CN105293468A - Method for efficiently preparing sulphur-doped hollow carbon spheres - Google Patents
Method for efficiently preparing sulphur-doped hollow carbon spheres Download PDFInfo
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- CN105293468A CN105293468A CN201510739156.6A CN201510739156A CN105293468A CN 105293468 A CN105293468 A CN 105293468A CN 201510739156 A CN201510739156 A CN 201510739156A CN 105293468 A CN105293468 A CN 105293468A
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- hollow carbon
- sulphur
- sulfur doping
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Abstract
The invention relates to a method for efficiently preparing sulphur-doped hollow carbon spheres. The method for efficiently preparing the sulphur-doped hollow carbon spheres comprises the following steps: firstly weighing a catalyst and a sulphur source, and mixing the catalyst with the sulphur source, wherein the catalyst is ferric acetylacetonate, the sulphur source is carbon disulfide, and the concentration of the catalyst in the sulphur source is 1-0.025g/ml; introducing the mixture into a tubular furnace, wherein temperature of the tubular furnace is 600-1350 DEG C; introducing inert gas as a carrier gas, inputting a reaction solution into an ejector inside the tubular furnace by virtue of a peristaltic pump, then spraying into a high-temperature region of the tubular furnace, and collecting products at the tail of the tubular furnace, so that carbon-coated iron nano core-shell particles are obtained; and putting the obtained carbon-coated iron nano core-shell particles into the mixed solution of hydrochloric acid and nitric acid, heating to 60-100 DEG C, carrying out magnetic stirring, filtering the obtained mixed liquor, adding deionized water for washing until filtrate is neutral, and immediately drying, so that the sulphur-doped hollow carbon spheres with high specific surface areas are obtained. The method for efficiently preparing the sulphur-doped hollow carbon spheres is easy to operate, simple in after-treatment, and applicable to industrial production.
Description
Technical field
The invention belongs to materialogy field, relate to a kind of nano material, specifically a kind of method efficiently preparing sulfur doping hollow carbon sphere.
Background technology
Along with the rise of nanotechnology, synthesize the research emphasis that the nano material with certain function becomes many researchers.In recent years, the actual application value of carbon nanomaterial and its concrete manifestation in the application more and more come into one's own.Carbon nanomaterial containing doped element (as boron, nitrogen phosphate and sulfur etc.), p-type or N-shaped structure is similar to because it can be formed, can adsorption charge or avtive spot is provided effectively, improve the electroconductibility of material simultaneously, be applied to related electronic devices material or support of the catalyst has important using value.The more sulfur doping carbon material of current research comprises gac, mesoporous carbon, carbon nanotube, carbon nanofiber, Graphene etc., by introducing sulfur-bearing functional group to material surface or directly introducing doped structure, improves the correlated performance of material.Nano graphite cage, as a kind of comparatively novel carbon nanomaterial, because it has good physicochemical property, is more and more subject to the favor of investigator.But in traditional preparation process, often need polystep reaction process, the cost of material of use is higher and have certain toxicity, energy consumption is large, and the product specific surface area simultaneously obtained and greying can not be taken into account, and limit the space that it further develops.Therefore, develop a kind of sulfur doping Nano graphite cage tool that is simple, efficient, environmental protection to be of great significance.
Through finding the literature search of prior art, the people such as TaoLi are at " ACSAppliedMaterials & Interfaces " 6(2014) be mentioned to a kind of method preparing sulfur doping porous carbon in " EnhancingtheLiStorageCapacityandInitialCoulombicEfficien cyforPorousCarbonsbySulfurDoping " (being improved lithium ion storage capacity and coulombic efficiency of porous carbon by sulfur doping) literary composition that 15950-15958 delivers, by quantitative pitch, toluene and BMS whisker are placed in high temperature process furnances and calcine, obtain presoma, pickling subsequently obtains the porous carbon of sulfur-bearing doped structure.Because the preparation of its presoma needs long-time high-temperature calcination in tube furnace, this restrict serialization and the scale operation of sulfur doping carbon nanomaterial, be also unfavorable for this kind of method to realize industrialization.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of method efficiently preparing sulfur doping hollow carbon sphere, the described this method efficiently preparing sulfur doping hollow carbon sphere solves the method preparing doped hollow carbon ball of the prior art needs long high-temperature calcination, is unfavorable for the technical problem of suitability for industrialized production.
The invention provides a kind of method efficiently preparing sulfur doping hollow carbon sphere, comprise the following steps:
(1)a step preparing the carbon-encapsulated iron nucleocapsid particles of sulfur doping, take catalyzer and sulphur source, catalyzer is mixed with sulphur source, described catalyzer is ferric acetyl acetonade, described sulphur source is dithiocarbonic anhydride, the concentration of described catalyzer in sulphur source is 1g/ml ~ 0.025g/ml, above-mentioned substance is passed in a tube furnace, the temperature of described tube furnace is 600 ~ 1350 DEG C, and pass into rare gas element as carrier gas, reaction soln is input to the injector of tube furnace inside through peristaltic pump, spray into tube furnace high-temperature zone subsequently, product is collected at tube furnace afterbody, obtain carbon-coated iron nano core-shell particle,
(2) steps preparing sulfur doping hollow carbon sphere, carbon-coated iron nano core-shell particle step (1) obtained is placed in hydrochloric acid and nitric acid mixing solutions, be heated to 60 ~ 100 DEG C and magnetic agitation, gained mixed solution is filtered, adds deionized water rinsing, until filtrate is in neutral, dry immediately, obtain sulfur doping hollow carbon sphere.
Further, described rare gas element is argon gas, and flow velocity is 16 ~ 160 ls/h.
Further, described reaction soln peristaltic pump inputs, and input speed is 10 ~ 120 mls/hour.
Further, in the mixing solutions of hydrochloric acid and nitric acid, two kinds of sour volume ratios are V
nitre/ V
salt=10:1 ~ 0:1, described salpeter solution is technical pure salpeter solution, and described concentration of hydrochloric acid is 36%.
Further, in step (2), the magnetic agitation time is 1 ~ 6 hour.
The present invention is first by sulfur-bearing organic raw material and catalyst mix, with peristaltic pump above-mentioned mixed solution is input to the injector in tube furnace, by injector, mixed solution is sprayed into the high-temperature zone of tube furnace, by controlling the fluidized state of reactant under airflow function, generate the carbon-encapsulated iron particle of sulfur doping.Achieve the serialization preparation of collecting product from tube furnace one end input raw material to the other end, greatly improve efficiency; This nano core-shell particle is placed in hydrochloric acid and nitric acid mixing solutions, heating is magnetic agitation also, is filtered, adds deionized water wash by above-mentioned gained mixed solution, until filtrate is in neutral, dry immediately, the sulfur doping hollow carbon sphere of the high-specific surface area of iron particle must be removed.
The present invention is in the protection of argon gas and under carrying; utilize the catalytic effect of transition metal nanoparticles; through chemical vapour deposition in floating catalytic Reaktionsofen; graphite carbon-coating (graphite carbon-coating has a large amount of doping sulphur structure) is wrapped up around the nanoparticle formed; form the solid carbon ball being enclosed with metallics that diameter is 10 ~ 70nm; then carry out pickling and remove iron particle; obtain sulfur doping hollow carbon sphere; detect its wall thickness is 0.7 ~ 4nm; the graphite number of plies is 3 ~ 14 layers, and sulfur doping amount is about 3 ~ 5%.
The present invention compares with prior art, and its technical progress is significant.Apparatus structure of the present invention is simple, and easy handling, aftertreatment is simple and easy, is suitable for serialization, industrialization is produced on a large scale.
Embodiment
embodiment 1
Efficiently prepare a method for sulfur doping hollow carbon sphere, comprise the following steps:
(1) the carbon-encapsulated iron nucleocapsid particles of sulfur doping is prepared:
Catalyzer (ferric acetyl acetonade) and sulphur source (dithiocarbonic anhydride) are made into the reaction soln that concentration is 1g/ml and are placed in volumetric flask; Tube furnace temperature is risen to temperature of reaction 600 DEG C, and pass into argon gas, flow velocity is 80 ls/h; Sprayed into through the injector of electronic peristaltic pump by main reactor inside by reaction soln, the speed of spraying into is 30 mls/hour.In main reactor afterbody product collector, obtain being enclosed with in the carbon structure of iron particle the solid carbon ball of element sulphur of adulterating.
(2) hollow carbon sphere of sulfur-bearing doped structure is prepared
1. the particle that step (1) obtains is placed in hydrochloric acid and nitric acid mixing solutions, this liquor capacity is than being V
nitre/ V
salt=0:1, is heated to 60 DEG C, magnetic agitation 1 hour; Described salpeter solution is technical pure salpeter solution, and described concentration of hydrochloric acid is 36%.
2. gained mixture in above-mentioned steps is filtered, adds deionized water rinsing, until filtrate is in neutral, dry immediately, the sulfur doping hollow carbon sphere of iron particle must be removed.
Implementation result: forming mean diameter is the hollow carbon sphere of 10nm, and detect its wall thickness is 0.7nm, the graphite number of plies is 3 layers, and pore size distribution concentrates on 1.8nm, and sulphur content is 3wt%, specific surface area 700m
2/ g.
embodiment 2
Efficiently prepare a method for sulfur doping hollow carbon sphere, comprise the following steps:
(1) the carbon-coated iron nano core-shell particle of sulfur-bearing doped structure is prepared
Catalyzer (ferric acetyl acetonade) and sulphur source (dithiocarbonic anhydride) are made into the reaction soln that concentration is 0.1g/ml and are placed in volumetric flask; Tube furnace temperature is risen to temperature of reaction 900 DEG C, and pass into argon gas, flow velocity is 120 ls/h; Sprayed into through the injector of electronic peristaltic pump by main reactor inside by reaction soln, the speed of spraying into is 10 mls/hour.In main reactor afterbody product collector, obtain being enclosed with in the carbon structure of iron particle the solid carbon ball of element sulphur of adulterating.
(2) hollow carbon sphere of sulfur-bearing doped structure is prepared
1. the particle that step (1) obtains is placed in hydrochloric acid and nitric acid mixing solutions, this liquor capacity is than being V
nitre/ V
salt=1:1, is heated to 70 DEG C, magnetic agitation 4 hours; Described salpeter solution is technical pure salpeter solution, and described concentration of hydrochloric acid is 36%.
2. gained mixture in above-mentioned steps is filtered, adds deionized water rinsing, until filtrate is in neutral, dry immediately, the sulfur doping hollow carbon sphere of iron particle must be removed.
Implementation result: forming mean diameter is the hollow carbon sphere of 40nm, and detect its wall thickness is 3nm, the graphite number of plies is 10 layers, and pore size distribution concentrates on 3nm, and sulphur content is 4wt%, specific surface area 450m
2/ g.
embodiment 3
(1) hollow carbon sphere of sulfur-bearing doped structure is prepared
Catalyzer (ferric acetyl acetonade) and sulphur source (dithiocarbonic anhydride) are made into the reaction soln that concentration is 0.025g/ml and are placed in volumetric flask; Tube furnace temperature is risen to temperature of reaction 1350 DEG C, and pass into argon gas, flow velocity is 16 ls/h; Sprayed into through the injector of electronic peristaltic pump by main reactor inside by reaction soln, the speed of spraying into is 120 mls/hour.In main reactor afterbody product collector, obtain being enclosed with in the carbon structure of iron particle the solid carbon ball of element sulphur of adulterating.
(2) the hollow plumbago nanocages of sulfur-bearing doped structure is prepared
1. the particle that step (1) obtains is placed in hydrochloric acid and nitric acid mixing solutions, this liquor capacity is than being V
nitre/ V
salt=10:1, is heated to 100 DEG C, magnetic agitation 6 hours; Described salpeter solution is technical pure salpeter solution, and described concentration of hydrochloric acid is 36%.
2. gained mixture in above-mentioned steps is filtered, adds deionized water rinsing, until filtrate is in neutral, dry immediately, the sulfur doping hollow carbon sphere of iron particle must be removed.
Implementation result: forming diameter is the hollow carbon sphere of 70nm, and detect its wall thickness is 4nm, the graphite number of plies is 14 layers, and pore size distribution concentrates on 5nm, and sulphur content is 5wt%, specific surface area 250m
2/ g.
Claims (5)
1. efficiently prepare a method for sulfur doping hollow carbon sphere, it is characterized in that, comprise the following steps:
(1) step preparing the carbon-encapsulated iron nucleocapsid particles of sulfur doping, take catalyzer and sulphur source, catalyzer is mixed with sulphur source, described catalyzer is ferric acetyl acetonade, described sulphur source is dithiocarbonic anhydride, the concentration of described catalyzer in sulphur source is 1g/ml ~ 0.025g/ml, above-mentioned substance is passed in a tube furnace, the temperature of described tube furnace is 600 ~ 1350 DEG C, and pass into rare gas element as carrier gas, reaction soln is input to the injector of tube furnace inside through peristaltic pump, spray into tube furnace high-temperature zone subsequently, product is collected at tube furnace afterbody, obtain carbon-coated iron nano core-shell particle,
(2) steps preparing sulfur doping hollow carbon sphere, carbon-coated iron nano core-shell particle step (1) obtained is placed in hydrochloric acid and nitric acid mixing solutions, be heated to 60 ~ 100 DEG C and magnetic agitation, gained mixed solution is filtered, adds deionized water rinsing, until filtrate is in neutral, dry immediately, obtain sulfur doping hollow carbon sphere.
2. a kind of method efficiently preparing sulfur doping hollow carbon sphere according to claim 1, it is characterized in that: described rare gas element is argon gas, flow velocity is 16 ~ 160 ls/h.
3. a kind of method efficiently preparing sulfur doping hollow carbon sphere according to claim 1, it is characterized in that: described reaction soln peristaltic pump inputs, input speed is 10 ~ 120 mls/hour.
4. a kind of method efficiently preparing sulfur doping hollow carbon sphere according to claim 1, is characterized in that: in the mixing solutions of hydrochloric acid and nitric acid, two kinds of sour volume ratio V
nitre/ V
salt=10:1 ~ 0:1, described salpeter solution is technical pure salpeter solution, and described concentration of hydrochloric acid is 36%.
5. a kind of method efficiently preparing sulfur doping hollow carbon sphere according to claim 1, it is characterized in that: in step (2), the magnetic agitation time is 1 ~ 6 hour.
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Cited By (4)
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| CN107758640A (en) * | 2017-10-27 | 2018-03-06 | 华中科技大学 | A kind of preparation method and product of the hollow carbon of erythrocyte shape |
| CN108163833A (en) * | 2018-01-19 | 2018-06-15 | 北京航空航天大学 | A kind of method for preparing the mesoporous carbon nanomaterial of sulfur doping class graphene |
| CN109004215A (en) * | 2018-07-25 | 2018-12-14 | 上海应用技术大学 | A method of lithium cell negative pole material charcoal bag ferrous sulfide nano particle is prepared in situ |
| CN113937313A (en) * | 2021-10-13 | 2022-01-14 | 上海应用技术大学 | Preparation method of iron-sulfur-phosphorus co-doped nano porous graphite catalyst |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107758640A (en) * | 2017-10-27 | 2018-03-06 | 华中科技大学 | A kind of preparation method and product of the hollow carbon of erythrocyte shape |
| CN108163833A (en) * | 2018-01-19 | 2018-06-15 | 北京航空航天大学 | A kind of method for preparing the mesoporous carbon nanomaterial of sulfur doping class graphene |
| CN109004215A (en) * | 2018-07-25 | 2018-12-14 | 上海应用技术大学 | A method of lithium cell negative pole material charcoal bag ferrous sulfide nano particle is prepared in situ |
| CN113937313A (en) * | 2021-10-13 | 2022-01-14 | 上海应用技术大学 | Preparation method of iron-sulfur-phosphorus co-doped nano porous graphite catalyst |
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Application publication date: 20160203 |