CN105084352A - Preparation method of N-doped graphite nano cage with high specific surface area - Google Patents
Preparation method of N-doped graphite nano cage with high specific surface area Download PDFInfo
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- CN105084352A CN105084352A CN201510494953.2A CN201510494953A CN105084352A CN 105084352 A CN105084352 A CN 105084352A CN 201510494953 A CN201510494953 A CN 201510494953A CN 105084352 A CN105084352 A CN 105084352A
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Abstract
The invention provides a preparation method of an N-doped graphite nano cage with a high specific surface area. The preparation method comprises the steps that a catalyst, a nitrogen source and a carbon source are weighted; the catalyst is ferric acetylacetonate, the nitrogen source is a p-phenylenediamine or acetonitrile catalyst, and the catalyst, the nitrogen source and the carbon source are mixed to prepare a raw material solution; a vertical tubular furnace is heated to the temperature ranging from 500 DEG C to 1200 DEG C, nitrogen is fed to serve as carrier gas, the raw material solution is pumped into an ejector arranged on the upper portion of the vertical tubular furnace through an electronic peristaltic pump and sprayed into a high-temperature region of the tubular furnace through the ejector, and carbon-coated iron nano core-shell particles containing an N-doped structure are obtained in a tubular furnace tail portion product collector; the carbon-coated iron nano core-shell particles containing the N-doped structure are put in a mixed solution of distilled water and nitric acid and heated, magnetic stirring is conducted, obtained mixture is filtered and washed through deionized water till filtrate is neutral or close to neutral, freeze drying is conducted immediately, and the hollow N-doped graphite nano cage with the high specific surface area is obtained. The preparation method of the N-doped graphite nano cage with the high specific surface area is easy to operate, simple and easy in aftertreatment and suitable for industrial production.
Description
Technical field
The invention belongs to materialogy field, relate to a kind of nano material, specifically a kind of preparation method of N doping Nano graphite cage of high-specific surface area.
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 nitrogen-doped carbon material of current research comprises gac, mesoporous carbon, carbon nanotube, carbon nanofiber, Graphene etc., by introducing nitrogen-containing functional group to material surface or directly introducing doped structure (pyridine nitrogen, pyrroles's nitrogen etc.), improve 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 N 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 YuemingTan are at " ACSAppliedMaterials & Interfaces " 5(2013) preparation method mentioning a kind of ultra-thin graphitic carbon nano cage " SynthesisofUltrathinNitrogen-DopedGraphiticCarbonNanocag esasAdvancedElectrodeMaterialsforSupercapacitor " (synthesizing the advanced electrode materials of ultra-thin graphitic carbon nano cage for ultracapacitor) in a literary composition that 2241-2248 delivers, i.e. aniline, manganous nitrate and potassium permanganate mixing solutions, first at 180 DEG C, hydro-thermal reaction obtains presoma in 4 hours, then under argon shield 700 ~ 900
oc carries out carbonization 4 hours, obtains manganese monoxide/carbon complex (MnOC), then obtains the nano cages of similar rectangle through nitric acid treatment.The specific surface area of the graphitic carbon nano cage that the method obtains is 1088m
2g
-1, aperture is 0.22cm
3g
-1.Although the method synthesizes the ultra-thin graphitic carbon nano cage of high specific surface area, this process need two step building-up process, i.e. Hydrothermal Synthesis presoma and high temperature cabonization, the used time is longer, and the pattern of product and doping content are all comparatively difficult to control, and degree of graphitization is poor.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of preparation method of N doping Nano graphite cage of high-specific surface area, the preparation method of the N doping Nano graphite cage of described this high-specific surface area solves preparation method's complex process of the prior art, the pattern of product and doping content and is difficult to control, and the technical problem that degree of graphitization is poor.
The invention provides a kind of preparation method of N doping Nano graphite cage of high-specific surface area, comprise the following steps:
The step of the carbon-coated iron nano core-shell particle of (1) nitrogenous doped structure of preparation,
Take catalyzer, nitrogenous source, carbon source, described catalyzer is ferric acetyl acetonade, and described nitrogenous source is Ursol D or acetonitrile, and the mass ratio of catalyzer, Carbon and nitrogen sources is 5 ~ 20: 0 ~ 90: 5 ~ 80, and material solution is joined to obtain in above-mentioned substance mixing; Vertical tubular furnace is warming up to 500 ~ 1200 DEG C, and pass into nitrogen as carrier gas, material solution is input to the injector on vertical tubular furnace top through electronic peristaltic pump, spray into tube furnace high-temperature zone by injector, in tube furnace afterbody product collector, obtain the carbon-coated iron nano core-shell particle of nitrogenous doped structure;
(2) the carbon-coated iron nano core-shell particle of nitrogenous doped structure step (1) obtained is placed in distilled water and nitric acid mixing solutions, be heated to 60 ~ 90 DEG C and magnetic agitation, above-mentioned gained mixture is filtered, adds deionized water rinsing, until filtrate is in neutral or close neutral, lyophilize immediately, obtain the hollow N doping Nano graphite cage of high-specific surface area, its nitrogen content is at 0.8 ~ 3wt%, pore size distribution concentrates on 1.8 ~ 6nm, and specific surface area is 300 ~ 900m
2g
-1.
Further, the carbon source used in described step (1) is ethanol.
Further, in described step (1), the flow velocity of nitrogen is 40 ~ 160 ls/h.
Further, the injector that described step (1) Raw solution is input to vertical tubular furnace top through electronic peristaltic pump sprays into tube furnace high-temperature zone, and it is 10 ~ 120 mls/hour that electronic peristaltic pump controls material solution flow velocity.
Further, in described step (2), distilled water and concentrated nitric acid mixing solutions ratio are V
water/ V
acid=1: 10 ~ 4: 1.
Further, in described step (2), the magnetic agitation time is 2 ~ 6 hours.
Further, the mass percent concentration of described concentrated nitric acid is 65 ~ 98%.
The present invention uses non-toxic catalyst ferric acetyl acetonade, and providing a kind of can prepare the method for the controlled high-specific surface area Nano graphite cage of N doping content and aperture by rapid, high volume.Catalyzer, nitrogenous source are dissolved in carbon source to be mixed in proportion and to join to obtain material solution, material solution electronic peristaltic pump is input to the injector on vertical tubular furnace top, tube furnace high-temperature zone is sprayed into by injector, by controlling the processing parameters such as reactant composition, temperature of reaction, flow rate of carrier gas, obtain the nitrogenous doped structure carbon-coated iron nano core-shell particle of morphology controllable, then will directly obtain high graphitization degree, high-specific surface area N doping Nano graphite cage after its pickling deironing.
The present invention is in the protection of carrier gas and under carrying, utilize the catalytic effect of transition metal nanoparticles, through chemical vapour deposition in vertical floating catalyzed reaction stove, graphite carbon-coating (graphite carbon-coating has the N structure that adulterates in a large number) is wrapped up around the nanoparticle formed, form the carbon-coated iron nano core-shell particle that diameter is the nitrogenous doped structure of 20 ~ 50nm, then carry out pickling and remove kernel iron particle, obtain hollow plumbago nanocages, detect its wall thickness is 1 ~ 5nm, the graphite number of plies is 3 ~ 13 layers, pore size distribution concentrates on 1.8 ~ 6nm, nitrogen content is 0.8 ~ 3wt%, specific surface area 300 ~ 900m
2g
-1.
The present invention compares with prior art, and its technical progress is significant.The apparatus structure that method of the present invention uses is simple, and easy handling, aftertreatment is simple and easy, low in raw material price, is suitable for serialization, industrialization is produced on a large scale.
Embodiment
embodiment 1
(1) the carbon-coated iron nano core-shell particle of nitrogenous doped structure is prepared
Ferric acetyl acetonade, ethanol and acetonitrile are joined to obtain material solution in mass ratio at 5: 90: 5; Vertical tubular furnace is warming up to temperature of reaction 500 DEG C, and passes into nitrogen as carrier gas, flow velocity is 160 ls/h; The injector that material solution is input to tube furnace top through electronic peristaltic pump is sprayed into tube furnace high-temperature zone, and it is 30 mls/hour that electronic peristaltic pump controls material solution flow velocity.The carbon-coated iron nano core-shell particle of nitrogenous doped structure is obtained in tube furnace afterbody product collector.
(2) the hollow plumbago nanocages of nitrogenous doped structure is prepared
The carbon-coated iron nano core-shell particle of the nitrogenous doped structure 1. step (1) obtained is placed in distilled water and concentrated nitric acid mixing solutions (V
water/ V
acid=4: 1), 60 DEG C are heated to, magnetic agitation 6 hours;
2. gained mixture in above-mentioned steps is filtered, adds deionized water rinsing, until filtrate is in neutral or close neutral, dry immediately, the hollow N doping Nano graphite cage of iron particle must be removed.
Implementation result: form the hollow plumbago nanocages that mean diameter is 21nm, detect its wall thickness is 1nm, the graphite number of plies is 3 layers, and pore size distribution concentrates on 1.8nm, and nitrogen content is 0.8wt%, specific surface area 900m
2g
-1.
embodiment 2
(1) the carbon-coated iron nano core-shell particle of nitrogenous doped structure is prepared
Ferric acetyl acetonade, ethanol and acetonitrile are joined to obtain material solution in mass ratio at 20: 0: 80; Vertical tubular furnace is warming up to temperature of reaction 1200 DEG C, and passes into nitrogen as carrier gas, flow velocity is 60 ls/h; The injector that material solution is input to tube furnace top through electronic peristaltic pump is sprayed into tube furnace high-temperature zone, and it is 120 mls/hour that electronic peristaltic pump controls material solution flow velocity.The carbon-coated iron nano core-shell particle of nitrogenous doped structure is obtained in tube furnace afterbody product collector.
(2) the hollow plumbago nanocages of nitrogenous doped structure is prepared
The carbon-coated iron nano core-shell particle of the nitrogenous doped structure 1. step (1) obtained is placed in distilled water and concentrated nitric acid mixing solutions (V
water/ V
acid=1: 10), 90 DEG C are heated to, magnetic agitation 2 hours;
2. gained mixture in above-mentioned steps is filtered, adds deionized water rinsing, until filtrate is in neutral or close neutral, dry immediately, the hollow N doping Nano graphite cage of iron particle must be removed.
Implementation result: form the hollow plumbago nanocages that mean diameter is 50nm, detect its wall thickness is 5nm, the graphite number of plies is 10 layers, and pore size distribution concentrates on 6nm, and nitrogen content is 3wt%, specific surface area 300m
2g
-1.
embodiment 3
(1) the carbon-coated iron nano core-shell particle of nitrogenous doped structure is prepared
Ferric acetyl acetonade, ethanol and Ursol D are joined to obtain material solution in mass ratio at 10: 20: 70; Vertical tubular furnace is warming up to temperature of reaction 850 DEG C, and passes into nitrogen as carrier gas, flow velocity is 40 ls/h; The injector that material solution is input to tube furnace top through electronic peristaltic pump is sprayed into tube furnace high-temperature zone, and it is 10 mls/hour that electronic peristaltic pump controls material solution flow velocity.The carbon-coated iron nano core-shell particle of nitrogenous doped structure is obtained in tube furnace afterbody product collector.
(2) the hollow plumbago nanocages of nitrogenous doped structure is prepared
The carbon-coated iron nano core-shell particle of the nitrogenous doped structure 1. step (1) obtained is placed in distilled water and concentrated nitric acid mixing solutions (V
water/ V
acid=2: 1), 70 DEG C are heated to, magnetic agitation 3 hours;
2. gained mixture in above-mentioned steps is filtered, adds deionized water rinsing, until filtrate is in neutral or close neutral, dry immediately, the hollow N doping Nano graphite cage of iron particle must be removed.
Implementation result: form the hollow plumbago nanocages that diameter is 40nm, detect its wall thickness is 3nm, the graphite number of plies is 8 layers, and pore size distribution concentrates on 3.7nm, and nitrogen content is 1.9wt%, specific surface area 400m
2g
-1.
Claims (6)
1. a preparation method for the N doping Nano graphite cage of high-specific surface area, is characterized in that comprising the following steps:
The step of the carbon-coated iron nano core-shell particle of (1) nitrogenous doped structure of preparation,
Take catalyzer, nitrogenous source, carbon source, described catalyzer is ferric acetyl acetonade, and described nitrogenous source is Ursol D or acetonitrile, and the mass ratio of catalyzer, Carbon and nitrogen sources is 5 ~ 20: 0 ~ 90: 5 ~ 80, and material solution is joined to obtain in above-mentioned substance mixing; Vertical tubular furnace is warming up to 500 ~ 1200 DEG C, and pass into nitrogen as carrier gas, material solution is input to the injector on vertical tubular furnace top through electronic peristaltic pump, spray into tube furnace high-temperature zone by injector, in tube furnace afterbody product collector, obtain the carbon-coated iron nano core-shell particle of nitrogenous doped structure;
(2) the carbon-coated iron nano core-shell particle of nitrogenous doped structure step (1) obtained is placed in distilled water and nitric acid mixing solutions, be heated to 60 ~ 90 DEG C and magnetic agitation, above-mentioned gained mixture is filtered, adds deionized water rinsing, until filtrate is in neutral or close neutral, lyophilize immediately, obtain the hollow N doping Nano graphite cage of high-specific surface area, its nitrogen content is at 0.8 ~ 3wt%, pore size distribution concentrates on 1.8 ~ 6nm, and specific surface area is 300 ~ 900m
2g
-1.
2. the method for the N doping Nano graphite cage of synthesizing high specific surface area according to claim 1, is characterized in that: the carbon source used in described step (1) is ethanol.
3. the method for the N doping Nano graphite cage of synthesizing high specific surface area according to claim 1, is characterized in that: in described step (1), the flow velocity of nitrogen is 40 ~ 160 ls/h.
4. the method for the N doping Nano graphite cage of synthesizing high specific surface area according to claim 1, it is characterized in that: the injector that described step (1) Raw solution is input to vertical tubular furnace top through electronic peristaltic pump sprays into tube furnace high-temperature zone, it is 10 ~ 120 mls/hour that electronic peristaltic pump controls material solution flow velocity.
5. the method for the N doping Nano graphite cage of synthesizing high specific surface area according to claim 1, is characterized in that: in described step (2), distilled water and concentrated nitric acid mixing solutions ratio are V
water/ V
acid=1: 10 ~ 4: 1.
6. the method for the N doping Nano graphite cage of synthesizing high specific surface area according to claim 1, is characterized in that: in described step (2), the magnetic agitation time is 2 ~ 6 hours.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109004240A (en) * | 2018-07-25 | 2018-12-14 | 上海应用技术大学 | A kind of preparation method of high-specific surface area iron nitrogen C catalyst |
| CN110867590A (en) * | 2019-11-20 | 2020-03-06 | 上海应用技术大学 | Method for continuously preparing high-nitrogen-doped nano-porous graphite particles |
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| CN1583552A (en) * | 2004-05-27 | 2005-02-23 | 上海交通大学 | Method for mass preparing hollow nanometer carbon cages |
| CN102530922A (en) * | 2012-03-12 | 2012-07-04 | 南京大学 | Method for preparing nitrogen doping hollow carbon nanocages |
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2015
- 2015-08-13 CN CN201510494953.2A patent/CN105084352A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1583552A (en) * | 2004-05-27 | 2005-02-23 | 上海交通大学 | Method for mass preparing hollow nanometer carbon cages |
| CN102530922A (en) * | 2012-03-12 | 2012-07-04 | 南京大学 | Method for preparing nitrogen doping hollow carbon nanocages |
Non-Patent Citations (1)
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109004240A (en) * | 2018-07-25 | 2018-12-14 | 上海应用技术大学 | A kind of preparation method of high-specific surface area iron nitrogen C catalyst |
| CN109004240B (en) * | 2018-07-25 | 2021-09-28 | 上海应用技术大学 | Preparation method of high specific surface area iron nitrogen carbon catalyst |
| CN110867590A (en) * | 2019-11-20 | 2020-03-06 | 上海应用技术大学 | Method for continuously preparing high-nitrogen-doped nano-porous graphite particles |
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