CN108285143A - A kind of preparation method of biomass-based N doping thin layer graphite carbon material - Google Patents
A kind of preparation method of biomass-based N doping thin layer graphite carbon material Download PDFInfo
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- CN108285143A CN108285143A CN201810069435.XA CN201810069435A CN108285143A CN 108285143 A CN108285143 A CN 108285143A CN 201810069435 A CN201810069435 A CN 201810069435A CN 108285143 A CN108285143 A CN 108285143A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/01—Crystal-structural characteristics depicted by a TEM-image
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- 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
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- C—CHEMISTRY; METALLURGY
- 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
Abstract
A kind of preparation method of biomass-based N doping thin layer graphite carbon material, which is characterized in that include the following steps：1), using lignin as carbon source, by nitration reaction, nitro is introduced in lignin function group, nitro is then reduced into amino, obtain the lignin of N doping；2), the lignin of N doping is carbonized in an inert atmosphere；3) the thin layer graphite carbon material of N doping is obtained by chemical graft process.N doping thin layer graphite carbon material provided by the present invention has good degree of graphitization and relatively thin graphite linings, and synthetic method is simple, environmentally friendly using renewable lignin as carbon source, sustainable.
Description
Technical field
The invention belongs to biomass-based carbon material technical field, more particularly to a kind of biomass-based N doping thin layer graphite
The preparation method of carbon material.
Background technology
In recent years, the carbon material of hetero atom (such as nitrogen, boron, phosphorus, sulphur, cobalt) doping, the especially carbon with laminate structure
Nano material, because it is with larger specific surface area and pore volume, higher electric conductivity and good physics and chemical stabilization
It the advantages that property, is being catalyzed, adsorbent, the fields such as electrode material and battery have a wide range of applications.On the one hand, hetero atom is introduced into
After carbon structure, because it is different from carbon atom bond distance, valence electron and atomic size, nearby there is defect in site in adjacent carbon atom, electricity
Lotus is unevenly distributed, and the electroneutral of carbon material is damaged, and is more advantageous to the catalytic active center for constructing carbon material.On the other hand,
Coating carbon material has class graphite olefinic functionality, the migration and diffusion of electronics can be substantially improved, to improve the catalysis of carbon material
Activity.Therefore, the hollow carbon material for preparing Heteroatom doping has important research significance.
Currently, the presoma of carbon material synthesis depends on petrochemical intermediates, since the generation of oil is one
Very long geological process, while oil is the main energy sources of contemporary mankind society again, with the worsening shortages of fossil resource, to change
Carbon material shortage problem based on stone resource is also following, therefore finds a kind of other resources that can substitute oil, then
As a problem in the urgent need to address in 21 century carbon material scientific research.Lignin is that one kind is unformed, structure is multiple
Miscellaneous three-dimensional netted aromatics natural high polymer, because phosphorus content is between 55%~66% in lignin, it is possible to as
Prepare the presoma of carbon material.Therefore how to prepare carbon material using lignin replacement fossil energy and receive the wide of scientists
General concern, to realizing that lignin higher value application is of great significance.
Carbon material scientists are prepared for carbon source done many work using lignin, such as：Using ethyl alcohol as carbon source,
Carbonyl iron is source of iron, obtains the carbon ball of 30-50nm under 600-900 DEG C of high temperature using floating chemical vapour deposition technique, is made
Pt/C catalyst is prepared for low-temperature fuel cell for catalyst carrier.Using butane as carbon source, carbon has been obtained at 2000 DEG C
Iron clad material uses it for phenylacetylene hydrogenation synthesizing styrene, shows remarkable catalytic performance, is 99% in conversion ratio
In the case of, the selectivity of styrene has reached 86%.Think pyridine be carbon source be prepared for diameter 300nm or so N doping
Mesoporous carbon is applied on ultracapacitor, and specific capacity has reached 350F/g.Although small organic molecule prepares charcoal as carbon source
The advantages that ball has carbon source structure to fix, and reaction is easy to operate, and product catalyst activity is high, but carbon source is the centre based on fossil fuel
Body, it is unsustainable, and carbon material degree of graphitization prepared by such methods is low, graphitic carbon carbon-coating is thick, specific surface area is low and surface
The problems such as structure is uncontrollable, these all limit its large-scale production and application.
In order to overcome the deficiencies of the prior art, probe into a kind of easy to operate, at low cost prepares miscellaneous N doping thin layer graphite
The method of carbon material has great importance to play its performance advantage.
Invention content
To solve to be in the prior art that carbon source prepares carbon material with degree of graphitization is low, graphitic carbon carbon-coating using lignin
Thick, the problems such as specific surface area is low and surface texture is uncontrollable defect, the present invention provide a kind of biomass-based N doping thin layer stone
The preparation method of inkization carbon material.
A kind of preparation method of biomass-based N doping thin layer graphite carbon material, includes the following steps：
1), using lignin as carbon source, by nitration reaction, nitro is introduced in lignin function group, then also by nitro
Original obtains the lignin of N doping at amino；
2), the lignin of N doping is carbonized in an inert atmosphere；
3) the thin layer graphite carbon material of N doping is obtained by chemical graft process.
Further, lignin is dissolved in acetic anhydride in the step 1), is then slowly dropped into nitric acid, reacts at room temperature
Then 5h adjusts pH to neutrality, is finally extracted with organic solvent, obtain nitration of lignin.Preferably, the organic solvent is
Any one in tetrahydrofuran, carbon tetrachloride or dichloromethane.For example, by 1g lignin be dissolved in acetic anhydride (10ml,
0.1mol/L), it is then slowly dropped into 10ml nitric acid (0.1mol/L), three's mixed liquor reacts 5h, then uses hydrogen-oxygen at room temperature
Change sodium solution (1mol/L) and adjust PH to neutrality, is finally extracted with organic solvent, obtain nitration of lignin.
Further, the lignin derives from the vegetation quality of stalk, and the nitro of gained nitration of lignin is in phenyl ring
Ortho position on.
Further, nitration of lignin is dissolved in 50% ethanol solution, iron powder is added, instilled hydrochloric acid, be warming up to 130
DEG C, 6h is reacted, pH is then adjusted to alkalinity, N doping lignin is obtained after washing filtering.
Further, carbonization condition is in the step 2)：Carburizing temperature be 1000-1200 DEG C, heating rate be 2 DEG C/
Min, carbonization time 3h.
Further, chemical graft process is in the step 3)：It takes the graphitized carbon of N doping to be dissolved in ammonium persulfate to add
Enter the concentrated sulfuric acid, hydrogen peroxide is slowly added dropwise after being stirred to react 3h, after reaction, is centrifuged, washs, is dried in vacuo, obtain
The thin layer graphite carbon of N doping.
Advantageous effect：N doping thin layer graphite carbon material provided by the present invention have good degree of graphitization and compared with
Thin graphite linings, synthetic method is simple, environmentally friendly using renewable lignin as carbon source, sustainable.
Description of the drawings
The XRD spectrum figure of Fig. 1, biomass-based N doping thin layer graphite carbon material；
The Raman spectrograms of Fig. 2, biomass-based N doping thin layer graphite carbon material；
The TEM figures of Fig. 3, biomass-based N doping thin layer graphite carbon material；
The impedance diagram of Fig. 4, biomass-based N doping thin layer graphite carbon material.
Specific implementation mode
Embodiment 1
(1) first 1g lignin is placed in round-bottomed bottle, a concentration of 0.1mol/L solution of acetic anhydride of 10mL is added and 10ml is dense
Degree is 0.1mol/L nitric acid, stirs 5h at room temperature, then uses 1mol/L sodium hydroxide solutions to adjust PH to neutrality, finally uses tetrahydrochysene
Furans extracts, and obtains nitration of lignin；
(2) it takes 0.5g steps 1) to obtain nitration of lignin to be dissolved in 50% ethanol solution, a little iron powder is added, instill
2ml hydrochloric acid is warming up to 130 DEG C, reacts 6h, and sodium hydroxide solution (1mol/L) is then added dropwise and adjusts PH to alkalinity, through centrifuging, washing
It washs, dry, obtain N doping lignin；
(3) the N doping lignin presoma that step 2) obtains is placed in high temperature furnace, with 2 DEG C/min in argon gas atmosphere
Rate be warming up to 1200 DEG C, inert gas flow velocity 50mL/min.After 3h being carbonized at 1200 DEG C, cooled to room temperature,
Obtain the graphitized carbon of N doping of the present invention；
(4) it takes the graphitized carbon of the N doping of 0.2g steps 3) to be dissolved in 20ml ammonium persulfates (2mol/L), it is dense that 10ml is added
Sulfuric acid, three are easy that 1ml hydrogen peroxide is slowly added dropwise after being stirred to react 3h, after reaction, are centrifuged, wash, vacuum is done
It is dry, obtain the thin layer graphite carbon of final N doping.As shown in Fig. 1 x-ray crystal diffraction results, the position at three peaks exists respectively
26.1 °, 41.8 ° and 44.1 ° (002) for corresponding to graphitized carbon respectively, (100) and (101) crystal face.(002) diffraction maximum of crystal face
It is narrow and strong, illustrate that the material has higher degree of graphitization.The value of ID/IG is said 0.21 or so in Fig. 2 Raman spectrum results
The degree of graphitization that the material is illustrated is very high, as a result consistent with XRD.In the saturating color electromicroscopic photographs of Fig. 3 the transparency of the material compared with
Height illustrates that the number of plies of graphitized carbon is relatively thin.Fig. 4 results of AC impedance surface material conductivity is preferable, demonstrates the material
With higher degree of graphitization.
Embodiment 2
(1) first 1g lignin is placed in round-bottomed bottle, a concentration of 0.1mol/L solution of acetic anhydride of 10mL is added and 10ml is dense
Degree is 0.1mol/L nitric acid, stirs 5h at room temperature, then uses 1mol/L sodium hydroxide solutions to adjust pH to neutrality, finally uses tetrachloro
Methane takes, and obtains nitration of lignin；
(2) it takes 0.5g steps 1) to obtain nitration of lignin to be dissolved in 50% ethanol solution, a little iron powder is added, instill
2ml hydrochloric acid is warming up to 130 DEG C, reacts 6h, and sodium hydroxide solution (1mol/L) is then added dropwise and adjusts PH to alkalinity, through centrifuging, washing
It washs, dry, obtain N doping lignin.
(3) the N doping lignin presoma that step 2) obtains is placed in high temperature furnace, with 2 DEG C/min in argon gas atmosphere
Rate be warming up to 1200 DEG C, inert gas flow velocity 50mL/min.After 3h being carbonized at 1000 DEG C, cooled to room temperature,
Obtain the graphitized carbon of N doping of the present invention.
(4) it takes the graphitized carbon of the N doping of 0.2g steps 3) to be dissolved in 20ml ammonium persulfates (2mol/L), it is dense that 10ml is added
Sulfuric acid, three are easy that 1ml hydrogen peroxide is slowly added dropwise after being stirred to react 3h, after reaction, are centrifuged, wash, vacuum is done
It is dry, obtain the thin layer graphite carbon of final N doping.
Claims (7)
1. a kind of preparation method of biomass-based N doping thin layer graphite carbon material, which is characterized in that include the following steps：
1), using lignin as carbon source, by nitration reaction, nitro is introduced in lignin function group, is then reduced into nitro
Amino obtains the lignin of N doping；
2), the lignin of N doping is carbonized in an inert atmosphere；
3) the thin layer graphite carbon material of N doping is obtained by chemical graft process.
2. the preparation method of biomass-based N doping thin layer graphite carbon material as described in claim 1, which is characterized in that institute
It states in step 1) and lignin is dissolved in acetic anhydride, be then slowly dropped into nitric acid, react 5h at room temperature, then adjusting pH to neutrality,
It is finally extracted with organic solvent, obtains nitration of lignin.
3. the preparation method of biomass-based N doping thin layer graphite carbon material as claimed in claim 2, which is characterized in that institute
The organic solvent stated is any one in tetrahydrofuran, carbon tetrachloride or dichloromethane.
4. the preparation method of biomass-based N doping thin layer graphite carbon material as claimed in claim 2, which is characterized in that institute
The lignin stated derives from the vegetation quality of stalk, and the nitro of gained nitration of lignin is on the ortho position of phenyl ring.
5. the preparation method of biomass-based N doping thin layer graphite carbon material as claimed in claim 2, which is characterized in that will
Nitration of lignin is dissolved in 50% ethanol solution, and iron powder is added, and instills hydrochloric acid, is warming up to 130 DEG C, is reacted 6h, is then adjusted
PH obtains N doping lignin to alkalinity after washing filtering.
6. the preparation method of biomass-based N doping thin layer graphite carbon material as described in claim 1, which is characterized in that institute
Stating carbonization condition in step 2) is：Carburizing temperature is 1000-1200 DEG C, and heating rate is 2 DEG C/min, carbonization time 3h.
7. the preparation method of biomass-based N doping thin layer graphite carbon material as described in claim 1, which is characterized in that institute
Stating chemical graft process in step 3) is：It takes the graphitized carbon of N doping to be dissolved in ammonium persulfate and the concentrated sulfuric acid is added, be stirred to react 3h
After hydrogen peroxide is slowly added dropwise, after reaction, be centrifuged, wash, be dried in vacuo, obtain the thin layer graphite of N doping
Carbon.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012590A (en) * | 2018-08-24 | 2018-12-18 | 华南理工大学 | A kind of lignin-base transition metal-nitrogen-doped carbon material and its preparation and application |
| CN110518243A (en) * | 2019-08-20 | 2019-11-29 | 台州立拓能源有限公司 | Lignin is preparing the application in lithium battery graphite cathode material |
| CN116462193A (en) * | 2023-03-22 | 2023-07-21 | 广西宸宇新材料有限公司 | Modified graphite and preparation and application thereof in battery |
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| CN1268509A (en) * | 2000-04-20 | 2000-10-04 | 江苏省农药研究所 | Substituted phenyl heterocyclic compound weedicide |
| US20160237103A1 (en) * | 2009-02-11 | 2016-08-18 | Xyleco, Inc. | Processing biomass |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109012590A (en) * | 2018-08-24 | 2018-12-18 | 华南理工大学 | A kind of lignin-base transition metal-nitrogen-doped carbon material and its preparation and application |
| CN109012590B (en) * | 2018-08-24 | 2020-04-07 | 华南理工大学 | Lignin-based transition metal-nitrogen-doped carbon material and preparation and application thereof |
| CN110518243A (en) * | 2019-08-20 | 2019-11-29 | 台州立拓能源有限公司 | Lignin is preparing the application in lithium battery graphite cathode material |
| CN116462193A (en) * | 2023-03-22 | 2023-07-21 | 广西宸宇新材料有限公司 | Modified graphite and preparation and application thereof in battery |
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