CN106927499B - A kind of preparation method of multicomponent compound metal sulfide - Google Patents
A kind of preparation method of multicomponent compound metal sulfide Download PDFInfo
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- CN106927499B CN106927499B CN201710267871.3A CN201710267871A CN106927499B CN 106927499 B CN106927499 B CN 106927499B CN 201710267871 A CN201710267871 A CN 201710267871A CN 106927499 B CN106927499 B CN 106927499B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G11/00—Compounds of cadmium
- C01G11/02—Sulfides
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- 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
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- 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
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- 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
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
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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
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Abstract
The present invention is a kind of preparation method of multicomponent compound metal sulfide, comprising the following steps: 1) 0.1 gram to 1 gram sulfur-bearing metal complex is put into the high boiling organic solvent of 20 mL-100 mL, obtains uniform solution；2) by the uniform solution under stirring, the uniform solution of another sulfur-bearing metal complex is added after reaching relevant temperature, continues isothermal reaction 5 to 20 minutes for heating reaction；3) after cooling, centrifugal treating is carried out to product and takes obtained solid, is dried in succession with hexamethylene and deionized water washed product and after being centrifuged off by-product and impurity, obtains product composition metal sulfide.The preparation method of new multicomponent composition metal sulfide provided by the invention, easy to operate, reaction environment is friendly, and controllability is strong, can efficiently separate light induced electron and hole, and adjust the forbidden bandwidth of photochemical catalyst, and then improves photocatalysis efficiency.
Description
Technical field
The invention belongs to technical field of nano material, a kind of new multicomponent composition metal sulfide is particularly related to
Preparation method.
Background technique
With the rapid development of society, environmental pollution and energy deficiency have become two that human kind sustainable development faces
Big challenge.As a kind of cleaning, the cheap and reproducible energy, solar energy is developed into the energy and ring for solving to become increasingly conspicuous
The key of border problem.Photocatalysis technology has since it is converted into Hydrogen Energy, self-cleaning surface technology and photocatalytic degradation in solar energy
The application of machine compound etc. has been to be concerned by more and more people.With TiO2For representative traditional photochemical catalyst because its band gap it is wide
(3.2 eV) is narrow, can only respond ultraviolet light and near ultraviolet ray, low to the utilization rate of solar energy (about 5%), greatly restricts
Its marketing development, therefore instantly more sight have turned to transient metal sulfide.
The performance of CdS is ideal in metal sulfide, is to use more sulfide semiconductor light in photocatalysis research
Catalyst, forbidden band broadband are 2.4 eV, can be absorbed and use visible light.But single CdS is unstable under light illumination, Yi Fa
Third contact of a total solar or lunar eclipse corrosion, declines its catalytic activity rapidly.So our selections are compound by CdS and other metal sulfides, make the two shape
At CdS-MS (M=Zn, Cu, Ni, Fe etc.) composition metal sulfide, this way can be by adjusting Cd and M metallic atom
Number ratio adjusts the forbidden band of product to the width of most suitable light-catalyzed reaction.
The preparation method of metal sulfide mainly has hydro-thermal method, microemulsion method, solvent-thermal process method, sol-gel at present
Method and template etc..These methods all have the advantage of itself at corresponding aspect, and however, there are also certain defects.Such as water
The corresponding equipment requirement of thermal method is higher；Raw material used by sol-gel method is costly and longer the time required to reaction；Template
Then there are some limitations due to basis material for method etc.；
Therefore, it in order to which photocatalysis research can be more effectively applied in practice, seeks a kind of novel, easy, more
Perfect composition metal sulfide preparation method is necessary.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of preparation method of new multicomponent composition metal sulfide, the party
Method effectively prevents the compound of light induced electron and hole, improves the efficiency of its photochemical catalyzing.
In order to achieve the above object, the present invention is achieved by the following technical solutions:
The present invention is a kind of preparation method of multicomponent compound metal sulfide, and preparation method includes the following steps:
1) 0.1 gram to 1 gram sulfur-bearing metal complex is put into the high boiling organic solvent of 20 mL-100 mL, is obtained
One solution；
2) by the uniform solution under stirring, another sulfur-bearing is added in heating reaction after reaching relevant temperature
The uniform solution of metal complex continues isothermal reaction 5 to 20 minutes；
3) after cooling, centrifugal treating is carried out to product and takes obtained solid, uses hexamethylene and deionized water washed product in succession
And dried after being centrifuged off by-product and impurity, obtain product composition metal sulfide；Oleic acid after centrifugation is recyclable, drop
Low cost reduces environmental pollution.
A further improvement of the present invention is that: the metallic element of sulfur-bearing metal complex employed in the step 1)
Type includes: Cd, Zn, Cu, Ni, Fe, Co, Mn.
A further improvement of the present invention is that: in the step 1), the sulfur-bearing metal complex is organic in higher boiling
Solution temperature in solvent is 100 DEG C to 160 DEG C.
A further improvement of the present invention is that: heating temperature is 220 DEG C to 320 DEG C in the step 2, and final anti-
Temperature is answered to be higher than another sulfur-bearing metal complex decomposition temperature.
A further improvement of the present invention is that: its boiling point of high boiling organic solvent is matched containing sulfur metal in the step 1)
It closes on object decomposition temperature.
A further improvement of the present invention is that: the heat for another sulfur-bearing metal complex being added after in the step 2
Decomposition temperature must be higher than the decomposition temperature for the sulfur-bearing metal complex being first added in step 1).
A further improvement of the present invention is that: presoma is done with sulfur-bearing metal complex.
A further improvement of the present invention is that: in the step 1), sulfur-bearing metal complex is mercaptobenzothiazoler conjunction
Cadmium or mercaptobenzothiazoler close copper.
A further improvement of the present invention is that: in the step 2, another sulfur-bearing metal complex is sulfydryl benzo
Thiazole closes zinc or mercaptobenzothiazoler closes copper or mercaptobenzothiazoler closes nickel.
The beneficial effects of the present invention are: liquid phase thermal decomposition method of the present invention, easy to operate, and it is environmental-friendly, it obtains
The composition metal sulfide that nano particle is uniform, size, pattern, atomic ratio are controllable effectively prevents light induced electron and empty
Cave it is compound, improve the efficiency of its photochemical catalyzing.
Detailed description of the invention
Fig. 1 is the SEM figure of CdS-ZnS prepared by the embodiment of the present invention one.
Fig. 2 is the SEM figure of CdS-CuS prepared by the embodiment of the present invention three.
Fig. 3 is the SEM figure of CdS-NiS prepared by the embodiment of the present invention four.
Specific embodiment
In order to deepen the understanding of the present invention, the present invention is described further below in conjunction with drawings and examples, it should
The examples are only for explaining the invention, and not low protection scope of the present invention, which is constituted, to be limited.
As shown in Figure 1-3, the present invention is a kind of preparation method of multicomponent compound metal sulfide, it is characterised in that: described
Preparation method the following steps are included:
1) 0.1 gram to 1 gram sulfur-bearing metal complex is put into the high boiling organic solvent of 20 mL-100 mL, is obtained
One solution；
2) by the uniform solution under stirring, another sulfur-bearing is added in heating reaction after reaching relevant temperature
The uniform solution of metal complex continues isothermal reaction 5 to 20 minutes；
3) after cooling, centrifugal treating is carried out to product and takes obtained solid, uses hexamethylene and deionized water washed product in succession
And dried after being centrifuged off by-product and impurity, obtain product composition metal sulfide.
Wherein: the metallic element type of the sulfur-bearing metal complex employed in the step 1) include: Cd, Zn, Cu,
Ni,Fe,Co,Mn；
In the step 1), solution temperature of the sulfur-bearing metal complex in high boiling organic solvent is 100 DEG C
To 160 DEG C.
Heating temperature is 220 DEG C to 320 DEG C in the step 2, and end reaction temperature is higher than another kind and contains sulfur metal
Complex decomposition temperature；
Its boiling point of high boiling organic solvent is on sulfur-bearing metal complex decomposition temperature in the step 1).
The thermal decomposition temperature for another sulfur-bearing metal complex being added after in the step 2 must be higher than in step 1)
The decomposition temperature for the sulfur-bearing metal complex being first added；
Presoma is done with sulfur-bearing metal complex, and sulfur-bearing metal complex is by organic ligand (including the sulfydryl benzene containing sulfydryl
And thiazole, lauryl mercaptan, L-cysteine, mercaptoethanol, benzenethiol, thioacetic acid etc.), it is synthesized with corresponding soluble metallic salt
Corresponding metal complex.
In the step 1), sulfur-bearing metal complex is that mercaptobenzothiazoler closes cadmium or mercaptobenzothiazoler closes copper.
In the step 2, another sulfur-bearing metal complex is that mercaptobenzothiazoler closes zinc or mercaptobenzothiazoler closes
Copper or mercaptobenzothiazoler close nickel.
Embodiment one
0.44 g mercaptobenzothiazoler conjunction cadmium is added in the three-necked flask for filling 250 mL of 45 mL oleic acid, is held
It is continuous be stirred and heated to 100 DEG C dissolve solid after, continue to be heated to 240 DEG C of isothermal reactions to make within 5 minutes complex thermal decomposition completely,
The oleic acid solutions that mercaptobenzothiazoler closes zinc are added after being heated to 285 DEG C, mass volume ratio is 0.16 g: 15 mL, permanent
Temperature heating stops reaction after ten minutes, takes obtained solid after carrying out centrifugal treating to product, uses hexamethylene and deionized water in succession
Washed product is simultaneously centrifuged off by-product and impurity, obtains product CdS-ZnS composition metal sulfide.
Embodiment two
0.44 g mercaptobenzothiazoler conjunction copper is added in the three-necked flask for filling 250 mL of 45 mL oleic acid, is held
It is continuous be stirred and heated to 120 DEG C dissolve solid after, continue to be heated to 260 DEG C of isothermal reactions to make within 5 minutes complex thermal decomposition completely,
The oleic acid solutions that mercaptobenzothiazoler closes zinc are added after being heated to 285 DEG C, mass volume ratio is 0.16 g: 15 mL, permanent
Temperature heating stops reaction after ten minutes, takes obtained solid after carrying out centrifugal treating to product, uses hexamethylene and deionized water in succession
Washed product is simultaneously centrifuged off by-product and impurity, obtains product CuS-ZnS composition metal sulfide.
Embodiment three
0.44 g mercaptobenzothiazoler conjunction cadmium is added in the three-necked flask for filling 250 mL of 45 mL oleic acid, is held
It is continuous be stirred and heated to 100 DEG C dissolve solid after, continue to be heated to 240 DEG C of isothermal reactions to make within 5 minutes complex thermal decomposition completely,
The oleic acid solutions that mercaptobenzothiazoler closes copper are added after being heated to 260 DEG C, mass volume ratio is 0.16 g: 15 mL, permanent
Temperature heating stops reaction after ten minutes, takes obtained solid after carrying out centrifugal treating to product, uses hexamethylene and deionized water in succession
Washed product is simultaneously centrifuged off by-product and impurity, obtains product CdS-CuS composition metal sulfide.
Example IV
0.44 g mercaptobenzothiazoler conjunction cadmium is added in the three-necked flask for filling 250 mL of 45 mL oleic acid, is held
It is continuous be stirred and heated to 100 DEG C dissolve solid after, continue to be heated to 240 DEG C of isothermal reactions to make within 5 minutes complex thermal decomposition completely,
The oleic acid solutions that mercaptobenzothiazoler closes nickel are added after being heated to 270 DEG C, mass volume ratio is 0.16 g: 15 mL, permanent
Temperature heating stops reaction after ten minutes, takes obtained solid after carrying out centrifugal treating to product, uses hexamethylene and deionized water in succession
Washed product is simultaneously centrifuged off by-product and impurity, obtains product CdS-NiS composition metal sulfide.
Embodiment five
0.44 g mercaptobenzothiazoler conjunction copper is added in the three-necked flask for filling 250 mL of 45 mL oleic acid, is held
It is continuous be stirred and heated to 120 DEG C dissolve solid after, continue to be heated to 260 DEG C of isothermal reactions to make within 5 minutes complex thermal decomposition completely,
The oleic acid solutions that mercaptobenzothiazoler closes zinc are added after being heated to 270 DEG C, mass volume ratio is 0.16 g: 15 mL, permanent
Temperature heating stops reaction after ten minutes, takes obtained solid after carrying out centrifugal treating to product, uses hexamethylene and deionized water in succession
Washed product is simultaneously centrifuged off by-product and impurity, obtains product CuS-NiS composition metal sulfide.
It is controllable to obtain uniform nano particle, size, pattern, atomic ratio for liquid phase thermal decomposition method of the present invention
Composition metal sulfide effectively prevents the compound of light induced electron and hole, improves the efficiency of its photochemical catalyzing.
Claims (7)
1. a kind of preparation method of multicomponent compound metal sulfide, it is characterised in that: the preparation method comprises the following steps:
0.1 gram to 1 gram sulfur-bearing metal complex is put into the high boiling organic solvent of 20 mL-100 mL, is obtained uniform molten
Liquid；
By the uniform solution under stirring, heating reaction is added another kind after reaching relevant temperature and matches containing sulfur metal
The uniform solution of object is closed, is continued isothermal reaction 5 to 20 minutes；
After cooling, centrifugal treating is carried out to product and takes obtained solid, with hexamethylene and deionized water washed product and is centrifuged in succession
It is dried after removing by-product and impurity, obtains product composition metal sulfide；
Wherein: in the step 1), solution temperature of the sulfur-bearing metal complex in high boiling organic solvent is 100 DEG C
To 160 DEG C；
Heating temperature is 220 DEG C to 320 DEG C in the step 2, and end reaction temperature is higher than another sulfur-bearing metal combination
Object decomposition temperature.
2. a kind of preparation method of multicomponent compound metal sulfide according to claims 1, it is characterised in that: in the step
It is rapid 1) employed in the metallic element type of sulfur-bearing metal complex include: Cd, Zn, Cu, Ni, Fe, Co, Mn.
3. a kind of preparation method of multicomponent compound metal sulfide according to claims 1, it is characterised in that: in the step
It is rapid 1) in its boiling point of high boiling organic solvent on sulfur-bearing metal complex decomposition temperature.
4. a kind of preparation method of multicomponent compound metal sulfide according to claims 1, it is characterised in that: in the step
It is rapid 2) in after the thermal decomposition temperature of another sulfur-bearing metal complex that is added must be higher than first be added in step 1) containing sulfur metal
The decomposition temperature of complex.
5. a kind of preparation method of multicomponent compound metal sulfide according to claims 1, it is characterised in that: with sulfur-bearing gold
Metal complex does presoma.
6. a kind of preparation method of multicomponent compound metal sulfide according to claims 1, it is characterised in that: in the step
It is rapid 1) in, metal complex is that mercaptobenzothiazoler closes cadmium or mercaptobenzothiazoler and closes copper.
7. a kind of preparation method of multicomponent compound metal sulfide according to claims 1, it is characterised in that: in the step
It is rapid 2) in, another middle metal complex is that mercaptobenzothiazoler closes that zinc or mercaptobenzothiazoler close copper or mercaptobenzothiazoler closes
Nickel.
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| CN112607792B (en) * | 2020-12-17 | 2022-07-15 | 中国科学技术大学 | Sodium-ion battery negative electrode material, and preparation method and application thereof |
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