CN103073073A - Synthetic method of transition metal sulfide - Google Patents
Synthetic method of transition metal sulfide Download PDFInfo
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- CN103073073A CN103073073A CN201310036609XA CN201310036609A CN103073073A CN 103073073 A CN103073073 A CN 103073073A CN 201310036609X A CN201310036609X A CN 201310036609XA CN 201310036609 A CN201310036609 A CN 201310036609A CN 103073073 A CN103073073 A CN 103073073A
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Abstract
The invention relates to a synthetic method of transition metal sulfide, and belongs to the technical field of inorganic synthetic methods. The method comprises the steps that nitrate of transition metal (cobalt, nickel or cadmium) and excessive thiourea are mixed, react for 4-24h at 180-240 DEG C, and are cooled to a room temperature, washed and filtered, and sulfide of the transition metal (the cobalt, nickel or cadmium) is obtained. In a reaction system of the synthetic method, thiourea serves as a reactant and a fluxing agent, so that the problems that other substances are required to be added as a fluxing agent in the traditional fluxing agent method, foreign ions are introduced to cause pollution to a synthetic crystal, and transition metal sulfide cannot be synthesized by the traditional fluxing agent method are overcome; transition metal sulfide can be synthesized under a low-temperature fuse salt condition; adopted raw materials are cheap and easy to obtain; and the synthetic method is simple in synthetic technology, short in reaction period, small in energy consumption, environment-friendly, and low in equipment requirement, and is suitable for large-scale industrial production.
Description
Technical field
The invention belongs to the technical field of synthesis methods for inorganic compounds, specifically, is a kind of about take the nitrate of transition metals cobalt, nickel or cadmium and thiocarbamide as raw material, directly prepares the method for transient metal sulfide.
Background technology
The special construction of transient metal sulfide and composition make it have unique optics, electricity, magnetics, friction and catalytic performance, be widely used in the sun power convertor, solid lithium ion battery electrode materials, magneticsubstance, capacitance material, catalyzer and solid lubricant.Nanometer sulfuration cobalt dust is because its dimensional effect, makes that energy gap broadens, Absorption and emission spectra moves to the shortwave direction, and this all has material impact to optics, electricity and non-linear optical property.
At present the synthetic method of transient metal sulfide nano material has a lot, and prior synthesizing method relates to the reaction under high energy and the protection of inert gas more, and for example high temperature solid-state is synthesized, hydro-thermal, solvent thermal and organism thermolysis etc.Flux method also can't be synthesized transient metal sulfide.The most organic additives that add of existing synthetic method, perhaps complicated to the having relatively high expectations of reaction vessel, reactions steps, and inevitable effluent discharge contaminate environment, reaction cost is higher, is difficult to carry out mass industrialized production.
Summary of the invention
The technical problem to be solved in the present invention is to overcome prior art effluent discharge contaminate environment, and reaction cost is higher, is difficult to carry out the problems such as mass industrialized production, and a kind of synthetic method of transient metal sulfide is provided.Reach the simplification reactions steps, reaction process is pollution-free, and cost is low, can be used for the purpose of suitability for industrialized production.
Technical scheme of the present invention is: a kind of novel method of fusing assistant one step preparation transient metal sulfide, the steps include: transition metals cobalt, nickel or cadmium nitrate are mixed with excessive thiocarbamide, under 180 ℃ ~ 240 ℃ temperature (being lower than 180 ℃ of products that obtain the degree of crystallization deficiency) condition, reacted 4～24 hours, be cooled to room temperature, washing, filter, obtain the sulfide of transition metals cobalt, nickel and cadmium.Concrete technical scheme is as described below.
A kind of synthetic method of transient metal sulfide with transition metal nitrate and the thiocarbamide mixing of mol ratio 1: 5 ~ 10, was reacted 4～24 hours under 180 ~ 240 ℃ of temperature condition, was cooled to room temperature, washing, filtration, obtained transient metal sulfide.
Described transition metal nitrate is the nitrate (that is, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, nickelous nitrate or cadmium nitrate) of cobalt, nickel or cadmium.Corresponding product is the sulfide of cobalt, nickel or cadmium.
Described washing is to use deionized water wash 2 ~ 3 times.
In the reaction system of the present invention, thiocarbamide namely also exists as fusing assistant simultaneously as reactant, the mol ratio of transition metal nitrate and thiocarbamide is 1: 5 in theory, when the thiocarbamide mole dosage is lower than 5 times of transition metal nitrate, obtain the product of degree of crystallization deficiency, but consider the carrying out of reaction and the efficient of technique, the consumption of thiocarbamide should be 5～10 times of transition metal nitrate by mol.
Reaction conditions is minimum 180 ℃ of lower reactions 4 hours, and temperature of reaction is higher than 180 ℃, reaction will be more abundant greater than 4 hours in the reaction times.But, too high temperature of reaction or oversize reaction times, will waste energy, raise the cost, reduce production efficiency.Thus, preferred reaction conditions is to react 4 hours under 180 ~ 200 ℃ of conditions.
The resulting product of the present invention advanced powder x-ray diffraction, scanning electronic microscope and projection electron microscope test, and the result shows: prepared product is pure phase, is of a size of nano level transient metal sulfide.
Advantage of the present invention is: in the reaction system, thiocarbamide namely also exists as fusing assistant simultaneously as reactant, has overcome traditional flux method and has added other material as fusing assistant, introduces foreign ion composite crystals is polluted; Overcome simultaneously traditional flux method and can't synthesize the restriction of transient metal sulfide, by thiocarbamide namely as reactant simultaneously also as fusing assistant, reduced the temperature of melting salt system, can under the low temperature molten salt state, synthesize transient metal sulfide.Raw material of the present invention is cheap and easy to get, synthesis technique is simple, reaction time is short, temperature is low, energy consumption is little, friendly, low for equipment requirements to environment, be fit to large-scale commercial production.
Description of drawings
Fig. 1 is the X-ray diffractogram of embodiment 1,2,3 cobalt disulfide of differential responses time preparation under 180 ℃ of conditions.Wherein, (a) reaction 4h, (b) reaction 12h, (c) reaction 24h.
Fig. 2 is embodiment 1 reacts the cobalt disulfide of 4h preparation under 180 ℃ of conditions scanning electron microscope (SEM) photograph.
Fig. 3 is comparative example 1, embodiment 4 react the cobalt disulfide of 4h preparation under condition of different temperatures X-ray diffractogram.Wherein, (a) 150 ℃, (b) 200 ℃.
Fig. 4 is embodiment 5 material molar ratios 1: 10, the X-ray diffractogram of the cobalt disulfide of reaction 4h preparation under 180 ℃ of conditions.
Fig. 5 is comparative example 2 material molar ratios 1: 3, the X-ray diffractogram of the cobalt disulfide of reaction 4h preparation under 180 ℃ of conditions.
Fig. 6 is that embodiment 6 is at the X-ray diffractogram of the curing nickel of 180 ℃ of reaction 4h preparation.
Fig. 7 is that embodiment 6 is at the scanning electron microscope (SEM) photograph of the curing nickel of 180 ℃ of reaction 4h preparation.
Fig. 8 is that embodiment 7 is at the X-ray diffractogram of the Cadmium Sulfide of 180 ℃ of reaction 4h preparation.
Fig. 9 is that embodiment 7 is at the scanning electron microscope (SEM) photograph of the Cadmium Sulfide of 180 ℃ of reaction 4h preparation.
Embodiment
By following example the present invention is further set forth.
Embodiment 1:
Get the 0.30g Cobaltous nitrate hexahydrate and mix (cobalt, sulphur mol ratio 1: 5) with the 0.42g thiocarbamide, put into reaction vessel, 180 ℃ were reacted 4 hours, took out and were cooled to room temperature, and washing is filtered.Obtain black cobalt disulfide powder.Its X-ray diffractogram (XRD) is shown in Fig. 1 (a), and its scanning electron microscope (SEM) photograph (SEM) as shown in Figure 2.
Embodiment 2:
Get the 0.30g Cobaltous nitrate hexahydrate and mix (cobalt, sulphur mol ratio 1: 5) with the 0.42g thiocarbamide, put into reaction vessel, 180 ℃ were reacted 12 hours, took out and were cooled to room temperature, and washing is filtered.Obtain black cobalt disulfide powder.Its X-ray diffractogram (XRD) is shown in Fig. 1 (b).
Embodiment 3:
Get the 0.30g Cobaltous nitrate hexahydrate and mix (cobalt, sulphur mol ratio 1: 5) with the 0.42g thiocarbamide, put into reaction vessel, 180 ℃ were reacted 24 hours, took out and were cooled to room temperature, and washing is filtered.Obtain black cobalt disulfide powder.Its X-ray diffractogram (XRD) is shown in Fig. 1 (c).
Embodiment 4:
Get the 0.30g Cobaltous nitrate hexahydrate and mix (cobalt, sulphur mol ratio 1: 5) with the 0.42g thiocarbamide, put into reaction vessel, 200 ℃ were reacted 4 hours, took out and were cooled to room temperature, and washing is filtered.Obtain black cobalt disulfide powder.Its X-ray diffractogram (XRD) is shown in Fig. 3 (b).
Embodiment 5:
Get the 0.30g Cobaltous nitrate hexahydrate and mix (cobalt, sulphur mol ratio 1: 10) with the 0.84g thiocarbamide, put into reaction vessel, 180 ℃ were reacted 4 hours, took out and were cooled to room temperature, and washing is filtered.Obtain black cobalt disulfide powder.Its X-ray diffractogram (XRD) as shown in Figure 4.
Embodiment 6:
The reaction raw materials of replacing system is got the 0.30g Nickelous nitrate hexahydrate and is mixed (nickel, sulphur mol ratio 1: 5) with the 0.42g thiocarbamide, puts into reaction vessel, and 180 ℃ were reacted 4 hours, takes out and is cooled to room temperature, and washing is filtered.Obtain the black NiS 2 powder.Its X-ray diffractogram (XRD) as shown in Figure 6, its scanning electron microscope (SEM) photograph (SEM) is as shown in Figure 7.
Embodiment 7:
The reaction raw materials of replacing system is got 0.46g six nitric hydrate cadmiums and is mixed (cadmium, sulphur mol ratio 1: 5) with the 0.76g thiocarbamide, puts into reaction vessel, and 180 ℃ were reacted 4 hours, takes out and is cooled to room temperature, and washing is filtered.Obtain orange Cadmium Sulfide powder.Its X-ray diffractogram (XRD) as shown in Figure 8, its scanning electron microscope (SEM) photograph (SEM) is as shown in Figure 9.
Comparative example 1:
Get the 0.30g Cobaltous nitrate hexahydrate and mix (cobalt, sulphur mol ratio 1: 5) with the 0.42g thiocarbamide, put into reaction vessel, 150 ℃ were reacted 4 hours, took out and were cooled to room temperature, and washing is filtered.Obtain black cobalt disulfide powder.Its X-ray diffractogram (XRD) is shown in Fig. 3 (a), and temperature of reaction is lower than 180 ℃ of products that obtain the degree of crystallization deficiency.
Comparative example 2:
Get the 0.30g Cobaltous nitrate hexahydrate and mix (cobalt, sulphur mol ratio 1: 3) with the 0.246g thiocarbamide, put into reaction vessel, 180 ℃ were reacted 4 hours, took out and were cooled to room temperature, and washing is filtered.Obtain black cobalt disulfide powder.Its X-ray diffractogram (XRD) as shown in Figure 5, the reaction raw materials mol ratio is less than the product that obtains the degree of crystallization deficiency at 1: 5.
Claims (4)
1. the synthetic method of a transient metal sulfide with transition metal nitrate and the thiocarbamide mixing of mol ratio 1: 5 ~ 10, was reacted 4～24 hours under 180 ~ 240 ℃ of temperature condition, was cooled to room temperature, and washing, filtration obtain transient metal sulfide.
2. the synthetic method of transient metal sulfide according to claim 1 is characterized in that, described transition metal nitrate is the nitrate of cobalt, nickel or cadmium.
3. the synthetic method of transient metal sulfide according to claim 1 and 2 is characterized in that, after transition metal nitrate and thiocarbamide mixing, reaction is 4 hours under 180 ~ 200 ℃ of temperature condition.
4. the synthetic method of transient metal sulfide according to claim 1 and 2 is characterized in that, described washing is to use deionized water wash 2 ~ 3 times.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104846428A (en) * | 2015-04-13 | 2015-08-19 | 山东大学 | Method used for growth of transition metal chalcogenide crystals via metal fluxing agent method |
| CN106340396A (en) * | 2016-11-02 | 2017-01-18 | 信阳师范学院 | Method for preparing CdCo2S4 nano-structured super-capacitor electrode material using foam nickel as the substrate |
| 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 |
| CN106917105A (en) * | 2017-01-13 | 2017-07-04 | 太原理工大学 | A kind of water decomposition preparation method of self-supporting transient metal sulfide foam electrode |
| CN109589990A (en) * | 2017-09-30 | 2019-04-09 | 中国科学院金属研究所 | A kind of cobalt-based heterogeneous catalysis material and its preparation method and application |
| CN109607594A (en) * | 2018-12-18 | 2019-04-12 | 合肥学院 | A method of form controllable metal sulfide is prepared using polyacrylamide |
| CN109999837A (en) * | 2019-04-29 | 2019-07-12 | 淮北师范大学 | A kind of preparation method of the metal sulfide catalyst of surface defect state modification |
| RU2738586C1 (en) * | 2019-10-31 | 2020-12-14 | Федеральное государственное автономное образовательное учреждение высшего образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина" | Method of producing films of solid solutions of substitution of pbcds by ion-exchange transformation of cds films |
| CN112279306A (en) * | 2020-10-21 | 2021-01-29 | 南京晓庄学院 | Optimization method of sulfide nanocrystal, Sn-S-Co nanocrystal and optimized product thereof |
| CN115216296A (en) * | 2022-08-09 | 2022-10-21 | 烟台布莱特光电材料有限公司 | Synthesis method of efficient blue fluorescent powder for excitation of purple light LED |
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Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104846428B (en) * | 2015-04-13 | 2017-04-05 | 山东大学 | A kind of method that metal fusing agent method grows transient metal chalcogenide compound crystal |
| CN104846428A (en) * | 2015-04-13 | 2015-08-19 | 山东大学 | Method used for growth of transition metal chalcogenide crystals via metal fluxing agent method |
| CN106340396B (en) * | 2016-11-02 | 2018-03-09 | 信阳师范学院 | A kind of nickel foam is the CdCo of substrate2S4The preparation method of nanostructured electrode material for super capacitor |
| CN106340396A (en) * | 2016-11-02 | 2017-01-18 | 信阳师范学院 | Method for preparing CdCo2S4 nano-structured super-capacitor electrode material using foam nickel as the substrate |
| CN106917105B (en) * | 2017-01-13 | 2019-05-31 | 太原理工大学 | A kind of preparation method of water decomposition self-supporting transient metal sulfide foam electrode |
| CN106917105A (en) * | 2017-01-13 | 2017-07-04 | 太原理工大学 | A kind of water decomposition preparation method of self-supporting transient metal sulfide foam electrode |
| 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 |
| CN109589990A (en) * | 2017-09-30 | 2019-04-09 | 中国科学院金属研究所 | A kind of cobalt-based heterogeneous catalysis material and its preparation method and application |
| 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 |
| CN109607594A (en) * | 2018-12-18 | 2019-04-12 | 合肥学院 | A method of form controllable metal sulfide is prepared using polyacrylamide |
| CN109999837A (en) * | 2019-04-29 | 2019-07-12 | 淮北师范大学 | A kind of preparation method of the metal sulfide catalyst of surface defect state modification |
| CN109999837B (en) * | 2019-04-29 | 2022-04-12 | 淮北师范大学 | Preparation method of metal sulfide catalyst with surface defect state modification |
| RU2738586C1 (en) * | 2019-10-31 | 2020-12-14 | Федеральное государственное автономное образовательное учреждение высшего образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина" | Method of producing films of solid solutions of substitution of pbcds by ion-exchange transformation of cds films |
| CN112279306A (en) * | 2020-10-21 | 2021-01-29 | 南京晓庄学院 | Optimization method of sulfide nanocrystal, Sn-S-Co nanocrystal and optimized product thereof |
| CN112279306B (en) * | 2020-10-21 | 2021-07-06 | 南京晓庄学院 | Optimization method of sulfide nanocrystal, Sn-S-Co nanocrystal and optimized product thereof |
| CN115216296A (en) * | 2022-08-09 | 2022-10-21 | 烟台布莱特光电材料有限公司 | Synthesis method of efficient blue fluorescent powder for excitation of purple light LED |
| CN115216296B (en) * | 2022-08-09 | 2023-10-24 | 烟台布莱特光电材料有限公司 | Synthetic method of efficient blue fluorescent powder for excitation of ultraviolet LED |
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