CN109248693A - A kind of modified zinc blende nano-wire catalysis material and preparation method thereof - Google Patents
A kind of modified zinc blende nano-wire catalysis material and preparation method thereof Download PDFInfo
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- CN109248693A CN109248693A CN201811250196.4A CN201811250196A CN109248693A CN 109248693 A CN109248693 A CN 109248693A CN 201811250196 A CN201811250196 A CN 201811250196A CN 109248693 A CN109248693 A CN 109248693A
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- 239000000463 material Substances 0.000 title claims abstract description 49
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 40
- 239000002070 nanowire Substances 0.000 title claims abstract description 40
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical class [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052984 zinc sulfide Inorganic materials 0.000 claims abstract description 36
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000002042 Silver nanowire Substances 0.000 claims abstract description 22
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 20
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 15
- 230000001699 photocatalysis Effects 0.000 claims abstract description 12
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 12
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 238000007146 photocatalysis Methods 0.000 claims abstract description 9
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000000908 ammonium hydroxide Substances 0.000 claims abstract description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000005253 cladding Methods 0.000 claims abstract description 4
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 4
- 230000001476 alcoholic effect Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 13
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 229910052946 acanthite Inorganic materials 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- FSJWWSXPIWGYKC-UHFFFAOYSA-M silver;silver;sulfanide Chemical compound [SH-].[Ag].[Ag+] FSJWWSXPIWGYKC-UHFFFAOYSA-M 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- XYIBRDXRRQCHLP-UHFFFAOYSA-N ethyl acetoacetate Chemical compound CCOC(=O)CC(C)=O XYIBRDXRRQCHLP-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000012149 noodles Nutrition 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000004048 modification Effects 0.000 abstract description 15
- 238000012986 modification Methods 0.000 abstract description 15
- 239000005083 Zinc sulfide Substances 0.000 abstract description 11
- 230000005540 biological transmission Effects 0.000 abstract description 4
- 238000010521 absorption reaction Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 230000006641 stabilisation Effects 0.000 abstract 1
- 238000011105 stabilization Methods 0.000 abstract 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
- 239000001257 hydrogen Substances 0.000 description 11
- 229910052739 hydrogen Inorganic materials 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000004110 Zinc silicate Substances 0.000 description 3
- 239000006059 cover glass Substances 0.000 description 3
- XUARKZBEFFVFRG-UHFFFAOYSA-N silver sulfide Chemical compound [S-2].[Ag+].[Ag+] XUARKZBEFFVFRG-UHFFFAOYSA-N 0.000 description 3
- 229940056910 silver sulfide Drugs 0.000 description 3
- 235000019352 zinc silicate Nutrition 0.000 description 3
- XSMMCTCMFDWXIX-UHFFFAOYSA-N zinc silicate Chemical compound [Zn+2].[O-][Si]([O-])=O XSMMCTCMFDWXIX-UHFFFAOYSA-N 0.000 description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012826 global research Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000005622 photoelectricity Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005486 sulfidation Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- QSHCHNZBDZTUQK-UHFFFAOYSA-N zinc sulfanylidenesilver sulfide Chemical compound [S-2].[Zn+2].[Ag]=S QSHCHNZBDZTUQK-UHFFFAOYSA-N 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/20—Sulfiding
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
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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
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1088—Non-supported catalysts
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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 & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
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Abstract
It is using silver nanowires as supporter, the external sheath of the silver nanowires has the Ag of flaky nanometer structure the invention discloses a kind of modified zinc blende nano-wire catalysis material2S/ZnS.Preparation method of the invention: (1) dispersing silver nanowires in alcoholic solution, sequentially adds ammonium hydroxide under stirring conditions and ethyl orthosilicate is reacted, and obtains the silver nanowires predecessor of surface cladding layer of silicon dioxide；(2) hydro-thermal reaction will be carried out in predecessor, urea and zinc nitrate solution；(3) product and thiocarbamide obtained step (2) afterwards carries out hydro-thermal reaction to get modified zinc blende nano-wire catalysis material is arrived.Modification zinc blende nano-wire catalysis material of the invention is conducive to the quick transmission of the stabilization and electronics of material structure, be conducive to the separation of electron hole, increase photocatalysis efficiency, the forbidden bandwidth of the absorption sunlight of zinc sulphide can be improved, improve its absorptivity to sunlight, increase capacity usage ratio, improves photocatalytic activity.
Description
Technical field
The invention belongs to field of photocatalytic material more particularly to a kind of modified zinc blende nano-wire catalysis material and its systems
Preparation Method.
Background technique
Hydrogen energy source is a kind of clean energy resource with long-range development prospect, for how rationally efficiently obtain it at
For global research hotspot.And decomposing water with solar energy hydrogen manufacturing is to prepare one of important preparation method of Hydrogen Energy, it have green,
The features such as energy consumption is small, at low cost, therefore receive and significantly pay close attention to.
ZnS as a kind of II-VI important race's direct band-gap semicondictor material, it the fields such as photocatalysis, photoelectricity all
It has important application, and pure zinc sulphide can only absorb the ultraviolet band energy in sunlight because forbidden bandwidth is wider, and account for
Nearly 50% visible light part of solar energy then fails to efficiently use, and which greatly limits its capacity usage ratio and catalysis
Efficiency.
Summary of the invention
The technical problem to be solved by the present invention is to overcome the shortcomings of to mention in background above technology and defect, provide one
Modified zinc blende nano-wire catalysis material of kind and preparation method thereof.
In order to solve the above technical problems, technical solution proposed by the present invention are as follows:
A kind of modified zinc blende nano-wire catalysis material is using silver nanowires as supporter, outside the silver nanowires
Layer is coated with the Ag of flaky nanometer structure2S/ZnS。
Above-mentioned modification zinc blende nano-wire catalysis material, it is preferred that the modified zinc blende nano-wire photocatalysis material
Material diameter is 200~300nm.
Above-mentioned modification zinc blende nano-wire catalysis material, it is preferred that the Ag of the flaky nanometer structure2In S/ZnS
Ag2The mass percentage that the mass percentage of S is 15~20%, ZnS is 80~85%.
Above-mentioned modification zinc blende nano-wire catalysis material, it is preferred that the Ag2S/ZnS refers to Ag2S is doped in ZnS
In.
The inventive concept total as one, the present invention also provides a kind of preparations of modified zinc blende nano-wire catalysis material
Method, comprising the following steps:
(1) it is scattered in alcoholic solution in silver nanowires, sequentially adds ammonium hydroxide and ethyl orthosilicate under stirring conditions
It is reacted, washs, dries after the reaction was completed, obtain the silver nanowires predecessor of surface cladding layer of silicon dioxide；
(2) predecessor obtained in step (1), urea and zinc nitrate solution are added in reaction kettle and carry out hydro-thermal reaction,
After the completion of hydro-thermal reaction, product is centrifuged, it is dry；
(3) product and thiocarbamide that step (2) obtains afterwards are added in reaction kettle and carry out hydro-thermal reaction, hydro-thermal reaction is completed
Afterwards, product is centrifuged, is dried to get modified zinc blende nano-wire catalysis material is arrived.
In above-mentioned preparation method, on the one hand urea serves as the effect of precipitating reagent, and zinc ion can be made to be coated with two
The silver nanowires Surface Creation zinc silicate of silica；It can be conducive to the packet of zinc silicate on the other hand with activated silica
It covers.
Above-mentioned preparation method, it is preferred that in the step (2), the temperature of hydro-thermal reaction is 100 DEG C~120 DEG C, reaction
Time be 15~20h；In the step (3), the temperature of hydro-thermal reaction is 120 DEG C~150 DEG C, the time of reaction is 10~
15h。
Above-mentioned preparation method, it is preferred that the silver nanowires in the step (1) is prepared using following methods
: ferric chloride solution (using ethylene glycol as solvent), silver nitrate and polyvinylpyrrolidone addition ethylene glycol are uniformly dispersed, then
Resulting mixed solution is transferred to water heating kettle and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 120 DEG C~150 DEG C, reaction
Time is 1.5~2h；Wherein the mass ratio of ferric chloride solution, silver nitrate and polyvinylpyrrolidone is (20~25): (2.5~
3): (1~1.5).
Above-mentioned preparation method, it is preferred that in the step (1), the volume ratio of ammonium hydroxide and ethyl orthosilicate is 7.5:1；
The time of stirring is 4~6h.
Above-mentioned preparation method, it is preferred that in the step (2), surface coats the silver nanowires of layer of silicon dioxide
The mass ratio of predecessor and urea is (0.5~4): 1；The dosage ratio of urea and zinc nitrate solution is 1~20, and ratio unit is
g/mL；The concentration of the zinc nitrate solution is 0.1M.
Above-mentioned preparation method, it is preferred that in the step (3), the mass ratio of product and thiocarbamide that step (2) obtains afterwards
For (1~2): (10~30).
For pure zinc sulphide because of the wider energy that can only absorb the ultraviolet region in sunlight of forbidden bandwidth, capacity usage ratio is low.
The present invention makes it to visible light-responded using the band structure of the method transformation zinc sulphide of silver ion doping.Using silver nanowires
As template, surface is carried out using the method for coated with silica and is modified, conducive to the growth of the presoma zinc silicate of zinc；Vulcanized
Silver ion is spread from inside to outside in the zinc sulphide lattice for penetrating into outer layer in journey, formed lattice scale Uniform Doped zinc sulphide/
The surface layer nano-sheet tissue of silver sulfide, meanwhile, the steady of catalysis material structure is conducive to as support construction using silver nanowires
Fixed, silver-colored electric conductivity is superior, is also conducive to electronics and quickly transmits, increases photocatalysis efficiency.
Compared with the prior art, the advantages of the present invention are as follows:
(1) modification zinc blende nano-wire catalysis material of the invention is conducive to material structure with silver for support carrier
Stable and electronics quick transmission, is conducive to the separation of electron hole, increases photocatalysis efficiency；With silver sulfide modification vulcanization
Zinc is active constituent, can improve the forbidden bandwidth of the absorption sunlight of zinc sulphide, improve its absorptivity to sunlight, increase
Capacity usage ratio improves photocatalytic activity.
(2) outer layer is penetrated into using the method that silver ion is spread from inside to outside in preparation method sulfidation of the invention
In zinc sulphide lattice, zinc sulphide-silver sulfide nano line of lattice scale Uniform Doped is formed, the mode of this Uniform Doped is effective
Improve photocatalysis efficiency in ground.
(3) present invention makes it to visible light-responded using the band structure of the method transformation zinc sulphide of silver ion doping.
Detailed description of the invention
Fig. 1 is the surface sweeping electromicroscopic photograph of modification zinc blende nano-wire catalysis material prepared by the embodiment of the present invention 1.
Fig. 2 is the transmission electron microscope picture of modification zinc blende nano-wire catalysis material prepared by the embodiment of the present invention 1.
Fig. 3 is the XRD diffraction pattern of modification zinc blende nano-wire catalysis material prepared by the embodiment of the present invention 1.
Fig. 4 is that modification zinc blende nano-wire catalysis material prepared by the embodiment of the present invention 1 and pure the ZnS light under full spectrum are urged
Change and produces hydrogen contrast curve chart.
Fig. 5 is that modification zinc blende nano-wire catalysis material prepared by the embodiment of the present invention 1 and pure ZnS are produced under visible light
Hydrogen efficiency contrast curve chart.
Specific embodiment
To facilitate the understanding of the present invention, invention herein is done below in conjunction with Figure of description and preferred embodiment more complete
Face meticulously describes, but protection scope of the present invention is not limited to following specific embodiments.
Unless otherwise defined, all technical terms used hereinafter are generally understood meaning phase with those skilled in the art
Together.Technical term used herein is intended merely to the purpose of description specific embodiment, and it is of the invention to be not intended to limitation
Protection scope.
Unless otherwise specified, various raw material, reagent, the instrument and equipment etc. used in the present invention can pass through city
Field is commercially available or can be prepared by existing method.
Embodiment 1:
A kind of modification zinc blende nano-wire catalysis material of the invention, is core-shell structure, and internal layer is silver nanowires (support
Body), outer layer Ag2S/ZnS(Ag2S is doped in ZnS) flaky nanometer structure (active constituent)；Ag2S/ZnS flaky nanometer structure
Middle Ag2The percentage composition that the percentage composition of S is 16.7%, ZnS is 83.3%.
The preparation method of modification zinc blende nano-wire catalysis material of the invention, comprising the following steps:
(1) 6 × 10 are prepared by solvent of ethylene glycol-4The ferric chloride solution of M；
2g ferric chloride solution, 0.27g silver nitrate and 0.1g polyvinylpyrrolidone (molecular weight 1,300,000) are added
In 30mL ethylene glycol, then ultrasound 15min, is stirred for 12h；
Gained mixed solution is transferred in water heating kettle the hydro-thermal reaction 1.5h at 150 DEG C；
(2) (what is obtained is silver nanowires) after its centrifuge washing is added finally obtained reaction solution 5mL in step (1)
It is transferred in blue cover glass bottle after the alcohol ultrasound of 30mL is uniform and carries out magnetic agitation；
During magnetic agitation, 1.5mL ammonium hydroxide is first added dropwise, after stirring 2~3min, then the positive silicon of 0.02mL is added dropwise
Acetoacetic ester stirs centrifuge washing after 4h, and finally centrifugation product is placed in 60 DEG C of baking oven and is dried for 24 hours；
(3) 0.1M zinc nitrate solution is prepared；
The final desciccate merging for taking 15mg step (2) to obtain is placed in the blue cover glass bottle of 30mL deionized water, is added
Enter 0.6g urea and 0.5mL0.1M zinc nitrate solution, blue cover glass bottle is then put into baking oven the hydro-thermal reaction at 102 DEG C
18h is dried for 24 hours in 60 DEG C of baking ovens finally by reaction product centrifuge washing；
(4) powder for taking 30mg step (3) to obtain, which is dispersed in 30mL alcohol and deionized water mixed solution, (alcohol and to be gone
Ion water volume ratio is 1:1), it is ultrasonically treated 15min, 0.2g thiocarbamide is added thereto, is then transferred to above-mentioned solution
Hydro-thermal reaction 12h is dried finally by reaction product centrifuge washing in 60 DEG C of baking oven to get changing at 120 DEG C in water heating kettle
Property zinc blende nano-wire catalysis material.
Fig. 1 is the surface sweeping electromicroscopic photograph of modified zinc blende nano-wire catalysis material manufactured in the present embodiment, can by Fig. 1
Know, modified zinc blende nano-wire catalysis material is the one-dimensional nano line that there is multilevel structure on surface, diameter 200-300nm；Fig. 2
For the transmission electron microscope picture of modified zinc blende nano-wire catalysis material manufactured in the present embodiment, the modification zinc sulphide as seen from the figure
Nano wire catalysis material has nucleocapsid structure, and internal layer is silver nanowires, and outer layer is zinc sulphide/silver sulfide vulcanization of sheet
Object.Fig. 3 is the XRD diffraction pattern of modified zinc blende nano-wire catalysis material manufactured in the present embodiment, as can be seen from the figure originally
The main component for the modification zinc blende nano-wire catalysis material that embodiment is prepared.
Fig. 4 is that modified zinc blende nano-wire catalysis material manufactured in the present embodiment and pure the ZnS photocatalysis under full spectrum produce
Hydrogen contrast curve chart, pure ZnS hydrogen generation efficiency is 188.9umol/g/h as seen from the figure, and is modified zinc blende nano-wire photocatalysis material
Material hydrogen generation efficiency is 291.3umol/g/h；Fig. 5 is modified zinc blende nano-wire catalysis material manufactured in the present embodiment and pure
ZnS hydrogen generation efficiency contrast curve chart under visible light (wavelength is greater than 400 nanometers), as seen from the figure, pure ZnS is unglazed under visible light
Catalytic activity, hydrogen generation efficiency 0, and being modified zinc blende nano-wire catalysis material hydrogen generation efficiency is 24.7umol/g/h.
Claims (10)
1. a kind of modified zinc blende nano-wire catalysis material, which is characterized in that the modified zinc blende nano-wire photocatalysis material
Material is using silver nanowires as supporter, and the external sheath of the silver nanowires has the Ag of flaky nanometer structure2S/ZnS。
2. modified zinc blende nano-wire catalysis material as described in claim 1, which is characterized in that the modified zinc sulphide is received
The diameter of rice noodles catalysis material is 200~300nm.
3. modified zinc blende nano-wire catalysis material as described in claim 1, which is characterized in that the Ag2In S/ZnS
Ag2The mass percentage that the mass percentage of S is 15~20%, ZnS is 80~85%.
4. modified zinc blende nano-wire catalysis material as claimed in any one of claims 1 to 3, which is characterized in that described
Ag2S/ZnS refers to Ag2S is doped in ZnS.
5. a kind of preparation method of modified zinc blende nano-wire catalysis material, which comprises the following steps:
(1) it disperses silver nanowires in alcoholic solution, sequentially adds ammonium hydroxide under stirring conditions and ethyl orthosilicate carries out
Reaction is washed after the reaction was completed, is dried, and the silver nanowires predecessor of surface cladding layer of silicon dioxide is obtained；
(2) predecessor obtained in step (1), urea and zinc nitrate solution are added in reaction kettle and carry out hydro-thermal reaction, hydro-thermal
After the reaction was completed, product is centrifuged, dried；
(3) product and thiocarbamide that step (2) obtains afterwards are added in reaction kettle and carry out hydro-thermal reaction, it is right after the completion of hydro-thermal reaction
Product is centrifuged, is dried to get modified zinc blende nano-wire catalysis material is arrived.
6. preparation method as claimed in claim 5, which is characterized in that in the step (2), the temperature of hydro-thermal reaction is 100
DEG C~120 DEG C, the time of reaction is 15~20h；In the step (3), the temperature of hydro-thermal reaction is 120 DEG C~150 DEG C, reaction
Time be 10~15h.
7. preparation method as claimed in claim 5, which is characterized in that the silver nanowires in the step (1) is using following
What method was prepared: ferric chloride solution, silver nitrate and polyvinylpyrrolidone addition ethylene glycol being uniformly dispersed, then
Resulting mixed solution is transferred to water heating kettle and carries out hydro-thermal reaction, the temperature of hydro-thermal reaction is 120 DEG C~150 DEG C, reaction
Time is 1.5~2h；Wherein the mass ratio of ferric chloride solution, silver nitrate and polyvinylpyrrolidone is (20~25): (2.5~
3): (1~1.5).
8. such as the described in any item preparation methods of claim 5~7, which is characterized in that in the step (1), ammonium hydroxide and positive silicon
The volume ratio of acetoacetic ester is 7.5:1；The time of stirring is 4~6h.
9. such as the described in any item preparation methods of claim 5~7, which is characterized in that in the step (2), surface cladding one
The silver nanowires predecessor of layer silica and the mass ratio of urea are (0.5~4): 1；The amount ratio of urea and zinc nitrate solution
Value is 1~20, and ratio unit is g/mL；The concentration of the zinc nitrate solution is 0.1M.
10. such as the described in any item preparation methods of claim 5~7, which is characterized in that in the step (3), after step (2)
The product of acquisition and the mass ratio of thiocarbamide are (1~2): (10~30).
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| CN111715247A (en) * | 2020-06-19 | 2020-09-29 | 廖铁仙 | Silver sulfide/cobalt phosphide composite photocatalyst and preparation method thereof |
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| CN102716755A (en) * | 2012-07-17 | 2012-10-10 | 哈尔滨师范大学 | Silver sulfide/zinc sulfide compound semiconductor photocatalyst with ultraviolet light catalytic activity and preparation method thereof |
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