CN107282070B - Three-dimensional flower-shaped sulfur indium zinc micro-nanowire array and preparation method and application thereof - Google Patents
Three-dimensional flower-shaped sulfur indium zinc micro-nanowire array and preparation method and application thereof Download PDFInfo
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- 239000002070 nanowire Substances 0.000 title claims abstract description 57
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- YYKKIWDAYRDHBY-UHFFFAOYSA-N [In]=S.[Zn] Chemical compound [In]=S.[Zn] YYKKIWDAYRDHBY-UHFFFAOYSA-N 0.000 title claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 19
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- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- 238000003491 array Methods 0.000 claims abstract description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 46
- 229910052725 zinc Inorganic materials 0.000 claims description 46
- 239000011701 zinc Substances 0.000 claims description 46
- 238000006243 chemical reaction Methods 0.000 claims description 39
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 24
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- 150000002471 indium Chemical class 0.000 claims description 13
- 238000004140 cleaning Methods 0.000 claims description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 10
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- 238000001035 drying Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000005498 polishing Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- 238000007146 photocatalysis Methods 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 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
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- 235000018417 cysteine Nutrition 0.000 claims description 4
- 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 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
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 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
- 238000002156 mixing Methods 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
- 244000137852 Petrea volubilis Species 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000000227 grinding Methods 0.000 claims description 2
- SKWCWFYBFZIXHE-UHFFFAOYSA-K indium acetylacetonate Chemical compound CC(=O)C=C(C)O[In](OC(C)=CC(C)=O)OC(C)=CC(C)=O SKWCWFYBFZIXHE-UHFFFAOYSA-K 0.000 claims description 2
- 230000010355 oscillation Effects 0.000 claims description 2
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 4
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- 229910052739 hydrogen Inorganic materials 0.000 abstract description 4
- 239000001257 hydrogen Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
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- 231100000252 nontoxic Toxicity 0.000 abstract description 2
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- 239000000463 material Substances 0.000 description 10
- 238000000861 blow drying Methods 0.000 description 5
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- 238000006731 degradation reaction Methods 0.000 description 4
- 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
- 239000002086 nanomaterial Substances 0.000 description 4
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- 238000011161 development Methods 0.000 description 2
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- 238000003912 environmental pollution Methods 0.000 description 2
- 150000002466 imines Chemical class 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
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- 150000004763 sulfides Chemical class 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- -1 amine compounds Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
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- 238000002474 experimental method Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- ZJDCLINAWYFEFQ-UHFFFAOYSA-N indium;pentane-2,4-dione Chemical compound [In].CC(=O)CC(C)=O ZJDCLINAWYFEFQ-UHFFFAOYSA-N 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
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- 230000001590 oxidative effect Effects 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- UDWJTDBVEGNWAB-UHFFFAOYSA-N zinc indium(3+) sulfide Chemical compound [S-2].[Zn+2].[In+3] UDWJTDBVEGNWAB-UHFFFAOYSA-N 0.000 description 1
Images
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
Hair brushThe invention discloses a three-dimensional flower-shaped sulfur-indium-zinc micro-nanowire array and a preparation method and application thereof2S4Micro-nanowire arrays. ZnIn with three-dimensional flower sheet structure prepared by the invention2S4Micro-nanowire arrays, the pioneer on solid substrates; ZnIn prepared according to the method provided by the invention2S4The micro-nano wire array has the excellent characteristics of high specific surface area, low reflectivity, good light trapping property, less defects, repeated use and the like; the preparation method is simple, the process is easy to control, the cost is low, the preparation method is non-toxic and environment-friendly, and the preparation method has huge application prospects in the fields of photocatalytic hydrogen production, photocatalytic degradation of organic pollutants, artificial photosynthesis, photocatalytic sterilization, solar cells and the like.
Description
Technical Field
The invention belongs to the field of material preparation and solar energy application and conversion, and particularly relates to a three-dimensional flower-shaped sulfur indium zinc micro-nanowire array and a preparation method and application thereof.
Background
Along with the rapid development of the economy of all countries in the world, the demand of human beings on energy is higher and higher, and the call for environmental protection is also rising. However, the traditional fossil energy is a non-renewable energy and faces the trend of increasing exhaustion, and the fossil energy generates CO when being burned2、SO2And the harmful gases have great damage to the environment. Therefore, solving the problems of energy crisis and environmental pollution becomes two main problems facing the world at present, and all countries in the world take the establishment of a green, environment-friendly and sustainable new energy system as a national important development strategy. The semiconductor photocatalysis technology is an efficient and safe environment-friendly environment purification and hydrogen production technology, has huge application potential in solving the problems of environmental pollution and energy crisis, and has wide application in the fields of photocatalytic hydrogen production, photocatalytic degradation of organic pollutants, artificial photosynthesis, photocatalytic sterilization, solar cells and the like.
In recent yearsTransition metal sulfide type photocatalysts are widely researched and paid attention to, because sulfides generally have narrow forbidden band widths and can directly absorb visible light to generate photocatalytic reaction. Ternary sulfide ZnIn2S4As AB2X4One of the group of semiconductor devices has a band gap width of about 2.4eV, is a visible light responsive semiconductor material, has excellent optical properties and catalytic stability, and thus has received much attention in both the scientific and industrial fields. For example, a method for preparing a hierarchical flower-shaped ZnIn by a solvothermal method in Chinese patent with the publication number of CN102795661A2S4The ternary compound has better effect in the fields of photocatalytic degradation of organic matters, air purification and the like. Chinese patent with publication number CN103736501A, a ZnIn with homogeneous heterogeneous phase prepared by solvothermal method2S4The composite material can obviously degrade organic dyes such as methyl orange and the like by photocatalysis. In Chinese patent with publication number CN103908971A, ZnIn for selectively catalyzing and oxidizing coupled amine to generate imine is prepared by a hydrothermal method2S4The photocatalyst can selectively oxidize amine compounds to generate imine in the air under the irradiation of visible light. ZnIn prepared by the method2S4Have their own advantages, but also have many disadvantages. Such as ZnIn they produce2S4All are powder materials, have poor uniformity, are easy to agglomerate, and are not beneficial to recovery and reuse. It is known that for inorganic nanomaterials, the physical and chemical properties of the inorganic nanomaterials are greatly influenced by the factors such as morphology, size and structure. One-dimensional nano materials such as nanowires, nanotubes and the like have excellent characteristics of high specific surface area, good light limiting performance and the like, and are widely applied to the field of semiconductor catalysis of oxides, sulfides and the like. However, ZnIn is currently being treated2S4Most of the research is focused on multi-dimensional materials such as nano sheets and microspheres, and the preparation method still has a great challenge to the field of preparation of one-dimensional materials such as nano wires and nano tubes.
So far, only 3 references to ZnIn have appeared2S4The public report of the preparation of one-dimensional nanometer materials. For example, Gao, etc. adopts solvothermal method to prepare one-dimensional ZnIn2S4Nanowires and nanotubes, but with surfactants and as powder material (Gou XL, Cheng FY, Shi YH, Zhang L, Peng SJ, Chen J, Shen PW.Journal of the American Chemical Society2006,128, 7222.). Wei et al synthesized ZnIn by two-step process2S4Nanowires, but surfactants are also employed and are powder materials (Wei QL.Chinese Journal of Inorganic Chemistry2010,26, 269.). Shi et al prepared ZnIn using polycarbonate as a template by a hydrothermal method2S4Nanowires and nanotubes, also powder materials (Shi L, Yin P, Dai Y).Langmuir the Acs Journal of Surfaces & Colloids2013,29, 12818.). ZnIn prepared by these methods2S4The one-dimensional nano material has the disadvantages of complex process, high cost and difficult recovery. Therefore, the method is simple, low in cost, large-area preparation and easy to recover ZnIn2S4The nanowire array film has important practical significance.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention provides the three-dimensional flower-shaped sulfur indium zinc micro-nanowire array and the preparation method and application thereof, the process is simple, the safety and the reliability are realized, the cost is low, and the three-dimensional flower-shaped sulfur indium zinc micro-nanowire array has a good application prospect in the field of solar photocatalysis.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of a three-dimensional flower-shaped sulfur indium zinc micro-nanowire array is characterized by comprising the following steps:
(1) firstly, grinding the cut zinc sheet to a certain degree to remove an oxide layer on the surface;
(2) cleaning and drying the polished zinc sheet in the step (1), and then putting the zinc sheet serving as a substrate into an inner container of a reaction kettle;
(3) mixing an indium source and a sulfur source according to a certain molar ratio, adding the mixture into a reaction kettle, adding a solvent, and stirring or ultrasonically dissolving to prepare a uniform solution with a certain concentration;
(4) will be provided withSealing the reaction kettle, controlling the temperature at 160 ~ 220 ℃ and the reaction time at 1 ~ 10 hours, naturally cooling the reaction kettle to room temperature after the reaction is finished, taking out a sample, cleaning and drying to obtain the three-dimensional flower-shaped ZnIn uniformly grown on the zinc sheet2S4Micro-nanowire array films.
The step (1) of pretreating the zinc sheet refers to polishing with sand paper of about 3000 meshes.
The step (2) of cleaning the zinc sheet refers to ultrasonic oscillation for 10min by using acetone, absolute ethyl alcohol and deionized water in sequence; the step (2) of drying the zinc sheet refers to drying by using an oven or an air gun with the temperature of not higher than 60 ℃.
The indium salt in the step (3) is indium chloride, indium nitrate, indium sulfate, indium acetate or indium acetylacetonate, and the concentration of the indium salt is 0.2-0.6M.
The organic solvent in the step (3) is ethylene glycol or a mixture of ethylene glycol and ethanol.
The sulfur source in the step (3) is sulfur powder, thiourea, cysteine or thioacetamide.
The molar ratio of the indium salt to the sulfur source in step (3) is 1:2 ~ 1: 8.
The reaction time in the step (4) is preferably 2-4h, and the reaction temperature is preferably 180 ~ 200 ℃.
A three-dimensional flower-like micro-nano wire array of indium zinc sulfide, which is prepared by any one of the methods.
Three-dimensional flower-shaped ZnIn2S4Micro-nanowire arrays are used in photocatalysis.
The invention prepares ZnIn with a three-dimensional flower sheet structure on a zinc sheet substrate by a one-step hydrothermal method2S4The micro-nano wire array film is originated on a solid substrate, has no template and no surfactant, not only has two-dimensional sheet structure characteristics, but also has the advantages of a nano wire array structure. Compared with the prior shape structure, the ZnIn prepared by the invention2S4The micro-nano wire array has high specific surface area, low reflectivity, good light trapping property, less defects andcan be repeatedly used, and the like. The preparation method is simple, the process is easy to control, the cost is low, the preparation method is non-toxic and environment-friendly, and the preparation method has huge application prospects in the fields of photocatalytic hydrogen production, photocatalytic degradation of organic pollutants, artificial photosynthesis, photocatalytic sterilization, solar cells and the like.
Compared with the prior art, the invention has the following advantages:
1. the raw materials used in the invention are relatively easy to obtain, the preparation process is simple, safe and reliable, the cost is low, and the method has a good application prospect in the field of solar photocatalysis.
2. The invention discloses a three-dimensional flower-shaped ZnIn directly grown on a conductive substrate2S4The micro-nanowire array belongs to a one-dimensional nano-micron material and has the excellent characteristics of high specific surface area, low reflectivity, good light trapping property, less defects, easiness in recycling and the like.
3. ZnIn prepared by the invention2S4The thickness of the nano-sheet on the surface of the micro-nano wire is about 5-10nm, so that the specific surface area is increased, the electron escape is facilitated, the recombination probability of a photon-generated carrier is greatly reduced, and the photocatalytic activity is improved.
4. The invention firstly obtains ZnIn by a one-step solvothermal method2S4Micro-nano wire arrays, which also provide a thought for preparing other multi-component compound nano wire arrays.
Drawings
FIG. 1 is a three-dimensional flower-like ZnIn grown on a zinc sheet substrate of example 12S4XRD patterns of micro-nanowire arrays;
FIG. 2 is a three-dimensional flower-like ZnIn grown on a zinc sheet substrate of example 12S4SEM images of micro-nanowire arrays at different resolutions;
FIG. 3 shows three-dimensional flower-shaped ZnIn grown on a zinc sheet substrate under different reaction times2S4Comparative figures for the degradation effect of micro-nanowire arrays.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1:
three-dimensional flower-shaped sulfur indium zinc (ZnIn)2S4) A method of preparing a micro-nanowire array, comprising the steps of:
(1) firstly, polishing a cut zinc sheet by 3000-mesh abrasive paper to remove an oxide layer on the surface;
(2) cleaning the polished zinc sheet in the step (1) for 10min by using acetone, absolute ethyl alcohol and deionized water in sequence, blow-drying by using an air gun, and then putting the zinc sheet serving as a substrate into an inner container of a reaction kettle;
(3) thioacetamide and indium chloride were mixed as follows: 1, adding the mixture into a reaction kettle, adding ethylene glycol, and stirring or ultrasonically dissolving to prepare a uniform solution with indium salt concentration of 0.4M;
(4) sealing the reaction kettle, controlling the temperature to be 200 ℃, and reacting for 2 hours; after the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the sample is taken out and cleaned and dried to obtain the three-dimensional flower-shaped ZnIn uniformly grown on the zinc sheet2S4Micro-nanowire array films.
FIG. 1 shows ZnIn obtained in this example2S4XRD pattern of the film; as can be seen from FIG. 1, almost all peaks except the peak of the zinc substrate corresponded to ZnIn2S4The peak of (2) is relatively sharp, indicating that the crystallinity is good.
FIG. 2 shows ZnIn obtained in this example2S4SEM image of the film; as can be seen from FIG. 2, the surface of the micro-nano wire is formed by obvious three-dimensional flower sheets, and the micro-nano wire grows more uniformly.
Example 2:
three-dimensional flower-shaped ZnIn2S4A method of preparing a micro-nanowire array, comprising the steps of:
(1) firstly, polishing a cut zinc sheet by 3000-mesh abrasive paper to remove an oxide layer on the surface;
(2) cleaning the polished zinc sheet in the step (1) for 10min by using acetone, absolute ethyl alcohol and deionized water in sequence, blow-drying by using an air gun, and then putting the zinc sheet serving as a substrate into an inner container of a reaction kettle;
(3) mixing thiourea and indium sulfate according to a ratio of 4: 1, adding the mixture into a reaction kettle, adding ethylene glycol, and stirring or ultrasonically dissolving to prepare a uniform solution with indium salt concentration of 0.2M;
(4) sealing the reaction kettle, controlling the temperature to be 160 ℃, and reacting for 10 hours; after the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the sample is taken out and cleaned and dried to obtain the three-dimensional flower-shaped ZnIn uniformly grown on the zinc sheet2S4Micro-nanowire array films.
Example 3:
three-dimensional flower-shaped ZnIn2S4A method of preparing a micro-nanowire array, comprising the steps of:
(1) firstly, polishing a cut zinc sheet by 3000-mesh abrasive paper to remove an oxide layer on the surface;
(2) cleaning the polished zinc sheet in the step (1) for 10min by using acetone, absolute ethyl alcohol and deionized water in sequence, blow-drying by using an air gun, and then putting the zinc sheet serving as a substrate into an inner container of a reaction kettle;
(3) cysteine and indium acetate were mixed as per 6: 1, adding the mixture into a reaction kettle, adding ethylene glycol, and stirring or ultrasonically dissolving to prepare a uniform solution with indium salt concentration of 0.4M;
(4) sealing the reaction kettle, controlling the temperature at 180 ℃ and reacting for 6 hours; after the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the sample is taken out and cleaned and dried to obtain the three-dimensional flower-shaped ZnIn uniformly grown on the zinc sheet2S4Micro-nanowire array films.
Example 4:
three-dimensional flower-shaped ZnIn2S4A method of preparing a micro-nanowire array, comprising the steps of:
(1) firstly, polishing a cut zinc sheet by 3000-mesh abrasive paper to remove an oxide layer on the surface;
(2) cleaning the polished zinc sheet in the step (1) for 10min by using acetone, absolute ethyl alcohol and deionized water in sequence, blow-drying by using an air gun, and then putting the zinc sheet serving as a substrate into an inner container of a reaction kettle;
(3) the sulfur powder and the acetylacetone indium were mixed in a ratio of 8: 1, adding the mixture into a reaction kettle, adding ethylene glycol, and stirring or ultrasonically dissolving to prepare a uniform solution with indium salt concentration of 0.6M;
(4) sealing the reaction kettle, controlling the temperature to be 220 ℃ and reacting for 2 hours; after the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the sample is taken out and cleaned and dried to obtain the three-dimensional flower-shaped ZnIn uniformly grown on the zinc sheet2S4Micro-nanowire array films.
Example 5:
(1) firstly, polishing a cut zinc sheet by 3000-mesh abrasive paper to remove an oxide layer on the surface;
(2) cleaning the polished zinc sheet in the step (1) for 10min by using acetone, absolute ethyl alcohol and deionized water in sequence, blow-drying by using an air gun, and then putting the zinc sheet serving as a substrate into an inner container of a reaction kettle;
(3) cysteine and indium nitrate were added as 2: 1, adding the mixture into a reaction kettle, adding ethylene glycol, and stirring or ultrasonically dissolving to prepare a uniform solution with indium salt concentration of 0.4M;
(4) sealing the reaction kettle, controlling the temperature to be 200 ℃, and reacting for 2 hours; after the reaction is finished, the reaction kettle is naturally cooled to room temperature, and the sample is taken out and cleaned and dried to obtain the three-dimensional flower-shaped ZnIn uniformly grown on the zinc sheet2S4Micro-nanowire array films.
Example 6:
three-dimensional flower-shaped ZnIn2S4In the preparation method of the micro-nanowire array, the temperature is controlled to be 160 ℃, and the reaction time is 10 hours; the other conditions are the same as the embodiment 1, and the three-dimensional flower which grows uniformly on the zinc sheet can be obtainedFlaky ZnIn2S4Micro-nanowire array films.
Example 7:
three-dimensional flower-shaped ZnIn2S4In the preparation method of the micro-nanowire array, the temperature is controlled at 220 ℃, and the reaction time is 1 hour; the other conditions are the same as the embodiment 1, and the three-dimensional flower-shaped ZnIn uniformly grown on the zinc sheet can be obtained2S4Micro-nanowire array films.
Example 8:
three-dimensional flower-shaped ZnIn2S4In the preparation method of the micro-nanowire array, the temperature is controlled at 180 ℃, and the reaction time is 6 hours; the other conditions are the same as the embodiment 1, and the three-dimensional flower-shaped ZnIn uniformly grown on the zinc sheet can be obtained2S4Micro-nanowire array films.
Example 9:
three-dimensional flower-shaped ZnIn2S4In the preparation method of the micro-nanowire array, the temperature is controlled to be 200 ℃, the reaction time is 4 hours, the concentration of indium salt is 0.2M, and other conditions are the same as the embodiment 1, so that the three-dimensional flower-shaped ZnIn uniformly grown on the zinc sheet can be obtained2S4Micro-nanowire array films.
Photocatalytic degradation experiment:
three-dimensional flower-like ZnIn obtained in the same way as the embodiment 1 under different reaction times and other conditions2S4The micro-nano wire array film degrades methyl orange at room temperature under the irradiation of simulated sunlight, the concentration of the methyl orange is 5mg/ml, the size of a zinc sheet is 3cm multiplied by 4cm, and ZnIn is arranged on the zinc sheet2S4The mass of the film is less than 10 mg. As can be seen from FIG. 3, the samples with reaction times ranging from 1 h to 10h all have better degradation effect on methyl orange, and the samples have the highest degradation efficiency at 2 h. ZnIn grown on zinc base compared with powder material2S4The micro-nanowire array film is easy to recycle, basically does not fall off in the degradation process, and is stable.
Claims (6)
1. A preparation method of a three-dimensional flower-shaped sulfur indium zinc micro-nanowire array is characterized by comprising the following steps:
(1) firstly, grinding the cut zinc sheet to a certain degree to remove an oxide layer on the surface; concretely, 3000-mesh sand paper is used for polishing;
(2) cleaning and drying the polished zinc sheet in the step (1), and then putting the zinc sheet serving as a substrate into an inner container of a reaction kettle;
(3) mixing indium salt and a sulfur source according to a certain molar ratio, adding the mixture into a reaction kettle, adding ethylene glycol, and stirring or ultrasonically dissolving to prepare a uniform solution with a certain concentration;
the indium salt in the step (3) is indium chloride, indium nitrate, indium sulfate, indium acetate or indium acetylacetonate, and the concentration of the indium salt is 0.2-0.6M;
the mol ratio of the indium salt to the sulfur source in the step (3) is 1:2 ~ 1: 8;
(4) sealing the reaction kettle, controlling the temperature at 160 ~ 220 ℃ and the reaction time at 1 ~ 10 hours, naturally cooling the reaction kettle to room temperature after the reaction is finished, taking out a sample, cleaning and drying to obtain the three-dimensional flower-shaped ZnIn uniformly grown on the zinc sheet2S4Micro-nanowire array films.
2. The method for preparing the three-dimensional flower-shaped sulfur indium zinc micro-nanowire array as claimed in claim 1, wherein the step (2) of cleaning the zinc sheet comprises the steps of sequentially performing ultrasonic oscillation on the zinc sheet for 10min by using acetone, absolute ethyl alcohol and deionized water; the step (2) of drying the zinc sheet refers to drying by using an oven or an air gun with the temperature of not higher than 60 ℃.
3. The method for preparing the three-dimensional flower-shaped sulfur indium zinc micro-nanowire array as claimed in claim 1, wherein the sulfur source in the step (3) is sulfur powder, thiourea, cysteine or thioacetamide.
4. The method for preparing the three-dimensional flower-like sulfur indium zinc micro-nanowire array as claimed in claim 1, wherein the reaction time in the step (4) is 2-4h, and the reaction temperature is 180 ~ 200 ℃.
5. A three-dimensional flower-like micro-nanowire array of zinc indium sulfide prepared according to any one of claims 1 to 4.
6. ZnIn in the form of three-dimensional flower according to claim 52S4Micro-nanowire arrays are used in photocatalysis.
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| 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 |
| 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 |
| 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 |
| 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 |
| 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 |
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