CN1911787A - Preparation method of nanometer metal sulfide - Google Patents
Preparation method of nanometer metal sulfide Download PDFInfo
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- CN1911787A CN1911787A CN 200610088468 CN200610088468A CN1911787A CN 1911787 A CN1911787 A CN 1911787A CN 200610088468 CN200610088468 CN 200610088468 CN 200610088468 A CN200610088468 A CN 200610088468A CN 1911787 A CN1911787 A CN 1911787A
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Abstract
The preparation process of nanometer metal sulfide includes the following steps: mixing transition metal oxide or transition metal powder and thiourea in the metal/sulfur molar ratio of 1 to 0.8-4 through grinding or ball milling for 1-4; setting the mixture in ceramic or clay crucible and heating inside muffle at some determined temperature within 200-500 deg.c for 4-8 hr; and taking out the crucible after cooling to room temperature and grinding or ball milling for 3-30 min to obtain the product. The preparation process of the present invention has short mixing time and short reaction time.
Description
One. technical field
The present invention relates to a kind of preparation method of nanometer sulfides powder, the preparation method of especially nano metal sulphide, and use solid state reaction.
Two. background technology
Transient metal sulfide is in optics, photoelectrochemistry, catalysis, light-emitting device, aspects such as semi-conductor even superconduction increasing application arranged
[1-3]The transition metal dichalcogenide that wherein has 3d valence electron shell structure is as FeS
2, CoS
2, NiS
2Deng having the pyrite structure usually.In recent years, these compounds have obtained paying attention to widely and using with its unique character, as photochromics and high energy density cells material etc.
[4-5]When the transition metallic sulfide had nanostructure, it was at optics, electricity, and the character of aspect uniquenesses such as catalysis can access further optimization.
The eastern Gui of Piao and this invention of Jin Hengfan " metallic sulfide and preparation method thereof " (number of patent application 02127680.3) need be put into a sealed vessel with the metal component of at least a powder or particle form with steel ball with sulphur; Rotation or vibrate described container or is rotated the rotator in the described container, by absorption of vibrations and pulverizing-welding-pulverizings blended or dispersive mixture, or the topochemistry welding of mixture, prepare metallic sulfide; Metallic sulfide is heat-treated; And to pulverizing through heat treated metallic sulfide and disperseing.The application does not conflict with foregoing invention.
Wu Qingsheng, Liu Jinku and Ding Yaping have applied for Chinese patent (number of patent application 03150857.X).This invention has proposed a kind of preparation method of metal sulfide semiconductor nanometer crystalline substance, relates to the method for producing the metal sulfide semiconductor nanometer crystalline substance with template.The application does not conflict with foregoing invention.
King's instruction, Zhuan Jing and Li Yadong application Chinese patent (patent No. 200510103028.9).It is raw material that inorganic salt, alkali metal hydroxide, sulfocompound are adopted in this invention, reacts in the mixed system of lipid acid, water, organic polar solvent, promptly can obtain the sulfide particles of dispersed nano level.The application does not conflict with foregoing invention.
M Bert difficult to understand; P Ma Kaodile has applied for Chinese patent (number of patent application 96198016.8).The preparation method of this sulfide is characterised in that the carbonate of at least a rare earth metal or supercarbonate contacted with the compound of at least a alkali metal, and with its heating in the presence of at least a gas that is selected from hydrogen sulfide or dithiocarbonic anhydride.The application does not conflict with foregoing invention.
Traditional method for preparing sulfide is that employing is directly vulcanized or with there being hypertoxic hydrogen sulfide to react, these methods may cause some environmental problems easily.And top some that mention adopts hydrothermal method, and sol-gel method etc. just synthesize in the laboratory, and the cost equipment requirements is higher, and is not suitable for large-scale industrial production, and these methods are just at some sulfide.
The present invention prepares the nanometer sulfide powder according to low-temperature solid phase reaction, especially transition metal, CdS or Ag
2S nanometer sulfide powder (comprises FeS
2, CoS
2, NiS
2, ZnS, CuS, CdS and Ag
2S), make the symbiosis product distillation of the target powder that generates in the reaction, thereby reach the separation and the purifying of product, obtain target powder by heating.The present invention utilizes the low-heat solid state reaction, does not use solvent, has highly selective, high yield, simple technological process and other advantages; Will with the symbiotic resultant of target compound by the mode that heating sublimation decomposes, solved the difficulty that the low-temperature solid phase reaction product is difficult to separation and purification preferably; The effect of tensio-active agent is played by the organism group of Sheng Chenging simultaneously, can be used as the low temperature solid state reaction is combined with the preparation of mesoporous material, reaches the solid phase method preparation and the purifying of nanometer product, avoids chemical method to prepare the wet scrubbing process of nano material.Products therefrom is crystal perfection, a pattern meso-porous nano powder clearly.The inventive method raw material is easy to get, and is easy and simple to handle, mild condition, and technical process is simple, need not complex apparatus, and reaction process is short, and productive rate height, transformation efficiency are almost near a hundred per cent.Because it has the advantage of cheap synthetic cost, can greatly promote the large-scale industrial production of mesoporous material, promote simultaneously this novel nano hole material in bulky molecular catalysis, absorption and separate, the research and the application of functional materials such as transmitter, micro element and light, electricity, magnetic.
Three. summary of the invention
The present invention seeks to: propose a kind of transition metal and (comprise FeS
2, CoS
2, NiS
2, ZnS, CuS, CdS and Ag
2S) preparation method of nanometer sulfide, especially a kind of series of carrying out solid state reaction with oxide compound or transition metal powders and thiocarbamide prepares the method for nanometer sulfide, and a kind of convenience is provided, and fast, cost is low, the preparation method of highly versatile.
Technical solution of the present invention is: the preparation method of nano metal sulphide is characterized in that the synthetic concrete experimental procedure of transition metal chalcogenide nanocrystal thing comprises that specific embodiment is:
(1) adopt abrading type to mix method, with transition metal oxide, silver suboxide or Cadmium oxide promptly (ferric oxide, cupric oxide, silver suboxide, zinc oxide, tricobalt tetroxide, nickel oxide, silver suboxide or Cadmium oxide) and thiocarbamide by following mixed: in the transition metal oxide in metal and the thiocarbamide mol ratio of element sulphur (stoichiometric ratio) be: 1: 0.8～4;
(2) mixture is ground or ball milling 0.1-4 hour, it is mixed; Especially grinding or ball milling control particle diameter is at the 1-10 micron;
(3) then the powder that mixes is packed into ceramic crucible and put into retort furnace carries out heat treated, and insulation is at 200 ℃--and between 500 ℃ certain is determined temperature 1-8 hour, and especially temperature rise rate is 1-8 ℃/minute, naturally cools to room temperature then.
Take out crucible when (4) treating that temperature is reduced to room temperature, product is ground or ball milling 3-30 minute promptly.Ethanol or ether are solvent during ball milling.
Characteristics of the present invention are:
1 reaction times is short, and preparation cycle is short.The mixing process of the raw material of the inventive method and the time of reaction process are all shorter, and the reaction times generally is no more than 5 hours, and the temperature of reaction is also lower, look different material, and temperature range has certain variation.
2 is with low cost.Cost of material of the present invention is comparatively cheap, and production unit requires very simple, does not relate to the higher equipment of cost such as autoclave, and the cost of scale operation is comparatively cheap.
3 pairs of environment of reduced contamination, present method can not relate to the use of organic solvent, can not produce waste water and waste residue.Produce in the gas and contain a small amount of SO
2, can effectively handle by proper method.
4 can synthesize multiple nanometer sulfide, have good versatility.Present method can be synthesized FeS
2, CoS
2, NiS
2, Ag
2S, CuS, TiS
2, many clocks such as CdS and ZnS nanometer sulfide.
With commercially available oxide compound (ferric oxide, cupric oxide, silver suboxide, zinc oxide, tricobalt tetroxide, nickel oxide, silver suboxide or Cadmium oxide) (analytical pure) and thiocarbamide (analytical pure).
Four, description of drawings
Fig. 1 is the corresponding embodiment 1 nano level Ni of the present invention
2The photo of S
Fig. 2 is the corresponding embodiment 2 nano level Ni of the present invention
2The photo of S
Fig. 3 is the photo of the corresponding embodiment 3 nano level ZnS of the present invention
Five. embodiment
Embodiment 1: stoichiometric ratio is 1: 1 a ferric oxide and thiocarbamide ground and mixed ten minutes in mortar, and the clay crucible of packing into is positioned in the retort furnace, and five hours calcinings are taken out through 300 degree, and the product that obtains carries out suitable grinding can obtain FeS
2, can produce gas SO when adopting excessive thiocarbamide (described stoichiometric ratio is that mol ratio is) reaction at 1: 3 o'clock
2, do not make the mixing of mill more even, other comes to the same thing.The effect of 300 ± 40 ° of calcination does not have remarkable difference, but when temperature is higher, can the corresponding shortening treatment time.Adopt cupric oxide or silver suboxide to have effect same.But the incinerating temperature is inequality.
Embodiment 2: stoichiometric ratio is that 1: 1.2 zinc oxide mixed in mortar ten minutes with thiocarbamide, the clay crucible of packing into is positioned in the retort furnace, and five hours calcinings are taken out through 400 degree, the product that obtains carries out suitable grinding can obtain ZnS, and the mixing of ball milling is more even.400 ± 50 ° effect also can.
Adopt silver suboxide to have effect same, the incinerating temperature is at 220 degree.
Embodiment 3: stoichiometric ratio is that 1: 2 nickel oxide mixed in mortar ten minutes with thiocarbamide, and pack into clay or ceramic crucible are positioned in the retort furnace, and five hours calcining is taken out through 250 degree, and the product that obtains carries out suitable grinding can obtain NiS
2, the mixing of ball milling is more even.± 30 ° of calcinings of five hours of 250 degree also can.Adopt zinc oxide, tricobalt tetroxide or silver suboxide to have effect same, but the incinerating temperature is inequality, states as follows.
Embodiment 4: stoichiometric ratio is that 1: 1 silver suboxide mixed in mortar ten minutes with thiocarbamide, and pack into clay or ceramic crucible are positioned in the retort furnace, and five hours calcining is taken out through 200 degree, and the product that obtains carries out suitable grinding can obtain FeS
2Adopt better effects if more than 5 hours, but can influence efficient, ± 25 ° of calcinings of five hours of 200 degree all can, the calcination processing more than 4 hours does not have remarkable difference.Time is relevant with the scope of temperature.
Adopt ferric oxide, zinc oxide, tricobalt tetroxide, nickel oxide or Cadmium oxide that equifinality is arranged.But it is inequality in retort furnace incinerating temperature, general respectively through 350 degree, 420 degree, 300 degree, 4 hours calcining of 450 degree.
According to The above results, this preparation transient metal sulfide synthetic method range of application of the present invention is wider.By the control reaction conditions, just can obtain sulfide through simple calcining from corresponding oxide compound, reaction conditions is simple, with low cost, speed of response is fast, does not need complicated conversion unit, invest lessly, very big application prospect is arranged, very big advantage is arranged with respect to traditional synthetic method.
With reference to the accompanying drawings, as can be seen from Figure 1 NiS
2The size distribution of particle is more even, and it is less to reunite, and is about 40-50nm, more approaching with the particle diameter (37.7nm) that the Scherrer formula is calculated.
Fig. 2 is the photo of the corresponding embodiment 2 nano level CuS of the present invention; As can be seen from the figure also relatively evenly, it is less to reunite, about 70nm, more approaching with the particle diameter (61.3nm) that the Scherrer formula is calculated for the size distribution of CuS particle.
The ZnS particle diameter is smaller as can be seen among Fig. 3, is evenly distributed, and is about 20-30nm, more approaching with the particle diameter (46.3nm) that the Scherrer formula is calculated.
Claims (4)
1, the preparation method of nano metal sulphide is characterized in that transition metal oxide or transition metal powders and thiocarbamide by following mixed: the mol ratio of element sulphur in metal and the thiocarbamide in the transition metal oxide: 1: 0.8～4;
(1) adopts grinding or ball milling to mix, be about to mixture and grind or ball milling 1-4 hour, it is mixed;
(2) then the powder that mixes is packed into pottery or clay crucible and put into retort furnace carry out heat treated, and insulation certain between 200 ℃-500 ℃ is determined temperature 4-8 hour;
Take out crucible when (3) treating that temperature is reduced to room temperature, product is ground or ball milling 3-30 minute promptly.
2, the preparation method of nano metal sulphide according to claim 1 is characterized in that grinding or ball milling is controlled particle diameter at the 1-10 micron.
3, the preparation method of nano metal sulphide according to claim 1 is characterized in that temperature rise rate is 3-8 ℃/minute, naturally cools to room temperature then.
4, the preparation method of nano metal sulphide according to claim 1, it is characterized in that crossing metal oxide, silver suboxide or Cadmium oxide is ferric oxide, cupric oxide, silver suboxide, zinc oxide, tricobalt tetroxide, nickel oxide, silver suboxide or Cadmium oxide, and interpolation ethanol or ether are solvent during ball milling.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7799311B2 (en) | 2007-09-28 | 2010-09-21 | Eveready Battery Company, Inc. | Processes for producing synthetic pyrite |
| CN104817103A (en) * | 2015-03-27 | 2015-08-05 | 淮北师范大学 | Solid phase reaction preparation method of cuprous sulfide nanopowder |
| CN107029756A (en) * | 2017-06-01 | 2017-08-11 | 新疆大学 | A kind of method that solid phase prepares zinc sulphide silver sulfide heterojunction composite |
| CN110002407A (en) * | 2018-01-05 | 2019-07-12 | 武汉大学 | A kind of method of carbon-thermal reduction synthesis metal sulfide |
| CN110803723A (en) * | 2019-12-03 | 2020-02-18 | 兰州理工大学 | Solid-phase synthesis method of high-purity nickel disulfide nanospheres |
| CN114100784A (en) * | 2021-12-02 | 2022-03-01 | 中国电子科技集团公司第四十六研究所 | Raw material processing method for growing CdS single crystal by PVT method |
| CN114195103A (en) * | 2021-12-30 | 2022-03-18 | 北京科技大学 | Preparation method of alkali metal and alkaline earth metal sulfide |
| CN114196982A (en) * | 2021-11-12 | 2022-03-18 | 西安理工大学 | For electrocatalysis of CO2Process for preparing reduced CuSe catalysts |
| CN115301195A (en) * | 2022-07-29 | 2022-11-08 | 中南大学 | Multi-metal sulfide material, preparation method thereof and application of multi-metal sulfide material as mercury adsorbent |
| CN115318258A (en) * | 2022-06-27 | 2022-11-11 | 中南大学 | Metal sulfide adsorbent based on mechanical ball milling and preparation method and application thereof |
| CN115624979A (en) * | 2022-10-19 | 2023-01-20 | 南京大学 | Application of modified black titanium dioxide in degradation of antibiotic wastewater |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0761816A (en) * | 1993-08-25 | 1995-03-07 | Idemitsu Kosan Co Ltd | Production of metallic sulfide powder |
| CN1185306C (en) * | 2001-02-26 | 2005-01-19 | 中国科学院长春应用化学研究所 | Process for preparing doped nm powder of zine sulfide |
| CN1757603A (en) * | 2005-10-27 | 2006-04-12 | 上海大学 | Method for preparing nanometer sulfides powder |
| CN1803632A (en) * | 2006-01-24 | 2006-07-19 | 唐百仲 | Method for preparing nanometer metallic sulfide |
-
2006
- 2006-08-25 CN CNB2006100884686A patent/CN100408471C/en not_active Expired - Fee Related
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7799311B2 (en) | 2007-09-28 | 2010-09-21 | Eveready Battery Company, Inc. | Processes for producing synthetic pyrite |
| CN104817103A (en) * | 2015-03-27 | 2015-08-05 | 淮北师范大学 | Solid phase reaction preparation method of cuprous sulfide nanopowder |
| CN104817103B (en) * | 2015-03-27 | 2016-04-27 | 淮北师范大学 | A kind of solid state reaction preparation method of cuprous sulfide nano-powder |
| CN107029756A (en) * | 2017-06-01 | 2017-08-11 | 新疆大学 | A kind of method that solid phase prepares zinc sulphide silver sulfide heterojunction composite |
| CN110002407A (en) * | 2018-01-05 | 2019-07-12 | 武汉大学 | A kind of method of carbon-thermal reduction synthesis metal sulfide |
| CN110002407B (en) * | 2018-01-05 | 2022-07-19 | 武汉大学 | Method for synthesizing metal sulfide by carbothermic reaction |
| CN110803723A (en) * | 2019-12-03 | 2020-02-18 | 兰州理工大学 | Solid-phase synthesis method of high-purity nickel disulfide nanospheres |
| CN114196982A (en) * | 2021-11-12 | 2022-03-18 | 西安理工大学 | For electrocatalysis of CO2Process for preparing reduced CuSe catalysts |
| CN114100784A (en) * | 2021-12-02 | 2022-03-01 | 中国电子科技集团公司第四十六研究所 | Raw material processing method for growing CdS single crystal by PVT method |
| CN114100784B (en) * | 2021-12-02 | 2023-08-22 | 中国电子科技集团公司第四十六研究所 | Raw material treatment method for growing CdS monocrystal by PVT method |
| CN114195103A (en) * | 2021-12-30 | 2022-03-18 | 北京科技大学 | Preparation method of alkali metal and alkaline earth metal sulfide |
| CN114195103B (en) * | 2021-12-30 | 2022-08-30 | 北京科技大学 | Preparation method of alkali metal and alkaline earth metal sulfide |
| CN115318258A (en) * | 2022-06-27 | 2022-11-11 | 中南大学 | Metal sulfide adsorbent based on mechanical ball milling and preparation method and application thereof |
| CN115318258B (en) * | 2022-06-27 | 2023-10-27 | 中南大学 | Metal sulfide adsorbent based on mechanical ball milling and preparation method and application thereof |
| CN115301195A (en) * | 2022-07-29 | 2022-11-08 | 中南大学 | Multi-metal sulfide material, preparation method thereof and application of multi-metal sulfide material as mercury adsorbent |
| CN115301195B (en) * | 2022-07-29 | 2023-05-23 | 中南大学 | Multi-metal sulfide material, preparation method thereof and application of multi-metal sulfide material as mercury adsorbent |
| CN115624979A (en) * | 2022-10-19 | 2023-01-20 | 南京大学 | Application of modified black titanium dioxide in degradation of antibiotic wastewater |
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