CN106391055A - ZnO/CdS/CuS nanometer array composite material preparation method - Google Patents
ZnO/CdS/CuS nanometer array composite material preparation method Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 239000011521 glass Substances 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910001868 water Inorganic materials 0.000 claims abstract description 21
- 238000000034 method Methods 0.000 claims abstract description 18
- 238000005342 ion exchange Methods 0.000 claims abstract description 8
- 239000000758 substrate Substances 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 15
- 239000002073 nanorod Substances 0.000 claims description 13
- 239000012528 membrane Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 8
- 239000010408 film Substances 0.000 claims description 7
- 239000002105 nanoparticle Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 6
- 239000002052 molecular layer Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 239000011701 zinc Substances 0.000 claims description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 5
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 5
- 238000000137 annealing Methods 0.000 claims description 5
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 5
- 239000010949 copper Substances 0.000 claims description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- 239000010409 thin film Substances 0.000 claims description 5
- 239000004246 zinc acetate Substances 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 238000013021 overheating Methods 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 claims 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 abstract description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 2
- 238000003980 solgel method Methods 0.000 abstract 1
- 238000007669 thermal treatment Methods 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 10
- 239000004065 semiconductor Substances 0.000 description 9
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 4
- 239000004312 hexamethylene tetramine Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 238000013459 approach Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000006303 photolysis reaction Methods 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 2
- 230000008033 biological extinction Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052798 chalcogen Inorganic materials 0.000 description 1
- 150000001787 chalcogens Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a ZnO/CdS/CuS nanometer array composite material preparation method which comprises the steps: firstly, ZnO seed layer solution is prepared through a sol-gel method; a ZnO seed layer is coated on an ITO glass substrate through a dipping-pulling method, and after thermal treatment, conductive glass where the ZnO seed layer grows is arranged in ZnO growth solution to be processed through hot water bath to obtain a ZnO nanometer rod; a sample where a ZnO nanometer array grows is arranged in thioacetamide solution, and a ZnO/ZnS nanometer array is obtained after water bath; CdS and CuS nanometer particles are deposited on a ZnO nanometer layer through an ion exchange method to obtain the ZnO/CdS/CuS nanometer array composite material.
Description
Technical field
The invention belongs to technical field of material, specially a kind of ZnO/CdS/CuS nanometer battle array for photoelectrocatalysiss
The preparation method of row composite.
Background technology
At present, environmental pollution and the just serious productive life affecting the mankind of energy crisis, and solve environmental pollution and
The act of the key of energy crisis is the breakthrough of New Green Energy source material.Solar energy is with its environmental protection, inexhaustible
The features such as become the mankind solve energy problem, realize the good approach of sustainable development.But though the utilization of solar energy is considerable, its material
Material problem is but bottleneck.How to study, develop and efficient utilization solar energy becomes as study hotspot both domestic and external, undoubtedly Hydrogen Energy is
Solve the excellent approach of this misgivings.Hydrogen Energy is as the secondary energy sources of green high-efficient, rich reserves, and originates as cleaning
Water, pollution-free after burning, it is the optimum carrier using solar energy.
All exploitation solar energys are converted in the approach of Hydrogen Energy, produce hydrogen using semiconductor light-catalyst, can be direct
Convert the solar into the chemical energy with hydrogen as carrier, therefore solar photolysis water hydrogen process is ideal at present and relatively
One of promising Hydrogen Energy development tool.Photocatalytic hydrogen production by water decomposition is broadly divided into two big class, i.e. PhotoelectrochemicalSystem System for Hydrogen Production and light
Catalyzing manufacturing of hydrogen.If the selection of photocatalyst plays weight lifting for photocatalytic water process and lightly acts on, its suitable band structure and light
Raw electronics is most important for promoting photolysis water hydrogen with efficiently separating of hole.Therefore, find suitable method to promote
Light induced electron separates, increases the utilization rate of photo-generated carrier with hole, and develops novel photocatalysis material and just become raising
In place of the key of solar energy decomposition water hydrogen generation efficiency.At present for the photocatalyst of broad stopband, one kind effectively widens it can
See that the means of photoresponse scope are introduced into transition metal ionss thus forming new electron donor or receptor.
ZnO, as a kind of new important direct semiconductor material with wide forbidden band of II-VI group, has excellent optics and electricity
Learn characteristic.The band gap of ZnO and exciton bind energy are larger, and ZnO energy gap is 3.37eV at room temperature, its exciton bind energy
Up to 60meV.ZnO has the feature of N-type semiconductor in the case of there is no any impurity in itself.In solar energy photodissociation Aquatic product hydrogen half
Conductor investigation of materials field, ZnO nano material is considered as the TiO that continues2Optimal semi-conducting material afterwards, reason is as follows：First,
ZnO belongs to semiconductor material with wide forbidden band (Eg：3.37eV)；Secondly, electronics has bigger mobility in ZnO, can reduce
The probability that photo-generate electron-hole is combined；Additionally, ZnO's is with low cost.In addition, One-Dimensional ZnO nano material (nano wire, is received
Rice rod, nanotube etc.) using its uniform particle sizes, draw ratio big the advantages of as current study hotspot.
Its wider energy gap due to ZnO, can only can not be by excited by visible light, so needing logical to ultraviolet light response
Cross inorganic narrow gap semiconductor sensitization wide bandgap semiconductor materials.And the chalcogen semiconductor such as CdS, CuS is as low energy gap photocatalysis
Agent can increase considerably the photoresponse to visible region for the light anode.Therefore, it is proposed that a kind of brand-new scheme, by CdS,
CuS and ZnO nano array are compounded to form ZnO/CdS/CuS nano-array composite it is intended to improve its PhotoelectrocatalytiPerformance Performance.
Content of the invention
It is an object of the invention to proposing a kind of preparation method of ZnO/CdS/CuS nano-array composite, Neng Gougai
The PhotoelectrocatalytiPerformance Performance of kind ZnO.
The preparation method of ZnO/CdS/CuS nano-array composite is it is characterised in that first pass through collosol and gel legal system
Standby ZnO Seed Layer solution；ZnO Seed Layer is coated in ito glass substrate using dipping-pulling method, after Overheating Treatment, will grow
The electro-conductive glass having ZnO Seed Layer is placed on processed by hot bath in ZnO growth solution, obtains ZnO nanorod；To grow
The sample of ZnO nano array is put in thioacetyl amine aqueous solution, and ZnO/ZnS nano-array is obtained after water-bath；Using ion
Exchange process deposits to CdS, CuS nanoparticle on ZnO nano layer, obtains ZnO/CdS/CuS nano-array composite.
The present invention is given at the specific process parameter on the basis of said method further：
1st, the technological parameter that ZnO Seed Layer is prepared：By zinc acetate (Zn (CH3COO)2·2H2) and ethylene glycol monomethyl ether O
(CH3OCH2CH2OH) mix and be added dropwise over a small amount of monoethanolamine (H2NCH2CH2OH), prepare 0.2～0.5mol/L ZnO seed
Layer colloidal sol.
2nd, prepare the technological parameter of ZnO plated film：ZnO plated film is completed on ITO electro-conductive glass using dipping-pulling method,
After drying at 80 DEG C, repeat the above steps carry out second membrane to ITO electro-conductive glass, after membrane terminates twice, ITO is conductive
Glass is placed and 1～4h is dried in baking oven.
3rd, prepare the technological parameter of ZnO nanorod：0.02～0.05mol/L nitric acid is put into after sample is made annealing treatment
In the mixed growth solution of zinc and hexamethylenetetramine, 5～12h is reacted in hot bath at 90 DEG C, is dried, obtains under the conditions of 60 DEG C
ZnO nanorod.
4th, prepare the technological parameter of ZnO/ZnS nano-array：Prepare 0.3～0.6mol/L thioacetyl amine aqueous solution (TAA),
ZnO nanorod sample is put in TAA solution, puts into 5～12h in 90 DEG C of water-bath after beaker sealing, obtain in ZnO nano
The ZnO/ZnS nano-array of ZnS nano thin-film is grown on array.
5th, prepare the technological parameter of ZnO/CdS nano-array composite：Using ion exchange, CdS nanoparticle is sunk
Amass on ZnO nano layer.Prepare the cadmium nitrate (Cd (NO of 0.005～0.01mol/L3)2) aqueous solution being transferred in water heating kettle,
Then the electro-conductive glass after processing is placed in water heating kettle, is placed in baking oven heating 2h under the conditions of 140 DEG C, spend after taking-up from
Sub- water is cleaned drying and is obtained ZnO/CdS nano-array composite.
6th, prepare the technological parameter of ZnO/CdS/CuS nano-array composite：From triethylene glycol as solvent, prepare
Copper nitrate (Cu (the NO of 0.005～0.01mol/L3)2) solution, heated and stirred until entirely molten and be cooled to room temperature, will have been prepared
Good ZnO/CdS adds above-mentioned solution, and after reaction 1～4h under room temperature, clean drying obtains ZnO/CdS/CuS nano-array and is combined
Material.
The mechanism of action of the present invention is：When semiconductor light-catalyst is subject to light irradiation, absorbs and be equal to or more than its forbidden band width
The photon of degree makes electronics be stimulated, and transits to conduction band from valence band and produces light induced electron, and produces light on valence band relevant position
Raw hole, forms photo-generate electron-hole pair.Light induced electron and photohole are respectively provided with very strong oxidability and reducing power.?
Photoelectricity acts on down simultaneously, H2O is generated O by Hole oxidation2, and the H in water+It is reduced generation H2.
The ZnO/CdS/CuS nano-array composite that the present invention is obtained, growth fraction comparatively dense, and be evenly distributed,
Scanning electron microscopic observation test result is as shown in Figure 1.The ZnO/CdS/CuS nano-array composite ultraviolet that the present invention is obtained can
After seeing light spectrophotometer and electrochemical workstation test, extinction reaches 395nm, and photoelectric current reaches 1.71mA cm2(1.2V
Vs Ag/AgCl), test result is respectively as shown in Figure 2 and Figure 3.
Beneficial effect
1st, a kind of ZnO/CdS/CuS nano-array composite, can be effectively improved easily compound the lacking of photo-generate electron-hole
Point, strengthens the absorption to visible ray.
2nd, a kind of preparation method of ZnO/CdS/CuS nano-array composite, preparation process is simple, low production cost
Honest and clean, be conducive to the utilization and extention of solar energy.
Brief description
Fig. 1 is the scanning electron microscope image of the ZnO/CdS/CuS nano-array composite of gained in embodiment.
Fig. 2 is the ZnO/CdS/CuS nano-array composite of gained in embodiment 1 through UV-Vis spectrophotometry luminosity
Measure test result.
Fig. 3 is that the ZnO/CdS/CuS nano-array composite of gained in embodiment 1 tests knot through electrochemical workstation
Really.
Specific embodiment
The following examples can make those skilled in the art be more completely understood by the present invention, but limits never in any form
The present invention.
Embodiment 1
First, by zinc acetate (Zn (CH3COO)2·2H2) and ethylene glycol monomethyl ether (CH O3OCH2CH2OH) mix and dropwise add
Enter a small amount of monoethanolamine (H2NCH2CH2OH), prepare the ZnO Seed Layer colloidal sol of 0.2mol/L；Adopt dipping-pulling method with 1mm/s
Speed complete on ITO electro-conductive glass ZnO plated film and in colloidal sol stop 20s, at 80 DEG C dry after, repeat the above steps
Second membrane is carried out to ITO electro-conductive glass, after membrane terminates twice places ITO electro-conductive glass in baking oven and 1h is dried；By sample
Product made annealing treatment with 400 DEG C and be incubated put into after 1h 0.04mol/L zinc nitrate and hexamethylenetetramine mixed growth molten
In liquid, at 90 DEG C, hot bath reaction 9h, is dried under the conditions of 60 DEG C, obtains ZnO nanorod.Prepare 0.5mol/L thioacetamide molten
Liquid (TAA), ZnO nanorod sample is put in TAA solution, puts into 7h in 90 DEG C of water-bath, obtain in ZnO after beaker sealing
The ZnO/ZnS nano-array of ZnS nano thin-film is grown on nano-array.Using ion exchange, CdS nanoparticle is deposited to
On ZnO nano layer.Prepare the cadmium nitrate (Cd (NO of 0.007mol/L3)2) aqueous solution being transferred in water heating kettle, then will process
Electro-conductive glass afterwards is placed in water heating kettle, is placed in heating 2h in baking oven under the conditions of 140 DEG C, and after taking-up, deionized water is cleaned and dried
Dry obtain ZnO/CdS nano-array composite.Prepare the copper nitrate (Cu (NO of 0.007mol/L3)2) solution, heated and stirred is straight
To entirely molten and be cooled to room temperature, the ZnO/CdS having prepared is placed in above-mentioned solution, after reaction 2h under room temperature, cleans and dry
Obtain ZnO/CdS/CuS nano-array composite.
The ZnO/CdS/CuS nano-array composite that the present invention is obtained, growth fraction comparatively dense, and be evenly distributed,
Scanning electron microscopic observation test result is as shown in Figure 1.The ZnO/CdS/CuS nano-array composite ultraviolet that the present invention is obtained can
After seeing light spectrophotometer and electrochemical workstation test, extinction reaches 395nm, and photoelectric current reaches 1.71mA cm2(1.2V
Vs Ag/AgCl), test result is respectively as shown in Figure 2 and Figure 3.
Embodiment 2
First, by zinc acetate (Zn (CH3COO)2·2H2) and ethylene glycol monomethyl ether (CH O3OCH2CH2OH) mix and dropwise add
Enter a small amount of monoethanolamine (H2NCH2CH2OH), prepare the ZnO Seed Layer colloidal sol of 0.3mol/L；Adopt dipping-pulling method with 1mm/s
Speed complete on ITO electro-conductive glass ZnO plated film and in colloidal sol stop 20s, at 80 DEG C dry after, repeat the above steps
Second membrane is carried out to ITO electro-conductive glass, after membrane terminates twice places ITO electro-conductive glass in baking oven and 2.5h is dried；Will
Sample is made annealing treatment with 400 DEG C and is incubated the mixed growth putting into 0.02mol/L zinc nitrate and hexamethylenetetramine after 1h
In solution, at 90 DEG C, hot bath reaction 5h, is dried under the conditions of 60 DEG C, obtains ZnO nanorod.Prepare 0.3mol/L thioacetamide
Solution (TAA), ZnO nanorod sample is put in TAA solution, puts into 5h in 90 DEG C of water-bath, obtain after beaker sealing
The ZnO/ZnS nano-array of ZnS nano thin-film is grown on ZnO nano array.Using ion exchange, CdS nanoparticle is deposited
To on ZnO nano layer.Prepare the cadmium nitrate (Cd (NO of 0.005mol/L3)2) aqueous solution being transferred in water heating kettle, then will locate
Electro-conductive glass after reason is placed in water heating kettle, is placed in heating 2h in baking oven, after taking-up, deionized water is cleaned under the conditions of 140 DEG C
Drying obtains ZnO/CdS nano-array composite.Prepare the copper nitrate (Cu (NO of 0.005mol/L3)2) solution, heated and stirred
Until entirely molten and be cooled to room temperature, the ZnO/CdS having prepared is placed in above-mentioned solution, after reaction 1h under room temperature, cleans and dry
Dry obtain ZnO/CdS/CuS nano-array composite.
Embodiment 3
First, by zinc acetate (Zn (CH3COO)2·2H2) and ethylene glycol monomethyl ether (CH O3OCH2CH2OH) mix and dropwise add
Enter a small amount of monoethanolamine (H2NCH2CH2OH), prepare the ZnO Seed Layer colloidal sol of 0.5mol/L；Adopt dipping-pulling method with 1mm/s
Speed complete on ITO electro-conductive glass ZnO plated film and in colloidal sol stop 20s, at 80 DEG C dry after, repeat the above steps
Second membrane is carried out to ITO electro-conductive glass, after membrane terminates twice places ITO electro-conductive glass in baking oven and 4h is dried；By sample
Product made annealing treatment with 400 DEG C and be incubated put into after 1h 0.05mol/L zinc nitrate and hexamethylenetetramine mixed growth molten
In liquid, at 90 DEG C, hot bath reaction 12h, is dried under the conditions of 60 DEG C, obtains ZnO nanorod.Prepare 0.6mol/L thioacetamide
Solution (TAA), ZnO nanorod sample is put in TAA solution, puts into 12h in 90 DEG C of water-bath, obtain after beaker sealing
The ZnO/ZnS nano-array of ZnS nano thin-film is grown on ZnO nano array.Using ion exchange, CdS nanoparticle is deposited
To on ZnO nano layer.Prepare the cadmium nitrate (Cd (NO of 0.01mol/L3)2) aqueous solution being transferred in water heating kettle, then will process
Electro-conductive glass afterwards is placed in water heating kettle, is placed in heating 2h in baking oven under the conditions of 140 DEG C, and after taking-up, deionized water is cleaned and dried
Dry obtain ZnO/CdS nano-array composite.Prepare the copper nitrate (Cu (NO of 0.01mol/L3)2) solution, heated and stirred until
Entirely molten and be cooled to room temperature, the ZnO/CdS having prepared is placed in above-mentioned solution, after reaction 4h under room temperature, cleans and dry
To ZnO/CdS/CuS nano-array composite.
The above, the only present invention preferably specific embodiment, but protection scope of the present invention is not limited thereto,
Any those familiar with the art the invention discloses technical scope in, the change or replacement that can readily occur in,
All should be included within the scope of the present invention.Therefore, protection scope of the present invention should be with scope of the claims
It is defined.
Claims (7)
- The preparation method of 1.ZnO/CdS/CuS nano-array composite is it is characterised in that first pass through sol-gal process preparation ZnO Seed Layer solution；ZnO Seed Layer is coated in ito glass substrate using dipping-pulling method, after Overheating Treatment, length is had The electro-conductive glass of ZnO Seed Layer is placed on processed by hot bath in ZnO growth solution, obtains ZnO nanorod；ZnO will be grown The sample of nano-array is put in thioacetyl amine aqueous solution, and ZnO/ZnS nano-array is obtained after water-bath；Using ion exchange Method deposits to CdS, CuS nanoparticle on ZnO nano layer, obtains ZnO/CdS/CuS nano-array composite.
- 2. the preparation method of ZnO/CdS/CuS nano-array composite as claimed in claim 1 is it is characterised in that described ZnO Seed Layer solution prepare technological parameter be：By zinc acetate (Zn (CH3COO)2·2H2) and ethylene glycol monomethyl ether O (CH3OCH2CH2OH) mix and be added dropwise over monoethanolamine (H2NCH2CH2OH), prepare the ZnO Seed Layer of 0.2～0.5mol/L Colloidal sol.
- 3. the preparation method of ZnO/CdS/CuS nano-array composite as claimed in claim 1 is it is characterised in that prepare The technological parameter of described ZnO plated film is：ZnO plated film is completed on ITO electro-conductive glass using dipping-pulling method, dries at 80 DEG C After dry, repeat the above steps carry out second membrane to ITO electro-conductive glass, after membrane terminates twice place ITO electro-conductive glass 1～4h is dried in baking oven.
- 4. the preparation method of ZnO/CdS/CuS nano-array composite as claimed in claim 1 is it is characterised in that prepare The technological parameter of described ZnO nanorod is：0.02～0.05mol/L zinc nitrate and six times are put into after sample is made annealing treatment In the mixed growth solution of tetramine, 5～12h is reacted in hot bath at 90 DEG C, is dried, obtains ZnO nanorod under the conditions of 60 DEG C.
- 5. the preparation method of ZnO/CdS/CuS nano-array composite as claimed in claim 1 is it is characterised in that prepare The technological parameter of described ZnO/ZnS nano-array is：Prepare 0.3～0.6mol/L thioacetyl amine aqueous solution (TAA), ZnO is received The excellent sample of rice is put in TAA solution, puts into 5～12h in 90 DEG C of water-bath, obtain in ZnO nano array after beaker sealing The ZnO/ZnS nano-array of growth ZnS nano thin-film.
- 6. the preparation method of ZnO/CdS/CuS nano-array composite as claimed in claim 1 is it is characterised in that prepare The technological parameter of described ZnO/CdS nano-array composite is：CdS nanoparticle is deposited to by ZnO using ion exchange In nanometer layer；Prepare the cadmium nitrate (Cd (NO of 0.005～0.01mol/L3)2) aqueous solution being transferred in water heating kettle, then will locate Electro-conductive glass after reason is placed in water heating kettle, is placed in heating 2h in baking oven, after taking-up, deionized water is cleaned under the conditions of 140 DEG C Drying obtains ZnO/CdS nano-array composite.
- 7. the preparation method of ZnO/CdS/CuS nano-array composite as claimed in claim 1 is it is characterised in that prepare The technological parameter of described ZnO/CdS/CuS nano-array composite：From triethylene glycol as solvent, prepare 0.005～ Copper nitrate (Cu (the NO of 0.01mol/L3)2), heated and stirred is until entirely molten and be cooled to room temperature, by the ZnO/CdS having prepared It is placed in above-mentioned solution, after reaction 1～4h under room temperature, clean drying obtains ZnO/CdS/CuS nano-array composite.
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