CN113213526B - CaIn 2 S 4 Hollow nanospheres, and preparation method and application thereof - Google Patents
CaIn 2 S 4 Hollow nanospheres, and preparation method and application thereof Download PDFInfo
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- CN113213526B CN113213526B CN202110597559.7A CN202110597559A CN113213526B CN 113213526 B CN113213526 B CN 113213526B CN 202110597559 A CN202110597559 A CN 202110597559A CN 113213526 B CN113213526 B CN 113213526B
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- 239000002077 nanosphere Substances 0.000 title claims description 44
- 238000002360 preparation method Methods 0.000 title claims description 21
- -1 calcium indium diethyldithiocarbamate Chemical compound 0.000 claims abstract description 28
- 239000002243 precursor Substances 0.000 claims abstract description 25
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 20
- LMBWSYZSUOEYSN-UHFFFAOYSA-N diethyldithiocarbamic acid Chemical compound CCN(CC)C(S)=S LMBWSYZSUOEYSN-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229950004394 ditiocarb Drugs 0.000 claims abstract description 20
- 150000002471 indium Chemical class 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000005979 thermal decomposition reaction Methods 0.000 claims abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 12
- 230000001699 photocatalysis Effects 0.000 claims description 10
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000001110 calcium chloride Substances 0.000 claims description 9
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- PSCMQHVBLHHWTO-UHFFFAOYSA-K indium(iii) chloride Chemical compound Cl[In](Cl)Cl PSCMQHVBLHHWTO-UHFFFAOYSA-K 0.000 claims description 9
- 150000003973 alkyl amines Chemical class 0.000 claims description 7
- GMYSDEOJMBLAKZ-UHFFFAOYSA-N calcium indium Chemical compound [Ca].[In] GMYSDEOJMBLAKZ-UHFFFAOYSA-N 0.000 claims description 7
- 229940116901 diethyldithiocarbamate Drugs 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000007146 photocatalysis Methods 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
- 125000005233 alkylalcohol group Chemical group 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 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
- 239000012295 chemical reaction liquid Substances 0.000 abstract description 9
- 238000010438 heat treatment Methods 0.000 abstract description 6
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000000463 material Substances 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 229910052976 metal sulfide Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 150000001356 alkyl thiols Chemical class 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001307 helium Substances 0.000 description 2
- 229910052734 helium Inorganic materials 0.000 description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000006303 photolysis reaction Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
- C01G15/006—Compounds containing, besides gallium, indium, or thallium, two or more other elements, with the exception of oxygen or hydrogen
-
- 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
-
- B01J35/23—
-
- B01J35/39—
-
- B01J35/51—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
-
- 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
Abstract
The invention discloses a CaIn 2 S 4 Mixing sodium diethyldithiocarbamate with calcium salt and indium salt to prepare calcium indium diethyldithiocarbamate, dispersing the calcium indium diethyldithiocarbamate serving as a precursor in a specific surfactant, heating to realize thermal decomposition of the precursor, and finally centrifuging, washing and drying reaction liquid to obtain CaIn with uniform appearance and size and good dispersibility 2 S 4 The nano hollow sphere is filled with CaIn 2 S 4 The technical blank for preparing the nano hollow sphere.
Description
Technical Field
The invention relates to the technical field of nano semiconductor materials, in particular to CaIn 2 S 4 Hollow nanospheres, and a preparation method and application thereof.
Background
The multi-element metal sulfide is widely applied to the visible light photocatalysis field due to the proper forbidden band width, in particular to ZnIn 2 S 4 And CaIn 2 S 4 . When the structure is a nano hollow sphere, the nano hollow sphere has the advantages of large specific surface area, low density and the like. The material can be used as a photocatalytic material for hydrogen production by water photolysis, organic pollutant photocatalytic degradation and CO photocatalytic reduction 2 And the like. To date, methods for preparing multi-metal sulfide hollow nanospheres have mainly focused on soft/hard template methods. These methods generally require introduction of a template and removal of the template by a special means after the reaction, and thus have disadvantages of complicated operation, low yield, and the like.
CaIn 2 S 4 As a ternary metal sulfide material, the forbidden band width is 2eV, so that the ternary metal sulfide material can respond in a 400-800nm visible light region, and has potential application in the catalytic fields of hydrogen production by photolysis of water, organic pollutant degradation by photocatalysis and the like. Preparation of CaIn at present 2 S 4 The method is mostly a hydrothermal method or a solvothermal method, and the CaIn is obtained 2 S 4 The appearance of the product is mostly flower-shaped or cluster-shaped. To date, no CaIn is available in the prior art 2 S 4 A method for preparing hollow nanospheres.
Disclosure of Invention
In view of the above, the present invention provides a CaIn 2 S 4 The hollow nanospheres, the preparation method and the application thereof fill in the CaIn 2 S 4 Technological blank for preparing hollow nanospheres, and prepared CaIn 2 S 4 The hollow nanospheres are uniform in shape and size and good in dispersity, and can be directly used as photocatalytic materials to be applied to the field of catalysis.
The technical scheme adopted by the invention is as follows:
CaIn 2 S 4 The preparation method of the hollow nanospheres specifically comprises the following steps:
step S1, preparing a calcium indium diethyl dithiocarbamate precursor by using calcium salt, indium salt and sodium diethyl dithiocarbamate;
step S2, dispersing the calcium indium diethyldithiocarbamate precursor in a specific surfactant, and carrying out thermal decomposition reaction in an inert gas atmosphere to obtain the product containing CaIn 2 S 4 The reaction solution of (1);
step S3, for the compound containing CaIn 2 S 4 The reaction solution (2) is centrifugally washed and dried to obtain CaIn 2 S 4 The hollow nanospheres.
Preferably, the specific steps of preparing the calcium indium diethyldithiocarbamate precursor by using the calcium salt, the indium salt and sodium diethyldithiocarbamate in step S1 are as follows:
dissolving calcium salt and indium salt and sodium diethyldithiocarbamate in a specific solvent according to a molar ratio of 1: 10-10: 1, uniformly stirring at normal temperature, standing for a set time, and performing washing, filtering, drying or baking procedures on the mixture by using the specific solvent to obtain a calcium indium diethyldithiocarbamate precursor;
preferably, the molar ratio of the calcium salt to the sodium diethyldithiocarbamate and the molar ratio of the indium salt to the sodium diethyldithiocarbamate are both 1: 6-6: 1.
Preferably, the calcium salt is any one of calcium carbonate, calcium acetate and calcium chloride, and the indium salt is any one of indium sulfate, indium nitrate and indium chloride.
Preferably, the specific solvent is one of deionized water, ethanol, toluene, and methanol.
Preferably, the amount ratio of the calcium indium diethyldithiocarbamate precursor dispersed in the specific surfactant in the step S2 is 1:8 to 8: 1.
Preferably, the temperature at which the calcium indium diethyldithiocarbamate precursor undergoes the thermal decomposition reaction in the specific surfactant in the step S2 is 160%
The reaction time is 0.5h-52h at the temperature.
Preferably, the specific surfactant is any one or a mixture of alkyl amine, alkyl alcohol, alkyl alkene and alkyl mercaptan.
The invention also provides CaIn prepared by the preparation method 2 S 4 The hollow nanospheres.
The invention also provides the CaIn 2 S 4 The hollow nanospheres are applied to the field of photocatalysis.
The invention has the beneficial effects that:
1. the method comprises the steps of preparing calcium indium diethyldithiocarbamate by mixing sodium diethyldithiocarbamate with calcium salt and indium salt by a wet chemical method, dispersing the calcium indium diethyldithiocarbamate serving as a precursor into a specific surfactant, heating to realize thermal decomposition of the precursor, and finally, carrying out heart washing and drying on reaction liquid to obtain CaIn with uniform appearance and size and good dispersibility 2 S 4 The nano hollow sphere is filled with CaIn 2 S 4 The technology of preparing the hollow nanospheres is blank. Prepared CaIn 2 S 4 The hollow nanospheres can be directly used as photocatalytic materials in the field of catalysis without removing a template, and have good application prospects and economic benefits.
2. The method has the advantages of simple and convenient operation process, low cost, short preparation flow, simple separation and purification process, short reaction time, rapid and large-scale preparation, and great improvement on CaIn 2 S 4 The production efficiency and the production quality of the hollow nanospheres.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows CaIn prepared by the method of the present invention 2 S 4 Transmission Electron Microscope (TEM) photographs of the hollow nanospheres.
FIG. 2 shows CaIn prepared by the method of the present invention 2 S 4 High magnification transmission electron microscopy (HRTEM) images of nano-hollows.
FIG. 3 is a flow chart of the method of the present invention.
Detailed Description
For better understanding of the technical solutions of the present invention, the following detailed descriptions of the embodiments of the present invention are provided with reference to the accompanying drawings.
It should be understood that the described embodiments are only some embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The present application is described in further detail below by way of specific embodiments in conjunction with the following figures.
The invention provides a CaIn 2 S 4 Mixing sodium diethyldithiocarbamate with calcium salt and indium salt to prepare calcium indium diethyldithiocarbamate, dispersing the calcium indium diethyldithiocarbamate serving as a precursor in a specific surfactant, heating to realize thermal decomposition of the precursor, and finally, carrying out heart washing and drying on reaction liquid to obtain CaIn with uniform appearance and size and good dispersibility 2 S 4 The hollow nanospheres.
CaIn of the invention 2 S 4 The preparation method of the hollow nanospheres specifically comprises the following steps:
and step S1, preparing a calcium indium diethyl dithiocarbamate precursor by using the calcium salt, the indium salt and sodium diethyl dithiocarbamate.
The preparation method of the calcium indium diethyl dithiocarbamate precursor comprises the following steps:
dissolving calcium salt and indium salt and sodium diethyldithiocarbamate in a specific solvent in a molar ratio of 1: 10-10: 1, wherein the molar ratio of the calcium salt to the sodium diethyldithiocarbamate is preferably 1: 6-6: 1, and the molar ratio of the indium salt to the sodium diethyldithiocarbamate is preferably 1: 6-6: 1. Then, stirring uniformly at normal temperature, standing for a set time, and then washing, filtering, drying or baking by using a specific solvent to obtain the calcium indium diethyl dithiocarbamate precursor.
The calcium salt can be selected from one of calcium carbonate, calcium acetate and calcium chloride, and the indium salt can be selected from one of indium sulfate, indium nitrate and indium chloride.
The specific solvent can be selected from one of deionized water, ethanol, toluene and methanol.
Step S2, dispersing the calcium indium diethyldithiocarbamate precursor in a specific surfactant, and carrying out thermal decomposition reaction in an inert gas atmosphere to obtain the product containing CaIn 2 S 4 The reaction solution of (1).
Specifically, the amount ratio of the calcium indium diethyldithiocarbamate precursor dispersed in the specific surfactant is 1: 8-8: 1.
The temperature of the calcium indium diethyl dithiocarbamate precursor in the specific surfactant for thermal decomposition reaction is 160 DEG
The reaction time is 0.5h-52h at the temperature. Preferably, the reaction temperature is 160-240 ℃, and the reaction time is 0.5-36 h.
The specific surfactant may be any one or a mixture of alkyl amine, alkyl alcohol, alkyl alkene and alkyl thiol.
Step S3, for CaIn 2 S 4 Centrifugally washing and drying the reaction solution to obtain CaIn 2 S 4 The hollow nanospheres.
The preparation method of the invention can be used for large-scale and rapid preparation of CaIn 2 S 4 Hollow nanospheres of CaIn 2 S 4 The hollow nanospheres can be directly used as photocatalytic materials to be applied to the field of catalysis, and have good application prospect and economic benefit.
FIG. 1 shows CaIn observed by Transmission Electron Microscopy (TEM) 2 S 4 Morphology of hollow nanospheres, from which it can be seen that CaIn prepared by the method of the present invention 2 S 4 The shape and the size of the hollow nanospheres are uniform.
FIG. 2 shows CaIn observed by high-magnification Transmission Electron microscopy (HRTEM) 2 S 4 Enlarged view of a part of the hollow nanosphere, from which CaIn is shown 2 S 4 Is in a nano hollow sphere structure.
The preparation method of ternary metal sulfide nanosheets of the present invention is described in detail below with reference to a number of specific examples.
In the first embodiment, the calcium salt is calcium chloride, the indium salt is indium chloride, the specific solvent is methanol, the specific surfactant is alkylamine, and the inert gas is helium.
CaIn 2 S 4 The specific preparation process of the hollow nanospheres is as follows:
step S1, dissolving 20mmol of calcium chloride, 20mmol of indium chloride and 100mmol of sodium diethyldithiocarbamate in 100ml of methanol, stirring for 3 hours at normal temperature, standing for layering, repeatedly washing with methanol for multiple times, filtering, and drying a filter cake in an oven for 6 hours to obtain a calcium indium diethyldithiocarbamate precursor;
step S2, dissolving and dispersing 0.6mmol of calcium indium diethyldithiocarbamate in 20mmol of alkylamine solution, heating to 160 ℃ for thermal decomposition reaction under the protection of helium gas, reacting for 18 hours to obtain the product containing CaIn 2 S 4 Reaction liquid of the hollow nanospheres.
S3, for CaIn 2 S 4 The reaction liquid of the hollow nanospheres is subjected to high-speed centrifugal washing and drying to obtain CaIn 2 S 4 Hollow nanosphere powder.
In the second embodiment, the calcium salt used in this embodiment is calcium chloride, the indium salt is indium chloride, the specific solvent is methanol, the specific surfactant is alkyl mercaptan, and the inert gas is argon.
CaIn 2 S 4 The specific preparation process of the hollow nanospheres is as follows:
and step S1, dissolving 20mmol of calcium chloride, 40mmol of indium chloride and 100mmol of sodium diethyldithiocarbamate in 100ml of methanol, stirring for 3 hours at normal temperature, standing for layering, repeatedly washing with methanol for multiple times, filtering, and drying a filter cake in an oven for 6 hours to obtain the calcium indium diethyldithiocarbamate precursor.
Step S2, dissolving and dispersing 0.7mmol of calcium indium diethyldithiocarbamate in 20mmol of alkyl mercaptan solution, heating to 200 ℃ under the protection of argon gas for thermal decomposition reaction, and obtaining CaIn-containing solution after reaction for 24 hours 2 S 4 Reaction liquid of the hollow nanospheres.
S3, for CaIn 2 S 4 Carrying out high-speed centrifugal washing and drying on reaction liquid of the hollow nanospheres to obtain CaIn 2 S 4 Hollow nanosphere powder.
In the third embodiment, the calcium salt used in this embodiment is calcium chloride, the indium salt is indium chloride, the specific solvent is methanol, the specific surfactant is a mixed solution of alkylamine and alkylthiol, and the inert gas is nitrogen.
CaIn 2 S 4 The specific preparation process of the hollow nanospheres is as follows:
and step S1, dissolving 20mmol of calcium chloride, 40mmol of indium chloride and 150mmol of sodium diethyldithiocarbamate in 100ml of water, stirring for 3 hours at normal temperature, standing for layering, repeatedly washing with water for multiple times, filtering, and drying a filter cake in an oven for 6 hours to obtain the calcium indium diethyldithiocarbamate precursor.
Step S2, dissolving and dispersing 0.4mmol of calcium indium diethyldithiocarbamate in a mixed solution of 20mmol of alkylamine and alkylthiol, heating to 280 ℃ for thermal decomposition reaction under the protection of nitrogen, and reacting for 36 hours to obtain the product containing CaIn 2 S 4 Reaction liquid of the hollow nanospheres.
S3, for CaIn 2 S 4 Carrying out high-speed centrifugal washing and drying on reaction liquid of the hollow nanospheres to obtain CaIn 2 S 4 Hollow nanosphere powder.
The method can rapidly prepare the CaIn with uniform appearance and size and good dispersibility by a wet chemical method 2 S 4 Hollow nanospheres, CaIn prepared therefrom 2 S 4 The hollow nanospheres can be directly used as photocatalytic materials in the field of catalysis without removing a template.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (5)
1. CaIn 2 S 4 The preparation method of the hollow nanospheres is characterized by comprising the following steps:
step S1, preparing a calcium indium diethyl dithiocarbamate precursor by using calcium salt, indium salt and sodium diethyl dithiocarbamate; the method for preparing the calcium-indium diethyl dithiocarbamate precursor by using the calcium salt, the indium salt and the sodium diethyl dithiocarbamate comprises the following specific steps: dissolving calcium salt and indium salt and sodium diethyldithiocarbamate in a specific solvent according to a molar ratio of 1: 10-10: 1, uniformly stirring at normal temperature, standing for a set time, and performing washing, filtering, drying or baking procedures on the mixture by using the specific solvent to obtain a calcium indium diethyldithiocarbamate precursor; the specific solvent is one of deionized water, ethanol, toluene and methanol;
step S2, dispersing the calcium indium diethyldithiocarbamate precursor in a specific surfactant, and performing inert gas atmosphereThermally decomposing to obtain CaIn 2 S 4 The reaction solution of (1); the temperature of the thermal decomposition reaction is 160-300 ℃, and the reaction time is 0.5-52 h; the specific surfactant is any one or a mixture of alkyl amine, alkyl alcohol, alkyl alkene and alkyl mercaptan;
step S3, for CaIn 2 S 4 The reaction solution (2) is centrifugally washed and dried to obtain CaIn 2 S 4 The hollow nanospheres.
2. The CaIn of claim 1 2 S 4 The preparation method of the hollow nanospheres is characterized in that the molar ratio of the calcium salt to the sodium diethyldithiocarbamate and the molar ratio of the indium salt to the sodium diethyldithiocarbamate are both 1: 6-6: 1.
3. The CaIn of any one of claims 1-2 2 S 4 The preparation method of the hollow nanospheres is characterized in that the calcium salt is any one of calcium carbonate, calcium acetate and calcium chloride, and the indium salt is any one of indium sulfate, indium nitrate and indium chloride.
4. CaIn prepared by the preparation method of any one of claims 1-3 2 S 4 The hollow nanospheres.
5. The CaIn of claim 4 2 S 4 The hollow nanospheres are applied to the field of photocatalysis.
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| CN106745199A (en) * | 2016-12-30 | 2017-05-31 | 东华大学 | A kind of method that atmospheric low-temperature prepares hollow indium sulfide microballoon without template |
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| US20050036938A1 (en) * | 2003-08-13 | 2005-02-17 | Taegwhan Hyeon | Method for synthesizing nanoparticles of metal sulfides |
| CN102633297A (en) * | 2012-04-11 | 2012-08-15 | 中国科学院苏州纳米技术与纳米仿生研究所 | Preparation method of general-purpose multi-metal sulfide nano-material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4728682A (en) * | 1985-09-30 | 1988-03-01 | The United States Of America As Represented By The Secretary Of The Navy | Metal ternary sulfides |
| CN106745199A (en) * | 2016-12-30 | 2017-05-31 | 东华大学 | A kind of method that atmospheric low-temperature prepares hollow indium sulfide microballoon without template |
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