CN102671590A - Preparation method of carbon coated magnetic nano-spherical iron sulfide - Google Patents
Preparation method of carbon coated magnetic nano-spherical iron sulfide Download PDFInfo
- Publication number
- CN102671590A CN102671590A CN2012101633905A CN201210163390A CN102671590A CN 102671590 A CN102671590 A CN 102671590A CN 2012101633905 A CN2012101633905 A CN 2012101633905A CN 201210163390 A CN201210163390 A CN 201210163390A CN 102671590 A CN102671590 A CN 102671590A
- Authority
- CN
- China
- Prior art keywords
- carbon
- preparation
- iron sulfide
- coated magnetic
- ferrocene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
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
Receive the influence of occurring in nature complicated geological environment; And element sulphur and the ferro element of forming iron sulfide all have abundant relatively valent state; Component and changes of crystal can both take place in the iron sulfide of each kind under Influence of Temperature, therefore naturally occurring iron sulfide is of a great variety.Verified at present and the iron sulfide mineral of clear and definite its crystal structure is divided into following several kinds according to the ratio between Fe and the S element, as shown in table 1.Wherein, The outside magnetic field effect show down magnetic magnetic iron ore with wait the 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 is closely got in touch, more important is that they have complicacy and abundant magnetic-structure-temperature relation.These unique character study the brilliant crystal structure of magnetic Nano for people and the relation of magnetic property provides good sample.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 in fields such as the depollution of environment, the storage of VHD magnetic, Magnetic Isolation, catalyst, biological medicine, sensings and uses widely and cause that people pay close attention to greatly.As, pyrite (FeS
2) semiconductor is for solar spectrum, has the suitable energy gap and the very high absorption coefficient of light, than high two one magnitude of crystalline silicon.Its component is cheap, and the content in the earth is abundant, 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 the solar cell material field.On the other hand, with FeS
2Li-FeS for cathode active material
2Battery has that specific energy is big, capacity is high, high discharge platform, memory time is long, cost is low and the advantage of environmental protection.FeS can be used for handling electroplated heavy metals waste water, and its advantage is: raw material sources are extensive, low price, simple to operate, and are good to the removal effect of heavy metal, and can not cause secondary pollution.Fe
1-xS is owing to have magnetic, can be used for the magnetic carrier etc. in electromagnetic shielding, magnetic storage, magnetic fluid, NMR contrast agent, the drug targeting treatment.
But most iron sulfide nano materials are unstable in air, are easy to oxidizedly, and synthetic method is less relatively, needs anhydrous and oxygen-free reaction condition and covering etc.At present commonly used have presoma pyrolysismethod, a hydro-thermal method etc.But general program more complicated, the reaction time is long, and used organic matter presoma is poisonous, and therefore contaminated environment is utilized simple synthetic method to prepare the iron sulfide nano material and is had very important significance.In addition, how making the iron sulfide nano material for preparing have good stable property also is the major issue that its preparation and application need solve.Only have at present to coat Fe7S8 through CNT and guarantee its stable preparation method, but reaction temperature is too high, technology and equipment too complicacy (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 preparation carbon-coated magnetic nanometer spherical iron sulfide (Fe
7S
8) new method, through adopting special formula and technology, overcome the deficiency in the conventional art, thereby realized the object of the invention.
The technical problem that the present invention solved can adopt following technical scheme to realize:
A kind of preparation method of carbon-coated magnetic nanometer spherical iron sulfide is characterized in that said preparation method comprises the steps:
1) selecting the derivative of ferrocene or ferrocene and ammonium persulfate for use 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 that mixes is packed in the 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) successively with deionized water and absolute ethyl alcohol to the cotton-shaped powder of black clean, drying, promptly obtain having the carbon-coated nano Fe of ferrimagnetism
7S
8Powder.
In a preferred embodiment of the invention, the derivative of said ferrocene is any one in ethyl dicyclopentadienyl iron, ferrocenyl methyl ketone, the ferrocenecarboxylic acid.
In a preferred embodiment of the invention, said closed reaction vessel inside is vacuum or fills in nitrogen, the argon gas any one.
In a preferred embodiment of the invention, said nanometer Fe
7S
8Particle is spherical, and diameter is concentrated and is distributed between 10 ~ 50nm.
In a preferred embodiment of the invention, said Fe
7S
8The thickness of the outer carbon that coats of particle is concentrated and is distributed between 5 ~ 20nm.
In a preferred embodiment of the invention, said Fe
7S
8The outer carbon that coats of particle is for being prone to the graphitized carbon structure.
Beneficial effect of the present invention is: reaction can prepare the spherical Fe of carbon-coated nano through ferrocene or derivatives thereof and ammonium persulfate single step reaction
7S
8Powder, technology is simple, need not special installation, and output can be easy to amplify volume production by raw material addition and the adjusting of container reaction compartment; Secondly, the spherical Fe of carbon-coated nano
7S
8Powder has good stable property; Once more, reaction temperature is merely between 150 ~ 250 ℃, has the characteristics of ultralow temperature, is that carbon current coats Fe
7S
8The minimum preparation temperature of nano material; At last, the magnetic Nano Fe of this method preparation
7S
8Particle is spherical, and diameter is concentrated and is distributed between 10 ~ 50nm, and the carbon shell of coating has easy graphitized carbon structure, and thickness is concentrated and is distributed between 5 ~ 20nm.
Description of drawings
Fig. 1 is the spherical Fe of the carbon-coated nano of embodiment 1 preparation
7S
8The X-ray diffractogram of particle.
Fig. 2 is the spherical Fe of the carbon-coated nano of embodiment 1 preparation
7S
8The secondary electron image of particle.
Fig. 3 is the spherical Fe of the carbon-coated nano of embodiment 1 preparation
7S
8The backscattered electron image of particle.
Fig. 4 is the spherical Fe of the carbon-coated nano of embodiment 1 preparation
7S
8The pattern of particle and image K-M.
Fig. 5 is the spherical Fe of the carbon-coated nano of embodiment 1 preparation
7S
8The high-resolution crystal lattice pattern picture of particle.
Fig. 6 is the spherical Fe of the 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 purpose and effect and be easy to understand and understand, below in conjunction with the specific embodiment, further set forth the present invention.
The present invention proposes a kind of preparation carbon-coated magnetic nanometer spherical iron sulfide (Fe
7S
8) new method.This method characteristics are: reaction can prepare the spherical Fe of carbon-coated nano through ferrocene or derivatives thereof and ammonium persulfate single step reaction
7S
8Powder, technology is simple, need not special installation, and output can be easy to amplify volume production by raw material addition and the adjusting of container reaction compartment; Secondly, the spherical Fe of carbon-coated nano
7S
8Powder has good stable property; Once more, reaction temperature is merely between 150 ~ 250 ℃, has the characteristics of ultralow temperature, is that carbon current coats Fe
7S
8The minimum preparation temperature of nano material; At last, the magnetic Nano Fe of this method preparation
7S
8Particle is spherical, and diameter is concentrated and is distributed between 10 ~ 50nm, and the carbon shell of coating has easy graphitized carbon structure, and thickness is concentrated and is distributed between 5 ~ 20nm.Its microstructure, form and composition characterize like Fig. 1 ~ shown in Figure 6.So preparation method proposed by the invention has characteristics such as equipment is simple, easy to operate, cost is low, efficient is high, environmental protection, be fit to suitability for industrialized production.
Basic principle of the present invention is: the ferrocene or derivatives thereof has reproducibility, can react with the strong oxidizer ammonium persulfate, and generate the nanometer spherical Fe with low-surface-energy at a certain temperature
7S
8Particle, and the self assembly of cracking dehydrogenation reaction takes place and generate to be prone to graphitized carbon material and to be coated on nanometer spherical Fe in cyclopentadiene in the ferrocene or derivatives thereof simultaneously
7S
8Particle surface.Different according to proportioning raw materials, have a spot of H
2S or SO
2Gaseous by-product produces, and tail gas can absorb processing in alkaline solution.
Embodiment 1
1 gram ferrocene is evenly mixed with 2 gram ammonium persulfates, and the volume of under glove box nitrogen protection atmosphere, packing into is a lock sealing also in the Pressure solution bullet of 50 milliliters of contraposition polyphenyl liners.Pressure solution bullet is heated to 200 ° of C, is incubated and is cooled to room temperature after 1 hour.With the cotton-shaped powder of the black that obtains with deionized water and absolute ethyl alcohol clean, drying, obtain the spherical Fe of 0.69 gram carbon-coated nano
7S
8Powder.
3 gram ferrocene are evenly mixed with 8 gram ammonium persulfates, and the volume of under glove box nitrogen protection atmosphere, packing into is a lock sealing also in the Pressure solution bullet of 50 milliliters of contraposition polyphenyl liners.Pressure solution bullet is heated to 200 ° of C, is incubated and is cooled to room temperature after 2 hours.With the cotton-shaped powder of the black that obtains with deionized water and absolute ethyl alcohol clean, drying, obtain the spherical Fe of 2.46 gram carbon-coated nanos
7S
8Powder.
Embodiment 3
2 gram ferrocene are evenly mixed with 4 gram ammonium persulfates, and the volume of under glove box nitrogen protection atmosphere, packing into is a lock sealing also in the Pressure solution bullet of 50 milliliters of contraposition polyphenyl liners.Pressure solution bullet is heated to 150 ° of C, is incubated and is cooled to room temperature after 4 hours.With the cotton-shaped powder of the black that obtains with deionized water and absolute ethyl alcohol clean, drying, obtain the spherical Fe of 1.54 gram carbon-coated nanos
7S
8Powder.
10 gram ferrocene are evenly mixed with 26 gram ammonium persulfates, and the volume of under glove box nitrogen protection atmosphere, packing into is in 200 milliliters of teflon-lined Pressure solution bullets and lock sealing.Pressure solution bullet is heated to 180 ° of C, is incubated and is cooled to room temperature after 3 hours.With the cotton-shaped powder of the black that obtains with deionized water and absolute ethyl alcohol clean, drying, obtain the spherical Fe of 9.25 gram carbon-coated nanos
7S
8Powder.
200 gram ferrocene are evenly mixed with 450 gram ammonium persulfates, and placing volume is the autoclave and the lock sealing of 5 liters of contraposition polyphenyl liners, is evacuated to 1.2 * 10
1Behind the Pa, autoclave is heated to 220 ° of C, is incubated and is cooled to room temperature after 4 hours.With the cotton-shaped powder of the black that obtains with deionized water and absolute ethyl alcohol clean, drying, obtain the spherical Fe of 162.35 gram carbon-coated nanos
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 describes in the foregoing description and the specification just explains principle of the present invention; Under the prerequisite that does not break away from spirit and scope of the invention, the present invention also has various changes and modifications, and these variations and improvement all fall in the scope of the invention that requires protection.The present invention requires protection domain to be defined by appending claims and equivalent thereof.
Claims (6)
1. the preparation method of a carbon-coated magnetic nanometer spherical iron sulfide is characterized in that, said preparation method comprises the steps:
1) selecting the derivative of ferrocene or ferrocene and ammonium persulfate for use 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 that mixes is packed in the 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) successively with deionized water and absolute ethyl alcohol to the cotton-shaped powder of black clean, drying, promptly 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 said ferrocene is any one in ethyl dicyclopentadienyl iron, ferrocenyl methyl ketone, the 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, said closed reaction vessel inside is vacuum or fills in nitrogen, the argon gas any one.
4. the preparation method of a kind of carbon-coated magnetic nanometer spherical iron sulfide according to claim 1 is characterized in that, said nanometer Fe
7S
8Particle 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, said Fe
7S
8The thickness of the outer carbon that coats of particle 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, said Fe
7S
8The outer carbon that coats of particle is for being prone to the graphitized carbon structure.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210163390.5A CN102671590B (en) | 2012-05-23 | 2012-05-23 | Preparation method of carbon coated magnetic nano-spherical iron sulfide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210163390.5A CN102671590B (en) | 2012-05-23 | 2012-05-23 | Preparation method of carbon coated magnetic nano-spherical iron sulfide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102671590A true CN102671590A (en) | 2012-09-19 |
| CN102671590B CN102671590B (en) | 2014-03-12 |
Family
ID=46804531
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210163390.5A Expired - Fee Related CN102671590B (en) | 2012-05-23 | 2012-05-23 | Preparation method of carbon coated magnetic nano-spherical iron sulfide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102671590B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103794762A (en) * | 2014-01-23 | 2014-05-14 | 上海海事大学 | Low-temperature oxidation preparation method of different carbon-coated nanocrystallines |
| CN104716319A (en) * | 2013-12-17 | 2015-06-17 | 华中科技大学 | Carbon-coated metal sulfide electrode material, preparation method and application thereof |
| 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 |
| CN108598378A (en) * | 2018-01-29 | 2018-09-28 | 齐鲁工业大学 | A kind of lithium/anode material of lithium-ion battery Fe1-xThe preparation method of S/C |
| CN114100634A (en) * | 2021-12-14 | 2022-03-01 | 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)
| 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 |
-
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 |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104716319A (en) * | 2013-12-17 | 2015-06-17 | 华中科技大学 | Carbon-coated metal sulfide electrode material, preparation method and application thereof |
| CN103794762A (en) * | 2014-01-23 | 2014-05-14 | 上海海事大学 | Low-temperature oxidation preparation method of different carbon-coated nanocrystallines |
| 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 |
| CN108598378A (en) * | 2018-01-29 | 2018-09-28 | 齐鲁工业大学 | A kind of lithium/anode material of lithium-ion battery Fe1-xThe preparation method of S/C |
| 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 |
| CN114100634A (en) * | 2021-12-14 | 2022-03-01 | 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 |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102671590B (en) | 2014-03-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Shen et al. | Implanting niobium carbide into trichoderma spore carbon: a new advanced host for sulfur cathodes | |
| Xia et al. | Facile synthesis of hematite quantum‐dot/functionalized graphene‐sheet composites as advanced anode materials for asymmetric supercapacitors | |
| Chang et al. | Hierarchical NiCo2S4@ NiCoP core-shell nanocolumn arrays on nickel foam as a binder-free supercapacitor electrode with enhanced electrochemical performance | |
| Sun et al. | Metal–Organic Framework Derived Honeycomb Co9S8@ C Composites for High‐Performance Supercapacitors | |
| Sun et al. | Mn3O4@ NC composite nanorods as a cathode for rechargeable aqueous Zn‐ion batteries | |
| CN102671590B (en) | Preparation method of carbon coated magnetic nano-spherical iron sulfide | |
| Zhang et al. | High-performance supercapacitors and batteries derived from activated banana-peel with porous structures | |
| Arnaiz et al. | Reduced graphene oxide decorated with SnO2 nanoparticles as negative electrode for lithium ion capacitors | |
| Xu et al. | Reactable ionic liquid assisted solvothermal synthesis of graphite-like C3N4 hybridized α-Fe2O3 hollow microspheres with enhanced supercapacitive performance | |
| CN103303912B (en) | A kind of preparation method of high specific surface area porous N doping graphitization nano carbon material | |
| Xu et al. | Large scale synthesis of nickel oxide/multiwalled carbon nanotube composites by direct thermal decomposition and their lithium storage properties | |
| Yin et al. | Millimeter‐Long Vertically Aligned Carbon‐Nanotube‐Supported Co3O4 Composite Electrode for High‐Performance Asymmetric Supercapacitor | |
| Han et al. | Nanocoating covalent organic frameworks on nickel nanowires for greatly enhanced-performance supercapacitors | |
| CN107393725A (en) | A kind of carbon material supported NiCo of porous, electrically conductive2O4Composite and its preparation method and application | |
| Wang et al. | Photoinduced homogeneous RuO2 nanoparticles on TiO2 nanowire arrays: A high-performance cathode toward flexible Li–CO2 batteries | |
| Kharangarh et al. | Synthesis of luminescent graphene quantum dots from biomass waste materials for energy‐related applications—an Overview | |
| Yang et al. | Chemical modification of the sp‐hybridized carbon atoms of graphdiyne by using organic sulfur | |
| Sun et al. | Polar Co9S8 anchored on Pyrrole-Modified graphene with in situ growth of CNTs as multifunctional Self-Supporting medium for efficient Lithium-Sulfur batteries | |
| CN104769755A (en) | Methods and compositions for making metal oxide-graphene composites | |
| CN102290253B (en) | Carbon-coated nano transition metal oxide and preparation method thereof | |
| CN106587156A (en) | Method for preparing g-C3N4/MoS2 nanocomposite with vulcanizing sintering method | |
| CN105271170A (en) | Preparation method of nano carbon and composite material of nano carbon | |
| Kan et al. | Sulfur-decorated nanomesh graphene for high-performance supercapacitors | |
| Xiang et al. | Booting the electrochemical properties of Fe-based anode by the formation multiphasic nanocomposite for lithium-ion batteries | |
| Chameh et al. | Decoration of metal organic frameworks with Fe2O3 for enhancing electrochemical performance of ZIF-(67 and 8) in energy storage application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140312 Termination date: 20180523 |