CN105905891A - Method for preparing porous graphene by catalytic cracking and self-activation method - Google Patents
Method for preparing porous graphene by catalytic cracking and self-activation method Download PDFInfo
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- CN105905891A CN105905891A CN201610504857.6A CN201610504857A CN105905891A CN 105905891 A CN105905891 A CN 105905891A CN 201610504857 A CN201610504857 A CN 201610504857A CN 105905891 A CN105905891 A CN 105905891A
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- porous graphene
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/20—Graphene characterized by its properties
- C01B2204/32—Size or surface area
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
Abstract
The invention discloses a method for preparing porous graphene by a catalytic cracking and self-activation method. The method is characterized by adopting calcium salts as catalysts to catalyze biomass cracking to generate cracked gas, wherein one part of the cracked gas is used for preparing a carbon source of graphene and the other part of the cracked gas is used for activating graphene to form a porous structure, thus achieving preparation of porous graphene through catalytic cracking and self-activation. The prepared porous graphene has specific area more than 800m<2>/g and pore size distribution of 10-50nm. With calcium salts as the catalysts, the method, compared with current preparation methods, is low in cost and pollution, can be used for preparing porous graphene on a large scale, is a brand-new universal method suitable for biomass and is beneficial to comprehensively solving the problems of biomass resource utilization and graphene application requirements.
Description
Technical field
The invention belongs to material with carbon element technical field, be specifically related to the preparation method of a kind of porous graphene.
Background technology
Due to three dimensional structure give grapheme material with big can and specific surface area, big porosity, interconnective
Conductive network and special microenvironment.Therefore, three-dimensional grapheme carries at flexible electrode, ultracapacitor, catalyst
The application in body, hydrogen storage material, sensor and environment remediation field increasingly receives publicity.Three-dimensional grapheme is not only
Have in Graphene excellent properties, also have the specific function characteristic that three-dimensional porous structure is brought, have wide
General application prospect.
At present, multiple method can be used to prepare porous graphene, can be divided mainly into template, chemical gaseous phase sink
Area method and solution self-assembly method etc..In these methods, template is a kind of effective to prepare three-dimensional grapheme
Method, but template used usually inorganic salt.Template needs to build template, system before preparing porous graphene preparation
Needing removing template after Bei, preparation process is complicated, relatively costly, is not suitable for industrialized production.Chemical gaseous phase deposits
Although method can obtain large scale continuous print three-dimensional grapheme, but needs to perform etching template after preparation, cost is relatively
High, it is impossible to meet the extensive demand in energy storage material and functional composite material field.Solution self-assembly method preparation three-dimensional
Graphene is relatively easy to realize industrialized production, is substantially that two-dimensional graphene prepares three-dimensional grapheme, but is used
Raw material be usually graphene oxide, preparation condition needs High Temperature High Pressure, can produce a large amount of in preparation process simultaneously
Poisonous and harmful substance, easily pollute environment, prepared by the Graphene being therefore not suitable for extensive industrialization.
Summary of the invention
The technical problem to be solved is to provide a kind of with biological material as raw material, with calcium salt for catalysis
Agent, low cost, low stain, the method for preparing porous graphene on a large scale.
Solve above-mentioned technical problem be the technical scheme is that biological material is pulverized and sieved after with calcium salt be catalyzed
Agent is 1:1～10 mix homogeneously in mass ratio, and gained mixture is warming up to 700～1600 DEG C in noble gas,
Constant temperature carbonization 1～10h, then carries out post processing by carbonized product, obtains porous graphene.
Above-mentioned biological material be in amygdalus pedunculata pall, Fructus Pruni shell, walnut shell any one or two or more；Institute
The calcium salt catalyst stated be in calcium nitrate, calcium formate, calcium acetate, calcium phosphate, calcium hydroxide any one or two
More than Zhong, preferably any one in calcium nitrate, calcium formate, calcium acetate.
Above-mentioned biological material is preferably 1:2～4 with the mass ratio of calcium salt catalyst.
Gained mixture is preferably warming up to 1000～1300 DEG C in noble gas by the present invention, constant temperature carbonization 4～6
H, wherein said heating rate be 5～50 DEG C/min, preferably heating rate be 20～35 DEG C/min.
Above-mentioned noble gas is argon, helium or nitrogen, and the flow velocity of noble gas is 200～1000mL/min.
Above-mentioned post processing is to be dried after acid, deionized water wash successively by carbonized product again, and wherein said acid is
Dust technology or dilute hydrochloric acid.
The present invention uses calcium salt to be catalyst first, and catalysis biomass cracking produces cracking gas, and a cracking gas part is used
The carbon source of Graphene prepared by work, and a part is used for activating Graphene and forms loose structure, it is achieved catalytic pyrolysis self-activation
Prepare porous graphene.
The present invention with calcium salt as catalyst, low cost for more current preparation method, low stain, it is possible to extensive
Prepare porous graphene, and the porous graphene specific area of preparation is more than 800m2/ g, pore-size distribution is 10～50nm.
The inventive method is a kind of brand-new universal method being applicable to biomass, is conducive to comprehensive solution biomass resource profit
By the problem with Graphene application demand.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of the porous graphene of embodiment 1 preparation.
Fig. 2 is the partial enlarged drawing of Fig. 1.
Fig. 3 is the transmission electron microscope picture of the porous graphene of embodiment 1 preparation.
Fig. 4 is the nitrogen adsorption desorption isollaothermic chart of the porous graphene of embodiment 1 preparation.
Fig. 5 is the Raman spectrogram of the porous graphene of embodiment 1 preparation.
Fig. 6 is the transmission electron microscope picture of the porous graphene of embodiment 2 preparation.
Fig. 7 is the transmission electron microscope picture of the porous graphene of embodiment 3 preparation.
Fig. 8 is the transmission electron microscope picture of the porous graphene of embodiment 4 preparation.
Detailed description of the invention
The present invention is described in more detail with embodiment below in conjunction with the accompanying drawings, but protection scope of the present invention not only limits
In these embodiments.
Embodiment 1
Cross 300 mesh sieves after being pulverized by amygdalus pedunculata pall, take the amygdalus pedunculata pall powder 10g after sieving, at room temperature,
Mix homogeneously with 30g calcium nitrate, load in porcelain example boat, porcelain example boat is put in tube furnace, is passed through argon
Gas, argon flow velocity is 500mL/min, is warming up to 1100 DEG C with the heating rate of 30 DEG C/min, and temperature at this
Keep 5h under degree, be naturally down to room temperature, sample is taken out, successively with after dust technology, deionized water wash 100 DEG C
Drying, obtain porous graphene (see Fig. 1～3), its yield is 9%.Can be obtained by Fig. 4, its specific surface area is
832m2/ g, aperture is 10～15nm.Fig. 5 proves that products therefrom is Graphene.
Embodiment 2
Cross 300 mesh sieves after being pulverized by Fructus Pruni shell, take the Fructus Pruni shell powder 10g after sieving, at room temperature, with 30g formic acid
Calcium mix homogeneously, loads in porcelain example boat, puts in tube furnace by porcelain example boat, be passed through argon, argon stream
Speed is 300mL/min, is warming up to 1250 DEG C with the heating rate of 30 DEG C/min, and keeps 6.5 at this temperature
H, is down to room temperature naturally, is taken out by sample, successively with 100 DEG C of drying after dust technology, deionized water wash,
To porous graphene (see Fig. 6), its yield is 11%, and specific surface area is 857m2/ g, aperture is 20～40nm.
Embodiment 3
Cross 300 mesh sieves after being pulverized by walnut shell, take the walnut shell powder 10g after sieving, at room temperature, with 30g
Calcium hydroxide mix homogeneously, loads in porcelain example boat, puts in tube furnace by porcelain example boat, be passed through helium,
Helium flow velocity is 500mL/min, is warming up to 1200 DEG C with the heating rate of 25 DEG C/min, and at this temperature
Keep 6h, be naturally down to room temperature, sample is taken out, successively with 100 DEG C of bakings after dust technology, deionized water wash
Dry, obtain porous graphene (see Fig. 7), its yield is 9.6%, and specific surface area is 815m2/ g, aperture be 30～
50nm。
Embodiment 4
Cross 200 mesh sieves after being pulverized by amygdalus pedunculata pall, take the amygdalus pedunculata pall powder 10g after sieving, at room temperature,
Mix homogeneously with 40g calcium acetate, load in porcelain example boat, porcelain example boat is put in tube furnace, is passed through helium
Gas, helium flow velocity is 500mL/min, is warming up to 1250 DEG C with the heating rate of 25 DEG C/min, and temperature at this
Keep 6h under degree, be naturally down to room temperature, sample is taken out, successively with after dust technology, deionized water wash 100 DEG C
Drying, obtain porous graphene (see Fig. 8), its yield is 12.2%, and specific surface area is 862m2/ g, aperture is
20～40nm.
Claims (10)
1. a catalytic pyrolysis self-activation method prepares porous graphene, it is characterised in that: biological material is pulverized
Mixing homogeneously for 1:1～10 in mass ratio with calcium salt catalyst after sieving, gained mixture heats up in noble gas
To 700～1600 DEG C, constant temperature carbonization 1～10h, then carbonized product is carried out post processing, obtain porous graphite
Alkene.
Catalytic pyrolysis self-activation method the most according to claim 1 prepares porous graphene, it is characterised in that:
Described biological material be in amygdalus pedunculata pall, Fructus Pruni shell, walnut shell any one or two or more.
Catalytic pyrolysis self-activation method the most according to claim 1 prepares porous graphene, it is characterised in that:
Described calcium salt catalyst be in calcium nitrate, calcium formate, calcium acetate, calcium phosphate, calcium hydroxide any one or
Two or more.
Catalytic pyrolysis self-activation method the most according to claim 1 prepares porous graphene, it is characterised in that:
Described calcium salt catalyst is any one in calcium nitrate, calcium formate, calcium acetate.
5. prepare porous graphene according to the catalytic pyrolysis self-activation method described in Claims 1 to 4 any one, its
It is characterised by: described biological material is 1:2～4 with the mass ratio of calcium salt catalyst.
6. prepare porous graphene according to the catalytic pyrolysis self-activation method described in Claims 1 to 4 any one, its
It is characterised by: gained mixture is warming up to 1000～1300 DEG C in noble gas, constant temperature carbonization 4～6h.
Catalytic pyrolysis self-activation method the most according to claim 6 prepares porous graphene, it is characterised in that:
Described heating rate is 5～50 DEG C/min.
Catalytic pyrolysis self-activation method the most according to claim 6 prepares porous graphene, it is characterised in that:
Described heating rate is 20～35 DEG C/min.
Catalytic pyrolysis self-activation method the most according to claim 1 prepares porous graphene, it is characterised in that:
Described noble gas is argon, helium or nitrogen, and the flow velocity of noble gas is 200～1000mL/min.
Catalytic pyrolysis self-activation method the most according to claim 1 prepares porous graphene, it is characterised in that:
Described post processing is to be dried after acid, deionized water wash successively by carbonized product again, and wherein said acid is dilute nitre
Acid or dilute hydrochloric acid.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112575310A (en) * | 2020-11-27 | 2021-03-30 | 重庆大学 | Method for preparing graphene film through low-temperature chemical vapor deposition |
| CN112678809A (en) * | 2020-12-30 | 2021-04-20 | 安徽工程大学 | Method for synthesizing graphene with hierarchical structure by catalyzing biomass |
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| CN104016341A (en) * | 2014-07-01 | 2014-09-03 | 济南圣泉集团股份有限公司 | Preparation method of porous graphene |
| CN104401992A (en) * | 2014-10-22 | 2015-03-11 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing activated carbon for super capacitor with fruit shells as raw material and application of activated carbon |
| CN104495842A (en) * | 2014-12-29 | 2015-04-08 | 新疆大学 | Method for preparing activated carbon by partially substituting potassium hydroxide by calcium hydroxide |
| CN105236408A (en) * | 2015-10-30 | 2016-01-13 | 上海市政工程设计研究总院（集团）有限公司 | Preparation method of continuous multilevel-pore activated carbon |
| CN105329892A (en) * | 2015-11-24 | 2016-02-17 | 吉林省凯禹生物质开发利用有限公司 | Method for producing capacitive carbon from rice husks |
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2016
- 2016-06-30 CN CN201610504857.6A patent/CN105905891A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104016341A (en) * | 2014-07-01 | 2014-09-03 | 济南圣泉集团股份有限公司 | Preparation method of porous graphene |
| CN104401992A (en) * | 2014-10-22 | 2015-03-11 | 深圳市贝特瑞新能源材料股份有限公司 | Method for preparing activated carbon for super capacitor with fruit shells as raw material and application of activated carbon |
| CN104495842A (en) * | 2014-12-29 | 2015-04-08 | 新疆大学 | Method for preparing activated carbon by partially substituting potassium hydroxide by calcium hydroxide |
| CN105236408A (en) * | 2015-10-30 | 2016-01-13 | 上海市政工程设计研究总院（集团）有限公司 | Preparation method of continuous multilevel-pore activated carbon |
| CN105329892A (en) * | 2015-11-24 | 2016-02-17 | 吉林省凯禹生物质开发利用有限公司 | Method for producing capacitive carbon from rice husks |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112575310A (en) * | 2020-11-27 | 2021-03-30 | 重庆大学 | Method for preparing graphene film through low-temperature chemical vapor deposition |
| CN112678809A (en) * | 2020-12-30 | 2021-04-20 | 安徽工程大学 | Method for synthesizing graphene with hierarchical structure by catalyzing biomass |
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