CN102671590B - Preparation method of carbon coated magnetic nano-spherical iron sulfide - Google Patents
Preparation method of carbon coated magnetic nano-spherical iron sulfide Download PDFInfo
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- CN102671590B CN102671590B CN201210163390.5A CN201210163390A CN102671590B CN 102671590 B CN102671590 B CN 102671590B CN 201210163390 A CN201210163390 A CN 201210163390A CN 102671590 B CN102671590 B CN 102671590B
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Abstract
The invention discloses a preparation method of carbon coated magnetic nano-spherical iron sulfide (Fe7S8) powder; ferrocene and derivatives of the ferrocene are further reacted with ammonium persulfate in one step to prepare carbon coated nano-spherical iron sulfide Fe7S8 powder. The magnetic nano Fe7S8 particle prepared by the method is spherical, the diameter is intensively distributed between 10 nm to 50nm, a coated carbon shell has a graphitizing carbon structure, and the thickness is intensively distributed between 5 nm to 20nm. The preparation method provided by the invention has the characteristics of simple equipment, easy operation, low cost, high efficiency, environmental protection and the like, and is suitable for industrial production; the prepared carbon coated magnetic nano-spherical Fe7S8 powder is good in stability, and the method has wide application prospects in the fields of environmental depollution, drug targeting, absorbing materials and the like.
Description
Technical field
The present invention relates to a kind of carbon-coated magnetic nanometer spherical iron sulfide (Fe
7s
8) preparation method of powder.
Background technology
Be subject to the impact of occurring in nature complicated geological environment, and the element sulphur that forms iron sulfide all has relative abundant valent state with ferro element, can there is the variation of component and crystal structure in the iron sulfide of each kind, therefore naturally occurring iron sulfide is of a great variety under the impact of temperature.Having verified at present the also iron sulfide mineral of clear and definite its crystal structure is divided into following several, as shown in table 1 according to the ratio between Fe and S element.Wherein, under outside magnetic field effect, show magnetic magnetic iron ore and wait axle magnetic pyrite the most people be concerned about, be not only because the circulation in these two kinds of compounds and biosphere and earth magnetics have closely to be contacted, more importantly they have complexity and abundant magnetic-structure-temperature relation.These unique character are studied the crystal structure of Magnetic Nanocrystals Containing and the relation of magnetic property provides good sample for people.Therefore, iron sulfide all has great significance in circulation, earth magnetics and the field of metallurgy in research origin of life, biosphere.
The title of the common iron sulfide of table 1, molecular formula and magnetic property thereof
In recent years, the further investigation of iron sulfide nano material shows that it has a wide range of applications and cause that people pay close attention to greatly in fields such as the depollution of environment, the storage of VHD magnetic, Magnetic Isolation, catalyst, biological medicine, sensings.As, pyrite (FeS
2) semiconductor is for solar spectrum, has suitable energy gap and the very high absorption coefficient of light, than high two orders of magnitude of crystalline silicon.Its component is cheap, the rich content in the earth, and environment compatibility is better, stable performance, and FeS
2can exist with the form of film, consumption is few, and cost is low, therefore, and FeS
2film has potential application prospect in solar cell material field.On the other hand, with FeS
2li-FeS for cathode active material
2battery has that specific energy is large, capacity is high, high discharge platform, memory time is long, cost is low and the advantage of environmental protection.FeS can be used for processing electroplated heavy metals waste water, and its advantage is: raw material sources are extensive, low price, simple to operate, good to the removal effect of heavy metal, and can not cause secondary pollution.Fe
1-xs is owing to having magnetic, can be used for magnetic carrier in electromagnetic shielding, magnetic storage, magnetic fluid, NMR contrast agent, drug targeting treatment etc.
But most iron sulfide nano materials are unstable in air, be easy to oxidizedly, synthetic method is relatively less, needs anhydrous and oxygen-free reaction condition and covering etc.At present conventional have presoma pyrolysismethod, a hydro-thermal method etc.But general program comparision is complicated, and the reaction time is long, and organic matter precursor used is poisonous, therefore contaminated environment is utilized simple synthetic method to prepare iron sulfide nano material and is had very important significance.In addition, it is also the major issue that its preparation and application need to solve that the iron sulfide nano material that how to make to prepare has good stability.Only has by CNT at present and be coated the preparation method that Fe7S8 guarantees its stability, but reaction temperature is too high, technology and equipment too complexity (Chinese patent, CN201010532478.0).In sum, it is very important finding a kind of simple and environment amenable synthetic method.
Summary of the invention
The object of the present invention is to provide a kind of carbon-coated magnetic nanometer spherical iron sulfide (Fe for preparing
7s
8) new method, by adopting special composition and engineering, overcome the deficiency in conventional art, thereby realized object of the present invention.
Technical problem solved by the invention can realize by the following technical solutions:
A preparation method for carbon-coated magnetic nanometer spherical iron sulfide, is characterized in that, described preparation method comprises the steps:
1) selecting the derivative of ferrocene or ferrocene and ammonium persulfate is raw material, and both are evenly mixed, and wherein the mol ratio of ferrocene or derivatives thereof and ammonium persulfate is 0.2:1 ~ 2.5:1;
2) raw material mixing is packed in withstand voltage closed reaction vessel, be heated to 150 ~ 250 ℃ and be incubated 0.5 ~ 4 hour, obtain the cotton-shaped powder of black after being cooled to room temperature;
3) with deionized water and absolute ethyl alcohol, the cotton-shaped powder of black is cleaned, is dried successively, obtain having the carbon-coated nano Fe of ferrimagnetism
7s
8powder.
In a preferred embodiment of the invention, the derivative of described ferrocene is any one in ethyl dicyclopentadienyl iron, ferrocenyl methyl ketone, ferrocenecarboxylic acid.
In a preferred embodiment of the invention, described closed reaction vessel inside is vacuum or fills any one in nitrogen, argon gas.
In a preferred embodiment of the invention, described nanometer Fe
7s
8particle is spherical, and diameter is concentrated and is distributed between 10 ~ 50nm.
In a preferred embodiment of the invention, described Fe
7s
8the thickness of the outer coated carbon of particle is concentrated and is distributed between 5 ~ 20nm.
In a preferred embodiment of the invention, described Fe
7s
8the outer coated carbon of particle is easy graphitized carbon structure.
Beneficial effect of the present invention is: reaction can be prepared the spherical Fe of carbon-coated nano by ferrocene or derivatives thereof and ammonium persulfate single step reaction
7s
8powder, technique is simple, and without special installation, and output can regulate by raw material addition and container reaction compartment, is easy to amplify volume production; Secondly, the spherical Fe of carbon-coated nano
7s
8powder has good stability; Again, reaction temperature is only, between 150 ~ 250 ℃, to have the feature of ultralow temperature, is the coated Fe of current carbon
7s
8the minimum preparation temperature of nano material; Finally, the magnetic Nano Fe that prepared by the method
7s
8particle is spherical, and diameter is concentrated and is distributed between 10 ~ 50nm, and coated carbon shell has easy graphitized carbon structure, and thickness is concentrated and is distributed between 5 ~ 20nm.
Accompanying drawing explanation
Fig. 1 is the spherical Fe of carbon-coated nano of embodiment 1 preparation
7s
8the X-ray diffractogram of particle.
Fig. 2 is the spherical Fe of carbon-coated nano of embodiment 1 preparation
7s
8the secondary electron image of particle.
Fig. 3 is the spherical Fe of carbon-coated nano of embodiment 1 preparation
7s
8the backscattered electron image of particle.
Fig. 4 is the spherical Fe of carbon-coated nano of embodiment 1 preparation
7s
8the pattern of particle and image K-M.
Fig. 5 is the spherical Fe of carbon-coated nano of embodiment 1 preparation
7s
8the high-resolution crystal lattice pattern picture of particle.
Fig. 6 is the spherical Fe of carbon-coated nano of embodiment 1 preparation
7s
8the power spectrum image of particle.
The specific embodiment
For technological means, creation characteristic that the present invention is realized, reach object and effect is easy to understand, below in conjunction with the specific embodiment, further set forth the present invention.
The present invention proposes a kind of carbon-coated magnetic nanometer spherical iron sulfide (Fe for preparing
7s
8) new method.This method feature is: reaction can be prepared the spherical Fe of carbon-coated nano by ferrocene or derivatives thereof and ammonium persulfate single step reaction
7s
8powder, technique is simple, and without special installation, and output can regulate by raw material addition and container reaction compartment, is easy to amplify volume production; Secondly, the spherical Fe of carbon-coated nano
7s
8powder has good stability; Again, reaction temperature is only, between 150 ~ 250 ℃, to have the feature of ultralow temperature, is the coated Fe of current carbon
7s
8the minimum preparation temperature of nano material; Finally, the magnetic Nano Fe that prepared by the method
7s
8particle is spherical, and diameter is concentrated and is distributed between 10 ~ 50nm, and coated carbon shell has easy graphitized carbon structure, and thickness is concentrated and is distributed between 5 ~ 20nm.Its microstructure, form and composition characterize as shown in Fig. 1 ~ Fig. 6.So preparation method proposed by the invention has the features such as equipment is simple, easy to operate, cost is low, efficiency is high, environmental protection, be applicable to suitability for industrialized production.
Basic principle of the present invention is: ferrocene or derivatives thereof has reproducibility, can react with strong oxidizer ammonium persulfate, and generate the nanometer spherical Fe with low-surface-energy at a certain temperature
7s
8particle, generates easy graphitized carbon material and is coated on nanometer spherical Fe and the self assembly of cracking dehydrogenation reaction occurs for cyclopentadiene in ferrocene or derivatives thereof simultaneously
7s
8particle surface.Different according to raw material proportioning, have a small amount of H
2s or SO
2gaseous by-product produces, and tail gas can absorb processing in alkaline solution.
Embodiment 1
1 gram of ferrocene is evenly mixed with 2 grams of ammonium persulfates, under glove box nitrogen protection atmosphere, pack volume into and be in the Pressure solution bullet of 50 milliliters of contraposition polyphenyl liners and lock sealing.Pressure solution bullet is heated to 200 ° of C, is cooled to room temperature after being incubated 1 hour.The cotton-shaped powder of the black obtaining is cleaned, is dried with deionized water and absolute ethyl alcohol, obtain 0.69 gram of spherical Fe of carbon-coated nano
7s
8powder.
3 grams of ferrocene are evenly mixed with 8 grams of ammonium persulfates, under glove box nitrogen protection atmosphere, pack volume into and be in the Pressure solution bullet of 50 milliliters of contraposition polyphenyl liners and lock sealing.Pressure solution bullet is heated to 200 ° of C, is cooled to room temperature after being incubated 2 hours.The cotton-shaped powder of the black obtaining is cleaned, is dried with deionized water and absolute ethyl alcohol, obtain 2.46 grams of spherical Fe of carbon-coated nano
7s
8powder.
Embodiment 3
2 grams of ferrocene are evenly mixed with 4 grams of ammonium persulfates, under glove box nitrogen protection atmosphere, pack volume into and be in the Pressure solution bullet of 50 milliliters of contraposition polyphenyl liners and lock sealing.Pressure solution bullet is heated to 150 ° of C, is cooled to room temperature after being incubated 4 hours.The cotton-shaped powder of the black obtaining is cleaned, is dried with deionized water and absolute ethyl alcohol, obtain 1.54 grams of spherical Fe of carbon-coated nano
7s
8powder.
10 grams of ferrocene are evenly mixed with 26 grams of ammonium persulfates, and under glove box nitrogen protection atmosphere, packing volume into is in 200 milliliters of teflon-lined Pressure solution bullets and lock sealing.Pressure solution bullet is heated to 180 ° of C, is cooled to room temperature after being incubated 3 hours.The cotton-shaped powder of the black obtaining is cleaned, is dried with deionized water and absolute ethyl alcohol, obtain 9.25 grams of spherical Fe of carbon-coated nano
7s
8powder.
200 grams of ferrocene are evenly mixed with 450 grams of ammonium persulfates, and being placed in volume is autoclave the lock sealing of 5 liters of contraposition polyphenyl liners, is evacuated to 1.2 * 10
1after Pa, autoclave is heated to 220 ° of C, is cooled to room temperature after being incubated 4 hours.The cotton-shaped powder of the black obtaining is cleaned, is dried with deionized water and absolute ethyl alcohol, obtain 162.35 grams of spherical Fe of carbon-coated nano
7s
8powder.
More than show and described basic principle of the present invention and principal character and advantage of the present invention.The technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and description, describes just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.The claimed scope of the present invention is defined by appending claims and equivalent thereof.
Claims (6)
1. a preparation method for carbon-coated magnetic nanometer spherical iron sulfide, is characterized in that, described preparation method comprises the steps:
1) selecting the derivative of ferrocene or ferrocene and ammonium persulfate is raw material, and both are evenly mixed, and wherein the mol ratio of ferrocene or derivatives thereof and ammonium persulfate is 0.2:1～2.5:1;
2) raw material mixing is packed in withstand voltage closed reaction vessel, be heated to 150～250 ℃ and be incubated 0.5～4 hour, obtain the cotton-shaped powder of black after being cooled to room temperature;
3) with deionized water and absolute ethyl alcohol, the cotton-shaped powder of black is cleaned, is dried successively, obtain having the carbon-coated nano Fe of ferrimagnetism
7s
8powder.
2. the preparation method of a kind of carbon-coated magnetic nanometer spherical iron sulfide according to claim 1, is characterized in that, the derivative of described ferrocene is any one in ethyl dicyclopentadienyl iron, ferrocenyl methyl ketone, ferrocenecarboxylic acid.
3. the preparation method of a kind of carbon-coated magnetic nanometer spherical iron sulfide according to claim 1, is characterized in that, described closed reaction vessel inside is vacuum or fills any one in nitrogen, argon gas.
4. the preparation method of a kind of carbon-coated magnetic nanometer spherical iron sulfide according to claim 1, is characterized in that, described nanometer Fe
7s
8powder is spherical, and diameter is concentrated and is distributed between 10～50nm.
5. the preparation method of a kind of carbon-coated magnetic nanometer spherical iron sulfide according to claim 1, is characterized in that, described Fe
7s
8the thickness of the outer coated carbon of powder is concentrated and is distributed between 5～20nm.
6. the preparation method of a kind of carbon-coated magnetic nanometer spherical iron sulfide according to claim 1, is characterized in that, described Fe
7s
8the outer coated carbon of powder is easy graphitized carbon structure.
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| CN104716319B (en) * | 2013-12-17 | 2017-07-18 | 华中科技大学 | Carbon-clad metal sulfide electrode material and its preparation method and application |
| CN103794762B (en) * | 2014-01-23 | 2016-03-23 | 上海海事大学 | The low-temperature oxidation preparation method that the coated variety classes of a kind of carbon is nanocrystalline |
| CN106953092A (en) * | 2017-04-14 | 2017-07-14 | 哈尔滨工业大学 | A kind of preparation method of positive material for lithium-sulfur battery |
| CN108598378B (en) * | 2018-01-29 | 2020-10-02 | 齐鲁工业大学 | Lithium/sodium ion battery negative electrode material Fe1-xPreparation method of S/C |
| CN114100634B (en) * | 2021-12-14 | 2023-11-10 | 宁波碧城生态科技有限公司 | Preparation method, product and application of magnetic multi-component iron-carbon composite Fenton-like catalyst |
| CN114291811A (en) * | 2021-12-29 | 2022-04-08 | 山西大学 | Simple carbon material magnetizing method |
Citations (4)
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|---|---|---|---|---|
| US6358562B1 (en) * | 1998-04-08 | 2002-03-19 | Forschungszentrum Karlsruhe Gmbh | Method for the production of coated particles |
| CN101780950A (en) * | 2009-09-22 | 2010-07-21 | 上海海事大学 | Method for preparing high specific surface area carbon nanofibers |
| CN102010690A (en) * | 2010-11-04 | 2011-04-13 | 浙江师范大学 | Carbon nanotube composite material filled with ferrous sulfide, preparation method and application thereof |
| CN102423671A (en) * | 2011-08-26 | 2012-04-25 | 浙江师范大学 | In situ preparation method for novel iron/carbon nano-tube grading nano-composite material |
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2012
- 2012-05-23 CN CN201210163390.5A patent/CN102671590B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6358562B1 (en) * | 1998-04-08 | 2002-03-19 | Forschungszentrum Karlsruhe Gmbh | Method for the production of coated particles |
| CN101780950A (en) * | 2009-09-22 | 2010-07-21 | 上海海事大学 | Method for preparing high specific surface area carbon nanofibers |
| CN102010690A (en) * | 2010-11-04 | 2011-04-13 | 浙江师范大学 | Carbon nanotube composite material filled with ferrous sulfide, preparation method and application thereof |
| CN102423671A (en) * | 2011-08-26 | 2012-04-25 | 浙江师范大学 | In situ preparation method for novel iron/carbon nano-tube grading nano-composite material |
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