CN106745199B - A kind of method that atmospheric low-temperature prepares hollow indium sulfide microballoon without template - Google Patents
A kind of method that atmospheric low-temperature prepares hollow indium sulfide microballoon without template Download PDFInfo
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- CN106745199B CN106745199B CN201611251981.2A CN201611251981A CN106745199B CN 106745199 B CN106745199 B CN 106745199B CN 201611251981 A CN201611251981 A CN 201611251981A CN 106745199 B CN106745199 B CN 106745199B
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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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
Abstract
The present invention relates to a kind of method that atmospheric low-temperature prepares hollow indium sulfide microballoon without template, under the conditions of magnetic agitation, indium salts aqueous solution and thioamides aqueous solution are mixed, adjust pH value, then reaction is heated in microwave open system, cooling, filtering, washing, freeze-drying to get.The present invention is not necessarily to template, and primary first-order equation can directly obtain product, and reaction midway is not necessarily to other additives；The hollow indium sulfide microballoon good dispersion being prepared, uniform particle sizes, size and wall thickness are controllable, and shape is uniform, and stability is high；Heating reaction is carried out using Microwave Assisted Process in normal-pressure open system, avoids hydro-thermal method or high temperature and high pressure that solvent-thermal method must use, safe, energy saving；Method and technical process are simple, environmental-friendly, and reaction carries out in water phase, and product is easily isolated and cleans, and yield is high, can be used for large-scale production.
Description
Technical field
The invention belongs to the preparation field of indium sulfide microballoon, more particularly to a kind of atmospheric low-temperature prepares hollow vulcanization without template
The method of indium microballoon.
Background technology
Indium sulfide In2S3It is a kind of semi-conducting material of direct narrow band gap, energy gap is 2-2.2eV at room temperature, is had
Good chemical stability and excellent photoelectricity, thermoelectricity capability.In2S3It is applied to optically and electrically equipment, too such as photovoltaic
Positive energy battery, photoconductor, superionic conductors, lithium ion battery.
At present to In2S3The research of material is more popular, the In of preparation2S3Also there are many different forms for product, include
Nanoparticulate, rodlike, band-like, tubulose and hollow microsphere etc..The synthesis of hollow microsphere mostly uses template, such as Gao with water
It is sulphur source and soft template to close the dimethyl sulphide that hydrazine reduction DMSO is generated, and is reacted 48 hours, is prepared at 180 DEG C using hydro-thermal method
The indium sulfide (Gao, Nanotechnology, 2006,17,320-324) of half-shell structure.
The method that template-free method prepares hollow indium sulfide microballoon also has been reported that, such as Y.Liu prepared using two-step method it is hollow
Indium sulfide microballoon：Carbon disulfide (CS is used first2) it is sulphur source, it is anti-at 180 DEG C using solvent-thermal method by solvent of absolute ethyl alcohol
Answer 12 hours, reaction solution continues to react 12 hours at 180 DEG C using solvent-thermal method after adding a certain amount of thiocarbamide later, it is final must
To hollow microsphere (Y.Liu, et al, Materials Chemistry and Physics, 2007,101,362-366)；
X.Cao etc. is first that sulphur source prepares indium sulfide colloid using thiocarbamide, later by indium sulfide colloidal dispersions in benzene, using solvent heat
Method is reacted 24 hours at 180 DEG C, and hollow indium sulfide microballoon (X.Cao et al, Colloids and Surfaces are prepared
A:Physicochem.Eng.Aspects,2007,297,183–190)；Shao Shaofeng etc. is sulphur source using thiocarbamide, is with amino acid
The In with multi-level nano-structure is prepared after being reacted 72 hours at 180 DEG C using hydro-thermal method in growth inhibitor2S3It is hollow micro-
Ball (Shao Shaofeng etc., Acta PhySico-Chimica Sinica, 2009,25,411-416)；L.Liu etc. is sulphur source using thiocarbamide, is adopted by solvent of water
It is reacted 24 hours at 150 DEG C with hydro-thermal method, hollow indium sulfide microballoon (L.Liu, et al, Cryst.Growth is prepared
Des.,2009,9,113-117)；S.Rengaraj is sulphur source using thiosemicarbazides, and solvent-thermal method is used by solvent of water/ethyl alcohol
Reacted 10-24 hours at 180 DEG C, obtain hollow indium sulfide microballoon (S.Rengaraj, et al, Langmuir, 2011,27,
5534–5541)；Nayak etc. is sulphur source using cystine, is reacted 30 hours, is obtained at 150 DEG C using hydro-thermal method in the presence of oxalic acid
To hollow indium sulfide microballoon (Nayak, et al, CrystEngComm, 2014,16,8064)；Shi etc. is sulphur source using thiocarbamide,
Reacted 24 hours at 165 DEG C using hydro-thermal method, obtain hollow indium sulfide microballoon (Shi, et al, RSC Adv., 2014,4,
17245–17248)。
All there are problems in the above method：First, hydro-thermal method or solvent-thermal method use small-sized hydrothermal reaction kettle
Equal high-tension apparatuses, complex process, disposable preparation amount are few, it is difficult to produce in batches；Secondly, reaction system must be heated to 150-180
DEG C, there are certain risks, take (10-24 hours), energy consumption is big；Third, part sulphur source toxicity is big, and carbon disulfide is easily waved
Hair, and there is cytotoxicity, thiosemicarbazides is extremely toxic substance, it is desirable that production equipment is closed, and operating personnel should dress protection and use
Tool causes to hinder for associated production.4th, organic solvent, such as ethyl alcohol, benzene, easy firing are mostly used in building-up process, part has
It is toxic.
Since its special form and hollow structure make hollow In2S3Microballoon has prodigious specific surface area, it will be made in crowd
It is multi-field that there is important application potential, it such as can be used for uvioresistant, coloring, the arrangement of special optical performance, catalytic performance and half
The fields such as conductor.But up to the present do not have also under normal pressure, low temperature in water phase without the hollow In of templated synthesis2S3The report of microballoon.
In order to preferably promote the use of hollow In2S3Microballoon, preparation process find operation more there is still a need for optimizing and improving
Simplicity, being easier to industrialized production, environmental-friendly preparation method improves reaction efficiency to reduce the reaction time.
Invention content
Technical problem to be solved by the invention is to provide a kind of atmospheric low-temperatures to prepare hollow indium sulfide microballoon without template
Method, of the invention preparation is simple, raw material is easy to get, suitable for large-scale production hollow indium sulfide microwave
Assistant preparation method.
The method that a kind of atmospheric low-temperature of the present invention prepares hollow indium sulfide microballoon without template, including：
Under the conditions of magnetic agitation, indium salts aqueous solution and thioamides aqueous solution are mixed, pH value is adjusted, is then opened in microwave
It puts and heats reaction in system, it is cooling, it filters, washing is freeze-dried to get hollow indium sulfide microballoon.
A concentration of 0.001-0.2mol/L of the indium salts aqueous solution, wherein indium salts are indium nitrate and/or inidum chloride.
A concentration of 0.001-0.2mol/L of the thioamides aqueous solution, wherein thioamides are thiopropionamide, 2-
Methyl thio propionamide (also referred to as thio-iso-butanamide), 2- in benzyl thioacetamide, Thionicotinamide one kind or
It is several.
The indium salts, the molar ratio of thioamides are 4：1-1：30.
The adjusting pH value is 1.5-3.5.
The adjusting pH value is adjusted using inorganic acid solution.
A concentration of 0.1-1mol/L of the inorganic acid solution, wherein inorganic acid are one kind or several of hydrochloric acid, sulfuric acid, nitric acid
Kind.
The heating in microwave open system, which is reacted, is：10-25min is reacted in microwave heating at 80-95 DEG C.
The present invention directly by indium source, sulphur source mix, adjust arrive suitable pH, microwave heating reaction after, by stand, from
The heart, washing, freeze-drying, you can the hollow indium sulfide microballoon with special appearance is prepared, preparation process is simple, is applicable in
In large-scale production.Meanwhile it by controlling water-soluble indium salts and the molar ratio of thioamides and the pH value of reaction solution, can obtain
To the hollow indium sulfide microballoon of size uniformity；By changing the concentration of reaction raw materials, the pH of microwave heating time and reaction solution
Value, can obtain having different sizes and wall thickness, inner wall smooth hollow indium sulfide microballoon.
The hollow indium sulfide microballoon wall thickness that the present invention is prepared is about 70-90nm, and diameter is about 700nm~1 μm.This hair
The bright indium sulfide microballoon kernel being prepared is hollow, spherome surface structure, when this makes hollow indium sulfide as elctro-catalyst, energy
Enough greatly improve the electrocatalytic oxidation property of indium sulfide.When as photochemical catalyst, since energy gap trend becomes smaller, can only it exist
It directly degrades under conditions of solar irradiation larger molecular organics, treated sewage uses.With other metal oxides or sulfide
Semiconductor is combined as in use, absorbability of the solar cell to light can be improved, substitutes the position of toxic cadmium sulfide.
Hollow indium sulfide is alternatively arranged as the raw material of fluorescent material.
Advantageous effect
(1) the method for the present invention is not necessarily to template, and primary first-order equation can directly obtain product, and reaction midway is not necessarily to other additives；
(2) the hollow indium sulfide microballoon good dispersion that the present invention is prepared, uniform particle sizes, size and wall thickness can
Control, shape is uniform, and stability is high；
(3) present invention heating reaction use Microwave Assisted Process, carried out in normal-pressure open system, avoid hydro-thermal method or
The high temperature and high pressure that person's solvent-thermal method must use, it is safe, it is energy saving；
(4) method and technical process of the invention are simple, environmental-friendly, and reaction carries out in water phase, and product is easily isolated
And cleaning, yield is high, can be used for large-scale production.
Description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph for the hollow indium sulfide microballoon that embodiment 1 is prepared；
Fig. 2 is the transmission electron microscope picture for the hollow indium sulfide microballoon that embodiment 1 is prepared；
Fig. 3 is the X-ray diffractogram for the hollow indium sulfide microballoon that embodiment 1 is prepared.
Specific implementation mode
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, people in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Embodiment 1
50mL 0.004mol/L indium nitrates aqueous solutions and 50mL 0.004mol/L 2- methyl-thiopropionamide is water-soluble
Liquid mixes, and later plus after 1mol/L aqueous hydrochloric acid solutions adjusting pH value to microwave heating reaction 15min at 2.2,90 DEG C, stands, goes
It except supernatant, centrifuges, washs, freeze-drying obtains product.Product wall thickness is 80nm, diameter~900nm.The SEM of product
Figure, TEM figures and XRD diagram are shown in attached drawing 1,2 and 3.
Embodiment 2
By 50mL 0.004mol/L indium nitrates aqueous solutions and 50mL 0.004mol/L 2- to benzyl thioacetyl aqueous amine
Solution mixes, quiet later plus after 0.5mol/L aqueous hydrochloric acid solutions adjusting pH value to microwave heating reaction 25min at 2.5,80 DEG C
It sets, removes supernatant, centrifuge, wash, freeze-drying obtains product.Product wall thickness 70nm, diameter~800nm.
Embodiment 3
50mL 0.008mol/L inidum chlorides aqueous solutions and 50mL 0.024mol/L 2- methyl-thiopropionamide is water-soluble
Liquid mixes, and later plus after 1mol/L aqueous hydrochloric acid solutions adjusting pH value to microwave heating reaction 15min at 2.2,90 DEG C, stands, goes
It except supernatant, centrifuges, washs, freeze-drying obtains product.The wall thickness of product is 70nm, diameter~900nm.
Embodiment 4
50mL 0.004mol/L indium nitrates aqueous solutions are mixed with 50mL 0.004mol/L thiopropionamide aqueous solutions, it
Afterwards plus after 0.1mol/L aqueous solution of nitric acid adjusting pH value to microwave heating reaction 20min at 2.5,85 DEG C, stand, removal upper layer is clear
Night centrifuges, and washs, and freeze-drying obtains product.The wall thickness of product is 85nm, diameter~900nm.
Embodiment 5
By 50mL 0.012mol/L indium nitrates aqueous solutions and 50mL 0.04mol/L 2- methyl-thiopropionamide aqueous solution
Mixing stands, goes later plus after 0.5mol/L aqueous hydrochloric acid solutions adjusting pH value to microwave heating reaction 15min at 2.2,90 DEG C
It except supernatant, centrifuges, washs, freeze-drying obtains product.The wall thickness of product is 85nm, diameter 1um.
Claims (5)
1. a kind of method that atmospheric low-temperature prepares hollow indium sulfide microballoon without template, including：
Under the conditions of magnetic agitation, indium salts aqueous solution and thioamides aqueous solution are mixed, adjust pH value, then opens body in microwave
Reaction is heated in system, it is cooling, it filters, washing is freeze-dried to get hollow indium sulfide microballoon；Wherein indium salts, thioamides rub
You are than being 4：1-1：30；The adjusting pH value is 1.5-3.5；The wherein described heating in microwave open system, which is reacted, is：80-95
10-25min is reacted in microwave heating under DEG C open condition.
2. the method that a kind of atmospheric low-temperature according to claim 1 prepares hollow indium sulfide microballoon without template, feature exist
In：A concentration of 0.001-0.2mol/L of the indium salts aqueous solution, wherein indium salts are indium nitrate and/or inidum chloride.
3. the method that a kind of atmospheric low-temperature according to claim 1 prepares hollow indium sulfide microballoon without template, feature exist
In：A concentration of 0.001-0.2mol/L of the thioamides aqueous solution, wherein thioamides are thiopropionamide, 2- methyl sulphur
For propionamide, 2- to one or more of benzyl thioacetamide, Thionicotinamide.
4. the method that a kind of atmospheric low-temperature according to claim 1 prepares hollow indium sulfide microballoon without template, feature exist
In：The adjusting pH value is adjusted using inorganic acid solution.
5. the method that a kind of atmospheric low-temperature according to claim 4 prepares hollow indium sulfide microballoon without template, feature exist
In：A concentration of 0.1-1mol/L of the inorganic acid solution, wherein inorganic acid are the one or more of hydrochloric acid, sulfuric acid, nitric acid.
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| CN110735151A (en) * | 2019-06-20 | 2020-01-31 | 常州大学 | Preparation method of titanium carbide composite indium zinc sulfide photo-anode |
| CN113213526B (en) * | 2021-05-31 | 2022-09-20 | 上海理工大学 | CaIn 2 S 4 Hollow nanospheres, and preparation method and application thereof |
| CN113461046B (en) * | 2021-07-28 | 2023-03-28 | 四川恒瑞天成科技有限公司 | Comb-shaped nitrogen-doped indium sulfide gas-sensitive material, preparation method and application |
| CN115020912A (en) * | 2022-06-06 | 2022-09-06 | 华南师范大学 | Nano flower-shaped indium sulfide-based diaphragm modification material and preparation method and application thereof |
| CN115367785A (en) * | 2022-08-23 | 2022-11-22 | 安徽工程大学 | High-efficiency photocatalyst micro/nano-thorn spherical indium sulfide and preparation method and application thereof, indium sulfide composite membrane and preparation method and application thereof |
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| CN101293192A (en) * | 2007-01-25 | 2008-10-29 | 中国科学院上海硅酸盐研究所 | Method for producing multi-layer hollow pellet or stephanoporate pellet with multi-chamber vesicle mould plate method |
| CN102643032A (en) * | 2011-02-22 | 2012-08-22 | 浙江大学 | Method for preparing In2S3 film by chemical bath deposition |
| CN105964275A (en) * | 2016-05-05 | 2016-09-28 | 齐齐哈尔大学 | Microwave-assistant one-step synthesis method of CuS/CdIn2S4/ZnIn2S4 composite photocatalyst |
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| FR2999557A1 (en) * | 2012-12-14 | 2014-06-20 | Commissariat Energie Atomique | SUSPENSION OF MONODISPERSED METAL SULFIDE AGGREGATES, PROCESS FOR PRODUCING THE SAME AND USES THEREOF |
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| CN101293192A (en) * | 2007-01-25 | 2008-10-29 | 中国科学院上海硅酸盐研究所 | Method for producing multi-layer hollow pellet or stephanoporate pellet with multi-chamber vesicle mould plate method |
| CN102643032A (en) * | 2011-02-22 | 2012-08-22 | 浙江大学 | Method for preparing In2S3 film by chemical bath deposition |
| CN105964275A (en) * | 2016-05-05 | 2016-09-28 | 齐齐哈尔大学 | Microwave-assistant one-step synthesis method of CuS/CdIn2S4/ZnIn2S4 composite photocatalyst |
Non-Patent Citations (1)
| Title |
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| "Sonochemical synthesis and characterization of cage-like β-indium sulphide powder";S. Gorai et al.;《Materials Chemistry and Physics》;20051231;第89卷;第332–335页 * |
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