CN106745199A - 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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- CN106745199A CN106745199A CN201611251981.2A CN201611251981A CN106745199A CN 106745199 A CN106745199 A CN 106745199A CN 201611251981 A CN201611251981 A CN 201611251981A CN 106745199 A CN106745199 A CN 106745199A
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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, the indium salts aqueous solution and the thioamides aqueous solution are mixed, adjust pH value, then the heating response in microwave open system, cooling, filter, washing, freeze-drying is obtained final product.Without template, primary first-order equation can directly obtain product to the present invention, and reaction midway is without other additives；The hollow indium sulfide microballoon good dispersion for preparing, uniform particle sizes, size and wall thickness are controllable, and shape is homogeneous, and stability is high；Heating response is carried out using Microwave Assisted Process in normal-pressure open system, it is to avoid hydro-thermal method or solvent-thermal method have to use for high temperature and high pressure, safe, energy saving；Method and technical process are simple, environment-friendly, and reaction is carried 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.In2S3Optically and electrically equipment, such as photovoltaic have been applied to it too
Positive energy battery, photoconductor, superionic conductors, lithium ion battery.
At present to In2S3The research of material is more popular, the In of preparation2S3Product also has various different forms, includes
Nanoparticulate, bar-shaped, banding, tubulose and hollow microsphere etc..Template being used the synthesis of hollow microsphere, such as Gao is with water more
The dimethyl sulphide for closing hydrazine reduction DMSO generations is sulphur source and soft template, is reacted 48 hours at 180 DEG C using hydro-thermal method, is prepared
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 prepares hollow using two-step method
Indium sulfide microballoon：First by carbon disulfide (CS2) 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 continuation after a certain amount of thiocarbamide is added afterwards is reacted 12 hours using solvent-thermal method at 180 DEG C, final
To hollow microsphere (Y.Liu, et al, Materials Chemistry and Physics, 2007,101,362-366)；
X.Cao etc. first by thiocarbamide for sulphur source prepares indium sulfide colloid, afterwards by indium sulfide colloidal dispersions in benzene, using solvent heat
Method is reacted 24 hours at 180 DEG C, prepares hollow indium sulfide microballoon (X.Cao et al, Colloids and Surfaces
A:Physicochem.Eng.Aspects,2007,297,183–190)；Shao Shaofeng etc. is sulphur source using thiocarbamide, is with amino acid
Growth inhibitor, after being reacted 72 hours at 180 DEG C using hydro-thermal method, prepares the In with multi-level nano-structure2S3It 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
Reacted 24 hours at 150 DEG C with hydro-thermal method, prepare hollow indium sulfide microballoon (L.Liu, et al, Cryst.Growth
Des.,2009,9,113-117)；S.Rengaraj is sulphur source using thiosemicarbazides, and solvent-thermal method is used by solvent of water/ethanol
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 at 150 DEG C using hydro-thermal method in the presence of oxalic acid, is obtained
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
Deng high-tension apparatus, complex process, disposable preparation amount is few, it is difficult to produce in batches；Secondly, reaction system must be heated to 150-180
DEG C, there is certain risk, take (10-24 hours), energy resource consumption is big；3rd, part sulphur source toxicity is big, and carbon disulfide is easily waved
Hair, and with CDCC, thiosemicarbazides is extremely toxic substance, it is desirable to which production equipment is closed, operating personnel should dress protection and use
Tool, is that associated production causes to hinder.4th, in building-up process to use organic solvent, such as ethanol, benzene, easy firing, part has more
It is toxic.
Because its special form and hollow structure make hollow In2S3Microballoon has very big specific surface area, will make it in crowd
It is multi-field with important application potential, such as can be used for uvioresistant, coloring, special optical performance arrange, 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, its preparation technology still needs and optimizes and improve, and finds operation more
Easy, being easier to industrialized production, environment-friendly preparation method, to reduce the reaction time, improves reaction efficiency.
The content of the invention
The technical problems to be solved by the invention are to provide a kind of atmospheric low-temperature and prepare hollow indium sulfide microballoon without template
Method, of the invention preparation is simple, raw material is readily available, suitable for large-scale production hollow indium sulfide microwave
Assistant preparation method.
The method that a kind of atmospheric low-temperature of the invention prepares hollow indium sulfide microballoon without template, including：
Under the conditions of magnetic agitation, the indium salts aqueous solution and the thioamides aqueous solution are mixed, adjust pH value, then opened in microwave
Heating response in system is put, is cooled down, filtering, washing, freeze-drying obtains final product hollow indium sulfide microballoon.
The concentration of the indium salts aqueous solution is 0.001-0.2mol/L, and wherein indium salts are indium nitrate and/or inidum chloride.
The concentration of the thioamides aqueous solution is 0.001-0.2mol/L, and wherein thioamides is thiopropionamide, 2-
Methyl thio propionamide (also referred to as thio-iso-butanamide), 2- to the one kind in benzyl thioacetamide, Thionicotinamide or
It is several.
The indium salts, the mol ratio of thioamides are 4：1-1：30.
The regulation pH value is 1.5-3.5.
The regulation pH value is adjusted using inorganic acid solution.
The concentration of the inorganic acid solution is 0.1-1mol/L, and wherein inorganic acid is hydrochloric acid, sulfuric acid, one kind of nitric acid or several
Kind.
The heating response in microwave open system is：Heating using microwave reaction 10-25min at 80-95 DEG C.
It is of the invention directly to mix indium source, sulphur source, regulation to suitable pH, after heating using microwave reaction, by standing, from
The heart, washing, freeze-drying, you can to prepare the hollow indium sulfide microballoon with special appearance, preparation process is simple is applicable
In large-scale production.Meanwhile, by controlling water-soluble indium salts and the mol ratio and the pH value of reaction solution of thioamides, can obtain
To the hollow indium sulfide microballoon of size uniformity；By the pH for changing concentration, microwave heating time and the reaction solution of reaction raw materials
Value, can obtain with different size and wall thickness, inner wall smooth hollow indium sulfide microballoon.
The hollow indium sulfide microballoon wall thickness about 70-90nm that the present invention is prepared, diameter is about 700nm~1 μm.This hair
The bright indium sulfide microballoon kernel for preparing is hollow, spherome surface structure, when this causes hollow indium sulfide as elctro-catalyst, energy
Enough greatly improve the electrocatalytic oxidation property of indium sulfide.During as photochemical catalyst, because energy gap tends to diminish, can only exist
Under conditions of solar irradiation directly degrade larger molecular organicses, treatment sewage use.With other metal oxides or sulfide
When being combined as semiconductor and using, it is possible to increase solar cell substitutes the position of poisonous cadmium sulfide to the absorbability of light.
Hollow indium sulfide is alternatively arranged as the raw material of fluorescent material.
Beneficial effect
(1) without template, primary first-order equation can directly obtain product to the inventive method, and reaction midway is without 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 homogeneous, and stability is high；
(3) heating response of the present invention uses Microwave Assisted Process, carried out in normal-pressure open system, it is to avoid hydro-thermal method or
Person's solvent-thermal method has to use for high temperature and high pressure, safe, energy saving；
(4) method of the present invention and technical process are simple, environment-friendly, and reaction is carried out in water phase, and product is easily isolated
And cleaning, yield is high, can be used for large-scale production.
Brief description of the drawings
Fig. 1 is the scanning electron microscope (SEM) photograph of the hollow indium sulfide microballoon that embodiment 1 is prepared；
Fig. 2 is the transmission electron microscope picture of the hollow indium sulfide microballoon that embodiment 1 is prepared；
Fig. 3 is the X-ray diffractogram of the hollow indium sulfide microballoon that embodiment 1 is prepared.
Specific embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content for having read instruction of the present invention, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.
Embodiment 1
The 50mL 0.004mol/L indium nitrates aqueous solution is water-soluble with 50mL 0.004mol/L 2- methyl-thiopropionamide
Liquid mixes, and adds 1mol/L aqueous hydrochloric acid solutions to adjust pH value to 2.2 afterwards, at 90 DEG C after heating using microwave reaction 15min, stands, and goes
Except supernatant, centrifugation, washing, freeze-drying obtains product.Product wall thickness is 80nm, diameter~900nm.The SEM of product
Figure, TEM figures and XRD are shown in accompanying drawing 1,2 and 3.
Embodiment 2
By the 50mL 0.004mol/L indium nitrates aqueous solution and 50mL 0.004mol/L 2- to benzyl thioacetyl aqueous amine
Solution mixes, and adds 0.5mol/L aqueous hydrochloric acid solutions to adjust pH value to 2.5 afterwards, quiet at 80 DEG C after heating using microwave reaction 25min
Put, remove supernatant, centrifugation, washing, freeze-drying obtains product.Product wall thickness 70nm, diameter~800nm.
Embodiment 3
The 50mL 0.008mol/L inidum chlorides aqueous solution is water-soluble with 50mL 0.024mol/L 2- methyl-thiopropionamide
Liquid mixes, and adds 1mol/L aqueous hydrochloric acid solutions to adjust pH value to 2.2 afterwards, at 90 DEG C after heating using microwave reaction 15min, stands, and goes
Except supernatant, centrifugation, washing, freeze-drying obtains product.The wall thickness of product is 70nm, diameter~900nm.
Embodiment 4
The 50mL 0.004mol/L indium nitrates aqueous solution is mixed with the 50mL 0.004mol/L thiopropionamide aqueous solution, it
Afterwards plus 0.1mol/L aqueous solution of nitric acid adjust pH value to 2.5, at 85 DEG C heating using microwave reaction 20min after, stand, removal upper strata it is clear
Night, centrifugation, washing, freeze-drying obtains product.The wall thickness of product is 85nm, diameter~900nm.
Embodiment 5
By the 50mL 0.012mol/L indium nitrates aqueous solution and 50mL 0.04mol/L 2- methyl-thiopropionamide aqueous solution
Mixing, adds 0.5mol/L aqueous hydrochloric acid solutions to adjust pH value to 2.2 afterwards, at 90 DEG C after heating using microwave reaction 15min, stands, and goes
Except supernatant, centrifugation, washing, freeze-drying obtains product.The wall thickness of product is 85nm, diameter 1um.
Claims (8)
1. a kind of method that atmospheric low-temperature prepares hollow indium sulfide microballoon without template, including：
Under the conditions of magnetic agitation, the indium salts aqueous solution and the thioamides aqueous solution are mixed, adjust pH value, then open body in microwave
Heating response in system, cooling, filtering, washing, freeze-drying obtains final product hollow indium sulfide microballoon.
2. the method that a kind of atmospheric low-temperature according to claim 1 prepares hollow indium sulfide microballoon without template, its feature exists
In：The concentration of the indium salts aqueous solution is 0.001-0.2mol/L, and 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, its feature exists
In：The concentration of the thioamides aqueous solution is 0.001-0.2mol/L, and wherein thioamides is thiopropionamide, 2- methyl sulphur
For propionamide, 2- to one or more in benzyl thioacetamide, Thionicotinamide.
4. the method that a kind of atmospheric low-temperature according to claim 1 prepares hollow indium sulfide microballoon without template, its feature exists
In：Indium salts, the mol ratio of thioamides are 4：1-1：30.
5. the method that a kind of atmospheric low-temperature according to claim 1 prepares hollow indium sulfide microballoon without template, its feature exists
In：The regulation pH value is 1.5-3.5.
6. the method that a kind of atmospheric low-temperature according to claim 1 prepares hollow indium sulfide microballoon without template, its feature exists
In：The regulation pH value is adjusted using inorganic acid solution.
7. the method that a kind of atmospheric low-temperature according to claim 6 prepares hollow indium sulfide microballoon without template, its feature exists
In：The concentration of the inorganic acid solution is 0.1-1mol/L, and wherein inorganic acid is one or more of hydrochloric acid, sulfuric acid, nitric acid.
8. the method that a kind of atmospheric low-temperature according to claim 1 prepares hollow indium sulfide microballoon without template, its feature exists
In：The heating response in microwave open system is：Heating using microwave reaction 10-25min under 80-95 DEG C of open condition.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110735151A (en) * | 2019-06-20 | 2020-01-31 | 常州大学 | Preparation method of titanium carbide composite indium zinc sulfide photo-anode |
| CN113213526A (en) * | 2021-05-31 | 2021-08-06 | 上海理工大学 | CaIn2S4Hollow nanosphere and preparation method and application thereof |
| CN113461046A (en) * | 2021-07-28 | 2021-10-01 | 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 |
| CN115959701A (en) * | 2023-02-20 | 2023-04-14 | 西南交通大学 | Preparation method and application of 3D self-assembly hydrangea-shaped indium sulfide |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110735151A (en) * | 2019-06-20 | 2020-01-31 | 常州大学 | Preparation method of titanium carbide composite indium zinc sulfide photo-anode |
| CN113213526A (en) * | 2021-05-31 | 2021-08-06 | 上海理工大学 | CaIn2S4Hollow nanosphere and preparation method and application thereof |
| 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 |
| CN113461046A (en) * | 2021-07-28 | 2021-10-01 | 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 |
| CN115959701A (en) * | 2023-02-20 | 2023-04-14 | 西南交通大学 | Preparation method and application of 3D self-assembly hydrangea-shaped indium sulfide |
| CN115959701B (en) * | 2023-02-20 | 2024-04-26 | 西南交通大学 | Preparation method and application of 3D self-assembled hydrangea-shaped indium sulfide |
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