CN101423200B - Novel preparation method of transient metal sulfide alloy - Google Patents
Novel preparation method of transient metal sulfide alloy Download PDFInfo
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- CN101423200B CN101423200B CN2008101531784A CN200810153178A CN101423200B CN 101423200 B CN101423200 B CN 101423200B CN 2008101531784 A CN2008101531784 A CN 2008101531784A CN 200810153178 A CN200810153178 A CN 200810153178A CN 101423200 B CN101423200 B CN 101423200B
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- metal sulfide
- transient metal
- preparation
- thiourea
- alloy
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Abstract
The invention discloses a novel preparation method of a transition metal sulfide alloy, comprising the steps as follows: step 1: soluble metal salt and thiourea or thiourea derivatives with the molar ratio of 1:6-1:13 are added into ionized water; step 2: after mixing the soluble metal salt and thiourea or thiourea derivatives, the solution is transferred to a high-pressure kettle; at the complextemperature of 120-150 DEG C, the soluble metal salt and thiourea or thiourea derivatives are sufficiently complexed to generate the complex; and step 3: the complex generated in the step 2 is heatedat the temperature of 200-240 DEG C to generate a transition metal sulfide. Compared with the existing preparation method of the transition metal sulfide alloy, the method has the advantages of simple required raw material, low cost, simple production process, easy controlling on the reaction condition, good consistency of the formed product, little pollution to the environment and needing no template agent, is beneficial for the batch production of the transition metal sulfide alloy and has important practical production significance.
Description
Technical field
The present invention relates to the alloy preparing technical field, particularly relate to a kind of novel preparation method of transient metal sulfide alloy.
Background technology
Transition element all is a metal, is transition metal again.With the metallographic phase ratio of main group element, they have characteristics such as fusing point height, boiling point height, hardness height, density are big.Most transition metal all is that the form with oxide compound or sulfide is present in the earth's crust, has only several simple substance such as gold and silver can stable existence.
Transient metal sulfide is one of relatively more active field of Recent study.Owing to have unique light, electricity, magnetic property and chemical property, thereby be widely applied to every field, for example, as the important presoma of solid lithium ion battery cathode material, commercial catalysts, photoelectron material, diagnostic materials, sulfuration glass, synthetic superconducting material, even can also be as photodiode.
Though the current synthetic method that many transient metal sulfides occur, but, methods such as these methods adopt usually that high temperature gas phase or high temperature solid-state are synthetic, ion exchange reaction is synthetic, organism pyrolysis and electrochemical synthesis, the needed raw material type of these methods is many, raw materials cost is high, and production technique more complicated, can't form mass production, be unfavorable for that the widespread production of transient metal sulfide is popularized.
Summary of the invention
In view of this, the purpose of this invention is to provide a kind of novel preparation method of transient metal sulfide alloy, it is simple, with low cost to have needed raw material, and production technique is simple, reaction conditions is easy to control, formed good product consistency, the advantage that environmental pollution is few, do not need template, help the mass production of transient metal sulfide alloy, be of great practical significance.
For this reason, the invention provides a kind of novel preparation method of transient metal sulfide alloy, may further comprise the steps:
The first step, soluble metallic salt and thiocarbamide or the thiourea derivative mol ratio according to 1: 6～1: 13 is joined in the ionized water;
Second goes on foot, after stirring solution is transferred in the autoclave, under 120～150 ℃ cooperation temperature soluble metallic salt and thiocarbamide or thiourea derivative is fully cooperated, and generates title complex;
The 3rd step, the title complex that second step was generated heat under 200～240 ℃ temperature, generate transient metal sulfide.
Preferably, also comprise step: the transient metal sulfide that the 3rd step was generated filters successively, washing, vacuum drying treatment.
Preferably, described soluble metallic salt is a water-soluble metal salt.
Preferably, described soluble metallic salt is a vitriol, or chlorate, or nitrate, or acetate.
Preferably, the described title complex generation preparation method that transient metal sulfide adopted is the self-template hydrothermal method.
Preferably, the transient metal sulfide alloy that is generated consist of MSx, x=1.0～2.0, the particle diameter of this transient metal sulfide alloy is 2 μ m.
By above technical scheme provided by the invention as seen, the present invention compares with existing transient metal sulfide alloy preparation method, it is simple, with low cost to have needed raw material, and production technique is simple, reaction conditions is easy to control, formed good product consistency, the advantage that environmental pollution is few, do not need template, help the mass production of transient metal sulfide alloy, be of great practical significance.
Description of drawings
Fig. 1 is X-ray diffraction (XRD) figure of transient metal sulfide, wherein, and the X-ray diffractogram of the transient metal sulfide that Figure 1A is generated for embodiment 2, the X-ray diffractogram of the transient metal sulfide that Figure 1B is generated for embodiment 3;
Fig. 2 is scanning electron microscope (SEM) figure of transient metal sulfide, wherein, the sem photograph of the transient metal sulfide that Fig. 2 A is generated for embodiment 1, the sem photograph of the transient metal sulfide that Fig. 2 B is generated for embodiment 2, the sem photograph of the transient metal sulfide that Fig. 2 C is generated for embodiment 3, the sem photograph of the transient metal sulfide that Fig. 2 D is generated for embodiment 4.
Embodiment
In order to make those skilled in the art person understand the present invention program better, the present invention is described in further detail below in conjunction with drawings and embodiments.
The invention provides a kind of transient metal sulfide (M-S, M are transition metal, and S is a sulphur) alloy novel preparation method, may further comprise the steps:
The first step, soluble metallic salt and thiocarbamide or the thiourea derivative mol ratio according to 1:6～1:13 is joined in the ionized water;
In preparation method provided by the invention, employed Synergist S-421 95 and sulphur source are thiocarbamide or thiourea derivative.
Described soluble metallic salt is a water-soluble metal salt, on the specific implementation, can be vitriol, or chlorate, or nitrate, or acetate etc.
Described transition metal M for example is cobalt Co, nickel.
In addition, among the preparation method provided by the invention, used solvent is a deionized water.
Second goes on foot, after stirring solution is transferred in the autoclave, under 120～150 ℃ cooperation temperature soluble metallic salt and thiocarbamide or thiourea derivative is fully cooperated, and generates title complex;
The 3rd step, the title complex that second step was generated heat under 200～240 ℃ temperature, generate transient metal sulfide.
It is the self-template hydrothermal method that above-mentioned title complex generates the preparation method that transient metal sulfide adopted.
In addition, in order to obtain clean, exsiccant transient metal sulfide, the present invention also comprised after the 3rd step:
The 4th step, the transient metal sulfide that the 3rd step was generated filter successively, washing, vacuum drying treatment.
Based on the novel preparation method of transient metal sulfide alloy that the invention described above provides, the transient metal sulfide alloy that is generated consist of MS
x, x=1.0～2.0, the particle diameter of this transient metal sulfide alloy is about 2 μ m (micron).
Technical scheme by the invention described above and specific embodiment as can be known, transient metal sulfide provided by the invention (M-S, M are transition metal, and S is a sulphur) alloy novel preparation method has following advantage:
1, raw material is simple and cost is lower, and reaction scheme is simple.
2, the simple and reaction conditions of production technique is easy to control.
By metal-salt is fully cooperated with thiocarbamide or thiourea derivative, then 200～240 ℃ of heating down.
3, it is good to generate the transient metal sulfide alloy consistency of product, helps mass production.
In view of the preparation process of transient metal sulfide alloy product of the present invention is to carry out in autoclave, it is few therefore to be subjected to external influence, and the transient metal sulfide alloy consistency of product that is generated is fine.
4, environmental pollution is few.
The reaction of transient metal sulfide alloy product preparation method provided by the invention is carried out in autoclave, therefore can not pollute environment in reaction process.Even when driving still, have a small amount of SO
2And H
2S overflows, but still can be by appropriate means to this a small amount of SO
2And H
2S effectively handles.
5, do not need template.
Metallic sulfide is as catalystic material, and adding bigger serface is one of target of research raising catalytic performance.For increasing specific surface area, often need in preparation process, add template.
Transient metal sulfide alloy product preparation method provided by the invention does not need external template, serves as sulphur source and Synergist S-421 95 by the thiocarbamide or derivatives thereof, fully generates title complex at 120～150 ℃ of following metal-salts and thiocarbamide (or thiourea derivative); Heat title complex down at 200～240 ℃ then, title complex decomposes the generation transient metal sulfide as template according to self structure, therefore, compares with no template sulfide, has bigger specific surface area.
Provide the specific embodiment that adopts novel preparation method of transient metal sulfide alloy of the present invention below:
Embodiment 1:
0.005mol rose vitriol and 0.065mol thiocarbamide are added in the 60ml deionized water, are transferred to after the stirring in the autoclave, heating 12h under 120 ℃ (hour), heat 6h down at 200 ℃ then; And the precipitation of the transient metal sulfide by filtration, washing, the above-mentioned generation of vacuum-drying successively.
Present embodiment 2 transient metal sulfide that generates consist of CoS
1.79Its sem photograph (SEM) is shown in accompanying drawing 2A.
Embodiment 2:
0.005mol cobalt chloride and 0.040mol 2,4-Dihydroxy benzaldehyde thiosemicarbazone are added in the 60ml deionized water, are transferred to after the stirring in the autoclave, heat 12h down, heat 24h down at 220 ℃ then at 130 ℃; And the precipitation of the transient metal sulfide by filtration, washing, the above-mentioned generation of vacuum-drying successively.
Present embodiment 2 transient metal sulfide that generates consist of CoS
1.65Its X-ray diffractogram (XRD) is shown in accompanying drawing 1A, and its sem photograph (SEM) is shown in accompanying drawing 2B.
Embodiment 3:
0.005mol nickelous chloride and 0.030mol thiocarbamide are added in the 60ml deionized water, are transferred to after the stirring in the autoclave, heat 12h down, heat 24h down at 220 ℃ then at 140 ℃; And the precipitation of the transient metal sulfide by filtration, washing, the above-mentioned generation of vacuum-drying successively.
Present embodiment 3 transient metal sulfide that generates consist of NiS
1.20Its X-ray diffractogram (XRD) is shown in accompanying drawing 1B, and its sem photograph (SEM) is shown in accompanying drawing 2C.
Embodiment 4:
0.005mol nickelous nitrate and 0.050mol thiocarbamide are added in the 60ml deionized water, are transferred to after the stirring in the autoclave, heat 12h down, heat 12h down at 240 ℃ then at 150 ℃; And the precipitation of the transient metal sulfide by filtration, washing, the above-mentioned generation of vacuum-drying successively.
Present embodiment 4 transient metal sulfide that generates consist of NiS
1.29Its sem photograph (SEM) is shown in accompanying drawing 2D.
The above only is a preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (4)
1. a transient metal sulfide preparation method is characterized in that, may further comprise the steps:
The first step, with solubility cobalt or nickel salt and thiocarbamide or 2,4-Dihydroxy benzaldehyde thiosemicarbazone joins in the ionized water according to 1: 6～1: 13 mol ratio; Described solubility cobalt or nickel salt are vitriol, chlorate, nitrate or acetate;
Second goes on foot, after stirring solution is transferred in the autoclave, makes solubility cobalt or nickel salt and thiocarbamide or 2 under 120～150 ℃ cooperation temperature, and 4-Dihydroxy benzaldehyde thiosemicarbazone fully cooperates, and generates title complex;
The 3rd step, the title complex that second step was generated heat under 200～240 ℃ temperature, generate transient metal sulfide.
2. transient metal sulfide preparation method as claimed in claim 1 is characterized in that, also comprises step:
The transient metal sulfide that the 3rd step was generated filters successively, washing, vacuum drying treatment.
3. transient metal sulfide preparation method as claimed in claim 1 or 2 is characterized in that, it is the self-template hydrothermal method that described title complex generates the preparation method that transient metal sulfide adopted.
4. transient metal sulfide preparation method as claimed in claim 1 or 2 is characterized in that, the transient metal sulfide that is generated consist of MS
x, x=1.0～2.0, wherein M is cobalt metal or nickel, the particle diameter of this transient metal sulfide is 2 μ m.
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| CN106749429A (en) * | 2017-01-13 | 2017-05-31 | 天津理工大学 | A kind of simple and easy method for preparing Thiourea cobalt complex as raw material with cobalt salt, thiocarbamide |
| CN109589990B (en) * | 2017-09-30 | 2022-02-11 | 中国科学院金属研究所 | Cobalt-based heterogeneous catalytic material and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4320030A (en) * | 1980-03-21 | 1982-03-16 | Gas Research Institute | Process for making high activity transition metal catalysts |
| CN1462258A (en) * | 2001-05-08 | 2003-12-17 | Lg化学株式会社 | Method for preparing single crystalline ZnS powder for phosphor |
| CN101113016A (en) * | 2007-07-05 | 2008-01-30 | 复旦大学 | Preparation method of starfish-shaped cadmium sulfide nanostructure |
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2008
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4320030A (en) * | 1980-03-21 | 1982-03-16 | Gas Research Institute | Process for making high activity transition metal catalysts |
| CN1462258A (en) * | 2001-05-08 | 2003-12-17 | Lg化学株式会社 | Method for preparing single crystalline ZnS powder for phosphor |
| CN101113016A (en) * | 2007-07-05 | 2008-01-30 | 复旦大学 | Preparation method of starfish-shaped cadmium sulfide nanostructure |
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