CN107282070A - A kind of three-dimensional flower piece shape sulfur-indium-zinc micro-nano nanowire arrays and its preparation method and application - Google Patents
A kind of three-dimensional flower piece shape sulfur-indium-zinc micro-nano nanowire arrays and its preparation method and application Download PDFInfo
- Publication number
- CN107282070A CN107282070A CN201710383926.7A CN201710383926A CN107282070A CN 107282070 A CN107282070 A CN 107282070A CN 201710383926 A CN201710383926 A CN 201710383926A CN 107282070 A CN107282070 A CN 107282070A
- Authority
- CN
- China
- Prior art keywords
- indium
- micro
- piece shape
- dimensional flower
- zinc
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002070 nanowire Substances 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 title claims abstract description 16
- 238000003491 array Methods 0.000 title claims abstract description 7
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 38
- 239000002184 metal Substances 0.000 claims abstract description 38
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 38
- 239000011701 zinc Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 15
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000005864 Sulphur Substances 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 229910052738 indium Inorganic materials 0.000 claims abstract description 7
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000002904 solvent Substances 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 27
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 230000035484 reaction time Effects 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 150000002471 indium Chemical class 0.000 claims description 11
- 238000005498 polishing Methods 0.000 claims description 9
- 239000000843 powder Substances 0.000 claims description 8
- 244000137852 Petrea volubilis Species 0.000 claims description 7
- 238000004140 cleaning Methods 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- 239000012456 homogeneous solution Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 4
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 4
- 235000018417 cysteine Nutrition 0.000 claims description 4
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- XURCIPRUUASYLR-UHFFFAOYSA-N Omeprazole sulfide Chemical compound N=1C2=CC(OC)=CC=C2NC=1SCC1=NC=C(C)C(OC)=C1C XURCIPRUUASYLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- VBXWCGWXDOBUQZ-UHFFFAOYSA-K diacetyloxyindiganyl acetate Chemical compound [In+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VBXWCGWXDOBUQZ-UHFFFAOYSA-K 0.000 claims description 3
- 229910000337 indium(III) sulfate Inorganic materials 0.000 claims description 3
- XGCKLPDYTQRDTR-UHFFFAOYSA-H indium(iii) sulfate Chemical compound [In+3].[In+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGCKLPDYTQRDTR-UHFFFAOYSA-H 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 230000001699 photocatalysis Effects 0.000 abstract description 8
- 230000015556 catabolic process Effects 0.000 abstract description 7
- 238000007146 photocatalysis Methods 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 208000007578 phototoxic dermatitis Diseases 0.000 abstract description 4
- 238000004577 artificial photosynthesis Methods 0.000 abstract description 3
- 239000000356 contaminant Substances 0.000 abstract description 3
- 230000007547 defect Effects 0.000 abstract description 3
- 238000002310 reflectometry Methods 0.000 abstract description 3
- 238000004500 asepsis Methods 0.000 abstract description 2
- 239000011941 photocatalyst Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 13
- 238000001035 drying Methods 0.000 description 5
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 4
- 229940012189 methyl orange Drugs 0.000 description 4
- 239000002071 nanotube Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000004425 Makrolon Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- -1 nanometer Line Substances 0.000 description 1
- 235000012149 noodles Nutrition 0.000 description 1
- 239000006250 one-dimensional material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000000505 pernicious effect Effects 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
Classifications
-
- 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
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
Abstract
The invention discloses a kind of three-dimensional flower piece shape sulfur-indium-zinc micro-nano nanowire arrays and its preparation method and application, using the zinc metal sheet by pretreatment as substrate, using indium source, sulphur source as presoma, by controlling the temperature and time of solvent thermal reaction, so as to prepare ZnIn2S4Micro-nano nanowire arrays.The ZnIn of three-dimensional flower laminated structure prepared by the present invention2S4Micro-nano nanowire arrays, are pioneering in solid substrate；The ZnIn prepared according to the method that the present invention is provided2S4Micro-nano nanowire arrays have specific surface area high, and reflectivity is low, and it is good to fall into photosensitiveness, and defect is less and being capable of the excellent specific property such as Reusability；And preparation method is simple, process is easily-controllable, with low cost, asepsis environment-protecting, in photocatalysis hydrogen production, photocatalysis degradation organic contaminant, artificial photosynthesis, photo-catalyst, and the field such as solar cell has huge application prospect.
Description
Technical field
Prepared the invention belongs to material and application of solar energy converts field, more particularly, to a kind of three-dimensional flower piece shape sulfur-indium-zinc
Micro-nano wire array and its preparation method and application.
Background technology
With countries in the world rapid economic development, the mankind are to the demand more and more higher of the energy, to the cry of environmental protection
Grow to even greater heights.But traditional fossil energy is a kind of non-renewable energy resources, the trend of increasingly depleted, and fossil energy are faced with
Source produces CO in burning2、SO2There is huge destruction to environment Deng pernicious gas.So solving energy crisis and environmental pollution
Problem becomes two major subjects that the world today faces, countries in the world all set up environmental protection, sustainable development it is new
Energy system is strategic as the significant development of country.Photocatalitic Technique of Semiconductor is a kind of environmentally friendly ring efficiently, safe
Border is purified and production hydrogen technology, is had huge application potential on environmental pollution and problem of energy crisis is solved, is urged at present in light
Change hydrogen manufacturing, photocatalysis degradation organic contaminant, artificial photosynthesis, photo-catalyst, the field such as solar cell is suffered from extensively
General application.
In recent years, transient metal sulfide type photochemical catalyst is widely studied and paid close attention to, because sulfide typically has
Narrower energy gap, directly can absorb visible ray and occur light-catalyzed reaction.Ternary sulfide ZnIn2S4It is used as AB2X4Type
A member in semiconductor, band gap width, in 2.4eV or so, is a kind of visible light-responded semi-conducting material, with excellent light
Property and catalytic stability are learned, thus extensive concern is received in scientific circles and industrial circle.Such as Publication No.
CN102795661A Chinese patent, a kind of flower-shaped ZnIn of classification is prepared for by solvent-thermal method2S4Ternary compound, is urged in light
Changing the fields such as degradation of organic substances, purification air has better effects.Publication No. CN103736501A Chinese patent, passes through solvent
Hot method is prepared for a kind of ZnIn with isomerism knot2S4Composite, substantially can have engine dyeing by photo-catalytic degradation of methyl-orange etc.
Material.Publication No. CN103908971A Chinese patent, is prepared for a kind of selective catalytic oxidation that is used for by hydro-thermal method and is coupled
Amine generates the ZnIn of imines2S4Photochemical catalyst, aminated compounds life can be selectively oxidized in atmosphere, under radiation of visible light
Into imines.ZnIn prepared by the above method2S4There is respective advantage, but also there are many deficiencies.The ZnIn that such as they prepare2S4
All it is powder body material, uniformity is poor, easily reunites, be unfavorable for reclaiming and reuse.It is well known that for inorganic nano material
For, the factor such as pattern, size, structure suffers from very big influence to its physicochemical properties.Monodimension nanometer material such as nanometer
Line, nanotube etc. have the excellent specific properties such as specific surface area is high, limit photosensitiveness is good, in the semiconductor catalytic field such as oxide, sulfide
Suffer from being widely applied.However, at present to ZnIn2S4Most of research all concentrate on the multidimensional material such as nanometer sheet, microballoon,
A huge challenge is still for the one-dimensional material field of material preparation such as nano wire, nanotube.
Up to the present, only occurred 3 on ZnIn2S4Open report prepared by monodimension nanometer material.Such as Gao is adopted
One-dimensional ZnIn is prepared for solvent-thermal method2S4Nano wire and nanotube, but employ surfactant and be powder body material
（Gou XL, Cheng FY, Shi YH, Zhang L, Peng SJ, Chen J, Shen PW.Journal of the American Chemical Society 2006, 128, 7222.）.ZnIn has been synthesized by two-step process in Wei etc.2S4Nanometer
Line, but also using surfactant and be powder body material（Wei QL.Chinese Journal of Inorganic Chemistry 2010, 26, 269.）.Shi etc. uses hydro-thermal method, using makrolon as template, is prepared for ZnIn2S4Nano wire
And nanotube, it is also powder body material（Shi L, Yin P, Dai Y.Langmuir the Acs Journal of Surfaces & Colloids 2013, 29, 12818.）.ZnIn prepared by these methods2S4Monodimension nanometer material, process compared with
For complexity, cost is higher and is not easily recycled.Therefore, a kind of simple, with low cost method, large area preparation are explored, is easily reclaimed
ZnIn2S4Nano-wire array film has important practical significance.
The content of the invention
To overcome the deficiencies in the prior art, the present invention provide a kind of three-dimensional flower piece shape sulfur-indium-zinc micro-nano wire array and its
Preparation method and application, process is simple, safe and reliable, with low cost, has in solar energy photocatalytic field before application well
Scape.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of preparation method of three-dimensional flower piece shape sulfur-indium-zinc micro-nano wire array, it is characterised in that this method uses following step
Suddenly：
（1）The zinc metal sheet cut is first carried out a certain degree of polishing, the oxide layer on surface is removed；
（2）Will（1）Zinc metal sheet after middle polishing is cleaned and dried, and is then put into as substrate in reactor inner bag；
（3）Indium source and sulphur source are added in reactor according to certain mixed in molar ratio, solvent is added, is then stirred
Or ultrasonic dissolution, it is made into certain density homogeneous solution；
（4）Reactor is sealed, 160 ~ 220 DEG C of temperature, 1 ~ 10 hour reaction time is controlled；After reaction terminates, reactor is natural
Room temperature is cooled to, takes out and is cleaned and dried after sample, you can obtain the three-dimensional flower piece shape ZnIn of the homoepitaxial on zinc metal sheet2S4It is micro--to receive
Nanowire arrays film.
Step（1）Described in zinc metal sheet carry out pretreatment refer to be polished with the sand paper of 3000 mesh or so.
Step（2）Described in zinc metal sheet carry out cleaning refer to successively use acetone, absolute ethyl alcohol, deionized water sonic oscillation
10min；Step（2）Described in zinc metal sheet be dried refer to be dried with not higher than 60 DEG C of baking oven or air gun.
Step（3）Described in indium salts be inidum chloride, indium nitrate, indium sulfate, indium acetate or Indium Tris acetylacetonate, described indium
The concentration of salt is 0.2-0.6M.
Step（3）Described in organic solvent for ethylene glycol or ethylene glycol and ethanol mixture.
Step（3）Described in sulphur source be sulphur powder, thiocarbamide, cysteine or thioacetamide.
Step（3）Described in indium salts and sulphur source mol ratio be 1:2~1:8.
Step（4）Described in reaction time be preferably 2-4h, preferably 180 ~ 200 DEG C of reaction temperature.
A kind of three-dimensional flower piece shape sulfur-indium-zinc micro-nano wire array according to any of the above-described methods described characterized in that, prepare
Obtain.
A kind of ZnIn of three-dimensional flower piece shape2S4Micro-nano wire array is in light-catalysed application.
The present invention is prepared for the ZnIn of three-dimensional flower laminated structure by one step hydro thermal method in zinc metal sheet substrate2S4Micro-nano
Nanowire array film, is pioneering in solid substrate, no template, surfactant-free not only possesses two-dimensional sheet architectural feature, also
With nanowire array structure advantage.Compared with existing appearance structure, ZnIn prepared by the present invention2S4Micro-nano wire array has
Specific surface area is high, and reflectivity is low, and it is good to fall into photosensitiveness, and defect is less and being capable of the excellent specific property such as Reusability.And preparation method is simple,
Process is easily-controllable, with low cost, asepsis environment-protecting, in photocatalysis hydrogen production, photocatalysis degradation organic contaminant, artificial photosynthesis, light
Catalytically bactericidal process, the field such as solar cell has huge application prospect.
Compared with prior art, advantage of the present invention is as follows：
1. the raw material used in the present invention are relatively easily obtained, preparation process is simple, safe and reliable, with low cost, in solar energy
Photocatalysis field has good application prospect.
2. the ZnIn of the three-dimensional flower piece shape of the direct growth disclosed by the invention in conductive substrates2S4Micro-nano wire array,
Belong to one-dimensional nano-micrometer material, with specific surface area is high, reflectivity is low, fall into the excellent spies such as photosensitiveness is good, defect is less, easy recovery
Property.
3. the ZnIn prepared by the present invention2S4Micro-nano wire, the general 5-10nm of nanometer sheet thickness on its surface, not only increases
Specific surface area, is conducive to electronics to escape, more greatly reduces the recombination probability of photo-generated carrier, improve photocatalytic activity.
4. the present invention, which is the step solvent-thermal method of first passage one, obtains ZnIn2S4Micro-nano wire array, this is also to prepare other
Multi-element compounds nano-wire array provides thinking.
Brief description of the drawings
Fig. 1 is grown in the ZnIn of the three-dimensional flower piece shape in zinc metal sheet substrate by embodiment 12S4The XRD of micro-nano wire array
Figure；
Fig. 2 is grown in the ZnIn of the three-dimensional flower piece shape in zinc metal sheet substrate by embodiment 12S4Micro-nano wire array difference is differentiated
SEM figures under rate；
Fig. 3 is by the ZnIn for the three-dimensional flower piece shape being grown under the differential responses time in zinc metal sheet substrate2S4Micro-nano wire array
Degradation effect compares figure.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1：
A kind of three-dimensional flower piece shape sulfur-indium-zinc（ZnIn2S4）The preparation method of micro-nano wire array, is comprised the steps of：
（1）First the zinc metal sheet cut is polished with 3000 mesh sand paper, the oxide layer on surface is removed；
（2）Will（1）Zinc metal sheet after middle polishing is carried out cleaning 10min, then is used air gun with acetone, absolute ethyl alcohol, deionized water successively
Drying, is then put into reactor inner bag as substrate；
（3）By thioacetamide and inidum chloride according to 2：1 mixed in molar ratio is added in reactor, adds ethylene glycol, so
After be stirred or ultrasonic dissolution, be made into indium salts concentration be 0.4M homogeneous solution；
（4）Reactor is sealed, 200 DEG C of temperature, 2 hours reaction time is controlled；After reaction terminates, reactor naturally cools to room
Temperature, takes out and is cleaned and dried after sample, you can obtain the three-dimensional flower piece shape ZnIn of the homoepitaxial on zinc metal sheet2S4Micro-nano wire array
Film.
Fig. 1 is the ZnIn that the present embodiment is obtained2S4The XRD of film；As shown in Figure 1, except the peak at zinc-base bottom, Ji Husuo
Some peaks all correspond to ZnIn2S4Peak, and its peak is more sharp, shows that its crystallinity is preferable.
Fig. 2 is the ZnIn that the present embodiment is obtained2S4The SEM figures of film；Its surface is by obvious three-dimensional flower piece as shown in Figure 2
Shape is constituted, and micro-nano rice noodles growth fraction is more uniform.
Embodiment 2：
A kind of ZnIn of three-dimensional flower piece shape2S4The preparation method of micro-nano wire array, is comprised the steps of：
（1）First the zinc metal sheet cut is polished with 3000 mesh sand paper, the oxide layer on surface is removed；
（2）Will（1）Zinc metal sheet after middle polishing is carried out cleaning 10min, then is used air gun with acetone, absolute ethyl alcohol, deionized water successively
Drying, is then put into reactor inner bag as substrate；
（3）By thiocarbamide and indium sulfate according to 4：1 mixed in molar ratio is added in reactor, adds ethylene glycol, is then carried out
Stirring or ultrasonic dissolution, are made into the homogeneous solution that indium salts concentration is 0.2M；
（4）Reactor is sealed, 160 DEG C of temperature, 10 hours reaction time is controlled；After reaction terminates, reactor is naturally cooled to
Room temperature, takes out and is cleaned and dried after sample, you can obtain the three-dimensional flower piece shape ZnIn of the homoepitaxial on zinc metal sheet2S4Micro-nano linear array
Row film.
Embodiment 3：
A kind of ZnIn of three-dimensional flower piece shape2S4The preparation method of micro-nano wire array, is comprised the steps of：
（1）First the zinc metal sheet cut is polished with 3000 mesh sand paper, the oxide layer on surface is removed；
（2）Will（1）Zinc metal sheet after middle polishing is carried out cleaning 10min, then is used air gun with acetone, absolute ethyl alcohol, deionized water successively
Drying, is then put into reactor inner bag as substrate；
（3）Cysteine and indium acetate are according to 6：1 mixed in molar ratio is added in reactor, adds ethylene glycol, Ran Houjin
Row stirring or ultrasonic dissolution, are made into the homogeneous solution that indium salts concentration is 0.4M；
（4）Reactor is sealed, 180 DEG C of temperature, 6 hours reaction time is controlled；After reaction terminates, reactor naturally cools to room
Temperature, takes out and is cleaned and dried after sample, you can obtain the three-dimensional flower piece shape ZnIn of the homoepitaxial on zinc metal sheet2S4Micro-nano wire array
Film.
Embodiment 4：
A kind of ZnIn of three-dimensional flower piece shape2S4The preparation method of micro-nano wire array, is comprised the steps of：
（1）First the zinc metal sheet cut is polished with 3000 mesh sand paper, the oxide layer on surface is removed；
（2）Will（1）Zinc metal sheet after middle polishing is carried out cleaning 10min, then is used air gun with acetone, absolute ethyl alcohol, deionized water successively
Drying, is then put into reactor inner bag as substrate；
（3）Sulphur powder and Indium Tris acetylacetonate are according to 8：1 mixed in molar ratio is added in reactor, adds ethylene glycol, Ran Houjin
Row stirring or ultrasonic dissolution, are made into the homogeneous solution that indium salts concentration is 0.6M；
（4）Reactor is sealed, 220 DEG C of temperature, 2 hours reaction time is controlled；After reaction terminates, reactor naturally cools to room
Temperature, takes out and is cleaned and dried after sample, you can obtain the three-dimensional flower piece shape ZnIn of the homoepitaxial on zinc metal sheet2S4Micro-nano wire array
Film.
Embodiment 5：
（1）First the zinc metal sheet cut is polished with 3000 mesh sand paper, the oxide layer on surface is removed；
（2）Will（1）Zinc metal sheet after middle polishing is carried out cleaning 10min, then is used air gun with acetone, absolute ethyl alcohol, deionized water successively
Drying, is then put into reactor inner bag as substrate；
（3）Cysteine and indium nitrate are according to 2：1 mixed in molar ratio is added in reactor, adds ethylene glycol, Ran Houjin
Row stirring or ultrasonic dissolution, are made into the homogeneous solution that indium salts concentration is 0.4M；
（4）Reactor is sealed, 200 DEG C of temperature, 2 hours reaction time is controlled；After reaction terminates, reactor naturally cools to room
Temperature, takes out and is cleaned and dried after sample, you can obtain the three-dimensional flower piece shape ZnIn of the homoepitaxial on zinc metal sheet2S4Micro-nano wire array
Film.
Embodiment 6：
A kind of ZnIn of three-dimensional flower piece shape2S4In the preparation method of micro-nano wire array, 160 DEG C of temperature, reaction time 10 are controlled
Hour；Other conditions are with case study on implementation 1, you can obtain the three-dimensional flower piece shape ZnIn of the homoepitaxial on zinc metal sheet2S4Micro-nano wire
Array film.
Embodiment 7：
A kind of ZnIn of three-dimensional flower piece shape2S4In the preparation method of micro-nano wire array, temperature, 220 DEG C, reaction time 1 are controlled
Hour；Other conditions are with case study on implementation 1, you can obtain the three-dimensional flower piece shape ZnIn of the homoepitaxial on zinc metal sheet2S4Micro-nano wire
Array film.
Embodiment 8：
A kind of ZnIn of three-dimensional flower piece shape2S4In the preparation method of micro-nano wire array, 180 DEG C of temperature, reaction time 6 are controlled
Hour；Other conditions are with case study on implementation 1, you can obtain the three-dimensional flower piece shape ZnIn of the homoepitaxial on zinc metal sheet2S4Micro-nano wire
Array film.
Embodiment 9：
A kind of ZnIn of three-dimensional flower piece shape2S4In the preparation method of micro-nano wire array, 200 DEG C of temperature, reaction time 4 are controlled
Hour, indium salts concentration is 0.2M, and other conditions are with case study on implementation 1, you can obtain the three-dimensional flower piece shape of the homoepitaxial on zinc metal sheet
ZnIn2S4Micro-nano wire array film.
Photocatalytic degradation is tested：
Use differential responses time, ZnIn of other conditions with a kind of three-dimensional flower piece shape obtained by case study on implementation 12S4Micro-nano
Nanowire array film, under room temperature and simulated solar light irradiation, degrades to methyl orange, and methyl orange concentration is 5mg/ml, zinc metal sheet
Size is ZnIn on 3cm × 4cm, zinc metal sheet2S4The quality of film is less than 10mg.As can be known from Fig. 3, sample of the reaction time from 1-10h
Product have preferable degradation effect to methyl orange, and sample has highest degradation efficiency in 2h.Compared to powder body material,
In the ZnIn of zinc-base bottom growth2S4Micro-nano wire array film is easily recycled, and will not be fallen off substantially in degradation process existing
As, and it is relatively stable.
Claims (10)
1. a kind of preparation method of three-dimensional flower piece shape sulfur-indium-zinc micro-nano wire array, it is characterised in that this method uses following step
Suddenly：
（1）The zinc metal sheet cut is first carried out a certain degree of polishing, the oxide layer on surface is removed；
（2）Will（1）Zinc metal sheet after middle polishing is cleaned and dried, and is then put into as substrate in reactor inner bag；
（3）Indium source and sulphur source are added in reactor according to certain mixed in molar ratio, solvent is added, is then stirred
Or ultrasonic dissolution, it is made into certain density homogeneous solution；
（4）Reactor is sealed, 160 ~ 220 DEG C of temperature, 1 ~ 10 hour reaction time is controlled；After reaction terminates, reactor is natural
Room temperature is cooled to, takes out and is cleaned and dried after sample, you can obtain the three-dimensional flower piece shape ZnIn of the homoepitaxial on zinc metal sheet2S4It is micro--to receive
Nanowire arrays film.
2. a kind of preparation method of three-dimensional flower piece shape sulfur-indium-zinc micro-nano wire array according to claim 1, its feature exists
In step（1）Described in zinc metal sheet carry out pretreatment refer to be polished with the sand paper of 3000 mesh or so.
3. a kind of preparation method of three-dimensional flower piece shape sulfur-indium-zinc micro-nano wire array according to claim 1, its feature exists
In step（2）Described in zinc metal sheet carry out cleaning refer to successively use acetone, absolute ethyl alcohol, deionized water sonic oscillation
10min；Step（2）Described in zinc metal sheet be dried refer to be dried with not higher than 60 DEG C of baking oven or air gun.
4. a kind of preparation method of three-dimensional flower piece shape sulfur-indium-zinc micro-nano wire array according to claim 1, its feature exists
In step（3）Described in indium salts be inidum chloride, indium nitrate, indium sulfate, indium acetate or Indium Tris acetylacetonate, described indium salts
Concentration is 0.2-0.6M.
5. a kind of preparation method of three-dimensional flower piece shape sulfur-indium-zinc micro-nano wire array according to claim 1, its feature exists
In step（3）Described in organic solvent for ethylene glycol or ethylene glycol and ethanol mixture.
6. a kind of preparation method of three-dimensional flower piece shape sulfur-indium-zinc micro-nano wire array according to claim 1, its feature exists
In step（3）Described in sulphur source be sulphur powder, thiocarbamide, cysteine or thioacetamide.
7. a kind of preparation method of three-dimensional flower piece shape sulfur-indium-zinc micro-nano wire array according to claim 1, its feature exists
In step（3）Described in indium salts and sulphur source mol ratio be 1:2~1:8.
8. a kind of preparation method of three-dimensional flower piece shape sulfur-indium-zinc micro-nano wire array according to claim 1, its feature
It is, step（4）Described in reaction time be preferably 2-4h, preferably 180 ~ 200 DEG C of reaction temperature.
9. a kind of three-dimensional flower piece shape sulfur-indium-zinc micro-nano wire array is characterized in that, according to any methods describeds of claim 1-7
Prepare.
10. the ZnIn of three-dimensional flower piece shape according to claim 92S4Micro-nano wire array is in light-catalysed application.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710383926.7A CN107282070B (en) | 2017-05-26 | 2017-05-26 | Three-dimensional flower-shaped sulfur indium zinc micro-nanowire array and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710383926.7A CN107282070B (en) | 2017-05-26 | 2017-05-26 | Three-dimensional flower-shaped sulfur indium zinc micro-nanowire array and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107282070A true CN107282070A (en) | 2017-10-24 |
| CN107282070B CN107282070B (en) | 2020-01-10 |
Family
ID=60094659
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710383926.7A Active CN107282070B (en) | 2017-05-26 | 2017-05-26 | Three-dimensional flower-shaped sulfur indium zinc micro-nanowire array and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107282070B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107841791A (en) * | 2017-11-07 | 2018-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of monocrystalline indium nano wire and products thereof and application |
| CN108409157A (en) * | 2018-03-19 | 2018-08-17 | 中国矿业大学 | A kind of ZnIn2S4 nanometer wafer arrays structure and preparation method thereof |
| CN108993554A (en) * | 2018-07-09 | 2018-12-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of three-dimensional sheet nano wire and products thereof and application |
| CN109052988A (en) * | 2018-10-19 | 2018-12-21 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of zinc indium sulphur nano-chip arrays film |
| CN111790404A (en) * | 2020-07-08 | 2020-10-20 | 齐鲁工业大学 | Defective type sulfur indium zinc microsphere visible light catalyst, preparation method and application |
| CN112960688A (en) * | 2021-02-04 | 2021-06-15 | 河南大学 | ZnIn2S4Sodium ion battery negative electrode material and preparation method thereof |
| CN114751655A (en) * | 2022-04-20 | 2022-07-15 | 重庆大学 | Indium sulfide-based heterostructure thin film electrode and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884090A (en) * | 2006-05-23 | 2006-12-27 | 南开大学 | ZnIn2S4 nano materials and their synthesis method and application |
| CN101805136A (en) * | 2010-03-11 | 2010-08-18 | 许昌学院 | Chemical method for preparing nano mesh-like sulfur-indium-zinc ternary compound optoelectronic film on ITO conductive glass in situ |
| CN103331175A (en) * | 2013-07-10 | 2013-10-02 | 黑龙江大学 | Preparation method of MoS2/ZnIn2S4 nanosheet composite material |
| CN106268868A (en) * | 2016-08-24 | 2017-01-04 | 江苏大学 | A kind of TiO2hollow ball superficial growth ZnIn2s4the preparation method and applications of composite photo-catalyst |
-
2017
- 2017-05-26 CN CN201710383926.7A patent/CN107282070B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1884090A (en) * | 2006-05-23 | 2006-12-27 | 南开大学 | ZnIn2S4 nano materials and their synthesis method and application |
| CN101805136A (en) * | 2010-03-11 | 2010-08-18 | 许昌学院 | Chemical method for preparing nano mesh-like sulfur-indium-zinc ternary compound optoelectronic film on ITO conductive glass in situ |
| CN103331175A (en) * | 2013-07-10 | 2013-10-02 | 黑龙江大学 | Preparation method of MoS2/ZnIn2S4 nanosheet composite material |
| CN106268868A (en) * | 2016-08-24 | 2017-01-04 | 江苏大学 | A kind of TiO2hollow ball superficial growth ZnIn2s4the preparation method and applications of composite photo-catalyst |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107841791A (en) * | 2017-11-07 | 2018-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of monocrystalline indium nano wire and products thereof and application |
| CN107841791B (en) * | 2017-11-07 | 2020-02-21 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of single crystal indium nanowire, product and application thereof |
| CN108409157A (en) * | 2018-03-19 | 2018-08-17 | 中国矿业大学 | A kind of ZnIn2S4 nanometer wafer arrays structure and preparation method thereof |
| CN108993554A (en) * | 2018-07-09 | 2018-12-14 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of three-dimensional sheet nano wire and products thereof and application |
| CN108993554B (en) * | 2018-07-09 | 2021-03-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of three-dimensional sheet nanowire, product and application thereof |
| CN109052988A (en) * | 2018-10-19 | 2018-12-21 | 上海纳米技术及应用国家工程研究中心有限公司 | A kind of preparation method of zinc indium sulphur nano-chip arrays film |
| CN109052988B (en) * | 2018-10-19 | 2022-04-05 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of zinc indium sulfide nanosheet array film |
| CN111790404A (en) * | 2020-07-08 | 2020-10-20 | 齐鲁工业大学 | Defective type sulfur indium zinc microsphere visible light catalyst, preparation method and application |
| CN111790404B (en) * | 2020-07-08 | 2022-07-26 | 齐鲁工业大学 | Defective sulfur indium zinc microsphere visible light catalyst, preparation method and application |
| CN112960688A (en) * | 2021-02-04 | 2021-06-15 | 河南大学 | ZnIn2S4Sodium ion battery negative electrode material and preparation method thereof |
| CN112960688B (en) * | 2021-02-04 | 2022-04-12 | 河南大学 | ZnIn2S4Sodium ion battery negative electrode material and preparation method thereof |
| CN114751655A (en) * | 2022-04-20 | 2022-07-15 | 重庆大学 | Indium sulfide-based heterostructure thin film electrode and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107282070B (en) | 2020-01-10 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107282070A (en) | A kind of three-dimensional flower piece shape sulfur-indium-zinc micro-nano nanowire arrays and its preparation method and application | |
| Pan et al. | Recent progress in 2D metal-organic framework photocatalysts: synthesis, photocatalytic mechanism and applications | |
| CN103272639B (en) | Copolymerization modified graphite-phase carbon nitride nanosheet visible-light-driven photocatalyst | |
| Huang et al. | Broad spectrum response flower spherical-like composites CQDs@ CdIn2S4/CdS modified by CQDs with up-conversion property for photocatalytic degradation and water splitting | |
| CN106222685B (en) | A kind of WO of photoelectrocatalysis water decomposition3The preparation method of-LDH laminated films | |
| Bashiri et al. | Photoelectrochemical water splitting with tailored TiO2/SrTiO3@ g-C3N4 heterostructure nanorod in photoelectrochemical cell | |
| CN102795661B (en) | Method for preparing hierarchical floriform ZnIn2S4 ternary compound | |
| CN107081166A (en) | A kind of g C3N4/TiO2Multilevel hierarchy and preparation method thereof | |
| CN108043436A (en) | The preparation method and applications of molybdenum carbide/sulfur-indium-zinc composite photo-catalyst | |
| CN110252346B (en) | MoS2/SnS2Preparation method and application of/r-GO composite photocatalyst | |
| CN105502286B (en) | A kind of porous nano NiFe2O4Preparation method | |
| Huang et al. | A S-scheme heterojunction of Co9S8 decorated TiO2 for enhanced photocatalytic H2 evolution | |
| CN105854921B (en) | A kind of synthetic method of large-area two-dimensional composite nano materials | |
| CN106268902B (en) | A kind of preparation method of g-C3N4 quantum dot, the quantum dot sensitized BiVO4 photochemical catalyst of Ag | |
| CN103638950A (en) | CuS nanosheet photocatalytic material and preparation method thereof | |
| CN114588888B (en) | Photocatalyst, and preparation method and application thereof | |
| CN106362774A (en) | Preparation method for 1D/2D vertical Cds/MoS2 catalyst used for hydrogen production | |
| CN111437884A (en) | Composite photocatalyst and preparation method thereof | |
| CN103878011A (en) | Method for synthesizing GaN: ZnO solid solution photocatalyst | |
| CN111644192A (en) | g-C3N4@CdxZn1-xSe composite photocatalyst and preparation method and application thereof | |
| CN106693994A (en) | Preparation and application of core-shell structure bismuth sulfide@copper sulfide composite microspheres | |
| CN107282075A (en) | A kind of composite photo-catalyst and preparation method thereof | |
| CN107308973B (en) | Basic cobalt phosphate nanoneedle composite LTON photocatalyst and preparation method and application thereof | |
| CN115007174A (en) | Two-dimensional CdIn 2 S 4 Nanosheet and preparation method and application thereof | |
| CN110026207B (en) | CaTiO3@ZnIn2S4Nano composite material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230828 Address after: 201306 C Building, 888 Huanhu West Second Road, Pudong New Area, Shanghai Patentee after: Shanghai Helan Nanotechnology Co.,Ltd. Address before: 200241 No. 28 East Jiangchuan Road, Shanghai, Minhang District Patentee before: SHANGHAI NATIONAL ENGINEERING RESEARCH CENTER FOR NANOTECHNOLOGY Co.,Ltd. |