 95 DEG C are heated 2.5 hours, obtain Au nanometer rods/ZnO disks
Shape heterojunction photocatalyst, product quality is 15mg.
Accompanying drawing 5 is the electron scanning micrograph of obtained Au nanometer rods/ZnO plate-like heterojunction photocatalysts.As schemed
Shown all to present uniform disk-like structure in very big scope, disk average diameter is 4 μm, and average thickness is 2 μm, wherein Au
Nanometer rods are uniformly modified in ZnO disc surfaces, a diameter of 18nm of Au nanometer rods, and length is 40nm.
Embodiment 3
Preparing Au nanometer rods colloidal solution by the use of CTAB as surfactant, (AuNR a diameter of 18nm, length is
The concentration of 47nm, Au atom is 0.492mM).By 25mL Au nanometer rods colloidal solution rotating speed be 6000rpm under conditions of from
The heart 6 minutes, is concentrated to volume for 5mL, then sequentially adds 120mL deionized waters, and concentration is 50mM zinc nitrate aqueous solution
2.5mL, concentration is 50mM hexamethylenetetramine aqueous solution 2.5mL, and subsequent 95 DEG C are heated 3 hours, obtain Au nanometer rods/ZnO
Plate-like heterojunction photocatalyst, product quality is 7mg.
The disk average diameter of plate-like hetero-junctions is 4 μm, and average thickness is 2 μm, wherein Au rod-like nanos uniform particle
Modify on the surface of ZnO nano disk, a diameter of 18nm of Au nanometer rods, length is 47nm.
Embodiment 4
Preparing Au nanometer rods colloidal solution by the use of CTAB as surfactant, (AuNR a diameter of 18nm, length is
The concentration of 40nm, Au atom is 0.492mM).By 55mL Au nanometer rods colloidal solution rotating speed be 7000rpm under conditions of from
The heart 8 minutes, is concentrated to volume for 10mL, then sequentially adds 240mL deionized waters, and concentration is 50mM zinc nitrate aqueous solution
5mL, concentration is 50mM hexamethylenetetramine aqueous solution 5mL, and subsequent 95 DEG C are heated 2 hours, obtain Au nanometer rods/ZnO plate-likes
Heterojunction photocatalyst, product quality is 15mg.
The disk average diameter of plate-like hetero-junctions is 4 μm, and average thickness is 2 μm, wherein Au rod-like nanos uniform particle
Modify on the surface of ZnO nano disk, a diameter of 18nm of Au nanometer rods, length is 40nm.
Embodiment 5
Preparing Au nanometer rods colloidal solution by the use of CTAB as surfactant, (AuNR a diameter of 18nm, length is
The concentration of 40nm, Au atom is 0.492mM).By 55mL Au nanometer rods colloidal solution rotating speed be 7000rpm under conditions of from
The heart 8 minutes, is concentrated to volume for 10mL, then sequentially adds 200mL deionized waters, and concentration is 10mM zinc nitrate aqueous solution
25mL, concentration is 10mM hexamethylenetetramine aqueous solution 25mL, and subsequent 80 DEG C are heated 2.5 hours, obtain Au nanometer rods/ZnO
Plate-like heterojunction photocatalyst, product quality is 15mg.
The disk average diameter of plate-like hetero-junctions is 4 μm, and average thickness is 2 μm, wherein Au rod-like nanos uniform particle
Modify on the surface of ZnO nano disk, a diameter of 18nm of Au nanometer rods, length is 40nm.
Embodiment 6
Preparing Au nanometer rods colloidal solution by the use of CTAB as surfactant, (AuNR a diameter of 18nm, length is
The concentration of 40nm, Au atom is 0.492mM).By 50mL Au nanometer rods colloidal solution rotating speed be 7000rpm under conditions of from
The heart 8 minutes, is concentrated to volume for 10mL, then sequentially adds 240mL deionized waters, and concentration is 20mM zinc nitrate aqueous solution
5mL, concentration is 20mM hexamethylenetetramine aqueous solution 5mL, and subsequent 95 DEG C are heated 2.5 hours, obtain Au nanometer rods/ZnO disks
Shape heterojunction photocatalyst, product quality is 6mg.
The disk average diameter of plate-like hetero-junctions is 3 μm, and average thickness is 1.5 μm, wherein Au rod-like nanos uniform particle
Modification on the surface of ZnO nano disk, a diameter of 18nm of Au nanometer rods, length is 40nm.
Claims (7)
1. a kind of preparation method of Au nanometer rods/ZnO plate-like heterojunction photocatalysts, its step is as follows：
(1) Au nanometer rods colloidal solution is prepared as primary reaction seed by the use of surfactant, the concentration of Au atoms is
0.492mM；
(2) 25~50mL Au nanometer rods colloidal solution for obtaining step (1) is concentrated to original volume by the method for centrifugation
10~20%, be then separately added into enriched product 120~240mL of deionized water, concentration be 10~50mM aqueous slkali
2.5~25mL, concentration are 10~50mM 2.5~25mL of zinc solution, are then heated 2~3 hours at 80~95 DEG C, so that
To Au nanometer rods/ZnO plate-like heterojunction photocatalysts.
2. a kind of preparation method of Au nanometer rods/ZnO plate-like heterojunction photocatalysts as claimed in claim 1, its feature exists
In：The diameter of primary reaction seed Au nanometer rods is 8~18nm, and length is 40~47nm.
3. a kind of preparation method of Au nanometer rods/ZnO plate-like heterojunction photocatalysts as claimed in claim 1, its feature exists
In：The range of speeds of centrifugation is 2000~14000rpm, and the time is 3~20 minutes.
4. a kind of preparation method of Au nanometer rods/ZnO plate-like heterojunction photocatalysts as claimed in claim 1, its feature exists
In：Zinc salt is in zinc acetate, zinc sulfate, zinc nitrate, zinc dihydrogen phosphate, zinc lactate, zinc gluconate, zinc citrate or zinc chloride
One kind.
5. a kind of preparation method of Au nanometer rods/ZnO plate-like heterojunction photocatalysts as claimed in claim 1, its feature exists
In：Aqueous slkali is ammoniacal liquor, sodium carbonate, sodium acid carbonate, calcium hydroxide, sodium hydroxide, potassium hydroxide, hexamethylenetetramine, three second
One kind in the aqueous solution of amine, triethylene diamine or tetramethylethylenediamine.
6. a kind of Au nanometer rods/ZnO plate-like heterojunction photocatalysts, it is characterised in that：It is by Claims 1 to 5 any one
Described method is prepared.
7. a kind of Au nanometer rods/ZnO plate-like heterojunction photocatalysts as claimed in claim 1, it is characterised in that：ZnO disks
Average diameter is 3~4 μm, and average thickness is 1.5~2.7 μm, and wherein the modification of Au rod-like nanos uniform particle is in ZnO disks
Surface, the diameter of Au nanometer rods is 8~18nm, and length is 40~47nm, and ZnO is wurtzite.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108452850A (en) * | 2018-03-28 | 2018-08-28 | 江苏师范大学 | A kind of in-situ synthetic method of ZnO/Au heterojunction photocatalysts and the preparation method of ZIF-7 |
| CN108722401A (en) * | 2018-05-31 | 2018-11-02 | 吉林大学 | A kind of bionic plant foliaceous Au/ZnO heterojunction photocatalysts and preparation method thereof |
| CN110841656A (en) * | 2019-11-27 | 2020-02-28 | 广州大学 | Photoelectric catalyst and preparation method and application thereof |
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| CN103480373A (en) * | 2013-09-05 | 2014-01-01 | 同济大学 | Preparation method for dandelion-shaped core-shell structure Au@ZnO heterojunction catalyst |
| CN105195144A (en) * | 2015-10-15 | 2015-12-30 | 吉林大学 | Method for synthetizing Au/ZnO bar-shaped heterojunction photocatalyst |
| CN106179337A (en) * | 2016-07-01 | 2016-12-07 | 吉林大学 | A kind of TiO2/ Au nanometer rods Hemicentrotus seu Strongylocentrotus shape heterojunction structure photocatalyst and preparation method thereof |
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|---|---|---|---|---|
| CN103480373A (en) * | 2013-09-05 | 2014-01-01 | 同济大学 | Preparation method for dandelion-shaped core-shell structure Au@ZnO heterojunction catalyst |
| CN105195144A (en) * | 2015-10-15 | 2015-12-30 | 吉林大学 | Method for synthetizing Au/ZnO bar-shaped heterojunction photocatalyst |
| CN106179337A (en) * | 2016-07-01 | 2016-12-07 | 吉林大学 | A kind of TiO2/ Au nanometer rods Hemicentrotus seu Strongylocentrotus shape heterojunction structure photocatalyst and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108452850A (en) * | 2018-03-28 | 2018-08-28 | 江苏师范大学 | A kind of in-situ synthetic method of ZnO/Au heterojunction photocatalysts and the preparation method of ZIF-7 |
| CN108722401A (en) * | 2018-05-31 | 2018-11-02 | 吉林大学 | A kind of bionic plant foliaceous Au/ZnO heterojunction photocatalysts and preparation method thereof |
| CN110841656A (en) * | 2019-11-27 | 2020-02-28 | 广州大学 | Photoelectric catalyst and preparation method and application thereof |
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