CN105923629B - The method that dipping recrystallization carbonization biomass prepares the compound Heteroatom doping porous carbon materials of transition metal - Google Patents
The method that dipping recrystallization carbonization biomass prepares the compound Heteroatom doping porous carbon materials of transition metal Download PDFInfo
- Publication number
- CN105923629B CN105923629B CN201610265252.6A CN201610265252A CN105923629B CN 105923629 B CN105923629 B CN 105923629B CN 201610265252 A CN201610265252 A CN 201610265252A CN 105923629 B CN105923629 B CN 105923629B
- Authority
- CN
- China
- Prior art keywords
- biomass
- porous carbon
- compound
- transition metal
- dipping
- 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.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/30—Making metallic powder or suspensions thereof using chemical processes with decomposition of metal compounds, e.g. by pyrolysis
-
- 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
-
- 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
- C01P2006/40—Electric properties
Abstract
The present invention is to provide a kind of methods that dipping recrystallization carbonization biomass prepares the compound Heteroatom doping porous carbon materials of transition metal.Step 1：Biomass is immersed in the aqueous solution of metal salt, and the method for the biomass economy vacuum freezedrying after immersion makes metal salt recrystallize to obtain product A in the hole of biomass；Step 2：High-temperature calcination will be carried out in product A merging tube furnace, and make biomass that carburizing reagent occur at high temperature, while metal salt decomposition reaction occurs, and obtain that transition metal will be compound while the porous carbon materials of Heteroatom doping.The present invention uses biomass for raw material, utilize biomass porous structure, prepare the biomass carbon material of base metal modification, compared with conventional high temperature is carbonized, the purpose for realizing activation trepanning can be synchronized in carbonisation using dipping recrystallization method carbonization, because prepared by porous carbon there is larger specific surface area, good electric conductivity, therefore still have strong energy stores and releasability at higher current densities.
Description
Technical field
The present invention relates to a kind of transition metal it is compound-preparation methods of Heteroatom doping porous carbon materials.
Background technology
In recent years, carbon material is paid close attention to by people, is had been widely used for as material that is a kind of inexpensive and stablizing
The fields such as gas separation, purifying water process, catalytic chromatography analysis, energy storage and photocatalysis.And the electricity of original carbon material
Performance is relatively weak, and up to the present, the capacitance of traditional active carbon material is substantially in 100-200Fg-1.Due to sp2It is miscellaneous
Connected carbon atom can be changed with abundant in the pi-electron of material surface free migration, heteroatomic incorporation by changing carbon material
Electronegativity, to be conducive to improve its electric property.In order to improve doped carbon material electrochemical performance, by changing presoma
Selection, different hetero atoms is incorporated into carbon material, such as：N, S, B, I, P etc., while control condition raising is heteroatomic
Content regulates and controls the type of miscellaneous element.Research shows that the miscellaneous constituent content of single doping carbon material is limited, it is unfavorable for carrying for material property
It is high.In order to improve the content of miscellaneous element, sight is turned to more doping and codope by researchers, improves containing for miscellaneous element whereby
Amount, and so that the chemical property of material is strengthened using the synergistic effect between different miscellaneous elements.At present prepared by report
Exotic atom doped carbon material synthesis method has：Heat treating process, vapour deposition process, hydro-thermal method, arc discharge, plasma method etc.,
The major defect of these methods is to equipment requirement height, and simultaneous reactions condition requires harshness, leads to the cost of material synthesized
It is higher, it is unfavorable for industrialized production, is less useful for the commercialization of product.
In order to further increase the capacitance of carbon material, transition metal oxide such as (Co3O4、MnO2、NiO、Fe3O4Deng) due to
A large amount of redox reaction can occurs with high specific capacitance value in it, compound to be carried out with carbon material, see
(Carbon,2007,45(7):2365-2373), however due to the poorly conductive of transition metal oxide, prepared answers
The chemical property of condensation material still needs to improve.
Invention content
The purpose of the present invention is to provide a kind of obtained porous carbons to have larger specific surface area, good conduction
Property, still have strong energy stores and releasability at higher current densities, simple, at low cost, the maneuverable dipping weight of step
The method that crystalline silicon carbide biomass prepares the compound Heteroatom doping porous carbon materials of transition metal.
The object of the present invention is achieved like this：
Step 1：Biomass is immersed in the aqueous solution of metal salt, the biomass economy vacuum freezedrying after immersion
Method makes metal salt recrystallize to obtain product A in the hole of biomass；
Step 2：High-temperature calcination will be carried out in product A merging tube furnaces, makes biomass that carburizing reagent occur at high temperature,
Metal salt decomposition reaction occurs simultaneously, obtains that transition metal is compound while the porous carbon materials of Heteroatom doping.
The present invention can also include：
1, the biomass is Hericium erinaceus, agaric, stalk, bean curd powder, rice hulls, sawdust or seaweed.
2, the aqueous solution of the metal salt is one or more of in the nitrate, phosphate or sulfate of Fe, Co, Ni or Mn
Mixture.
3, a concentration of 0.05~2molL of the aqueous solution of the metal salt-1。
4, the high-temperature calcination is to calcine 10~180 minutes in a vacuum or inert atmosphere, and calcination temperature is 600~1100
℃。
Compared with prior art, the present invention has following advantageous effect：
(1) present invention uses biomass for raw material, using biomass porous structure, prepares the biology of base metal modification
Matter carbon material can synchronize realization using dipping recrystallization method carbonization compared with conventional high temperature is carbonized in carbonisation
The purpose for activating trepanning, because prepared by porous carbon there is larger specific surface area, good electric conductivity, therefore close in high current
Still there are strong energy stores and releasability under degree.
(2) present invention is realized and is carbonized in biomass pyrolytic using heteroatomic metal salt solution is contained as carbonization medium
Synchronize in the process it is controllable introduce nonmetallic (N, P, S etc.) hetero atom in carbon material skeleton, while by metal (Fe, Co, Ni,
Mn etc.) with carbon material In-situ reaction, finally obtain that transition metal is compound while the carbon-based material of hetero atom codope, mixed with conventional
Miscellaneous method is compared, and one-step method of the present invention introduces that transition metal is compound and Heteroatom doping, and step is simple, at low cost, is easy behaviour
Make, reactant purity is high, and the introducing of transition metal can not only improve the electric conductivity of carbon-based material, and can also increase its counterfeit electricity
Hold, widen its voltage window, increase substantially its energy density, there is preferable application prospect.
Description of the drawings
Fig. 1 is the SEM figures for the Heteroatom doping porous carbon materials that embodiment 1 obtains.
Fig. 2 is that embodiment 1 obtains Heteroatom doping porous carbon materials in 5mVs-1Sweep the cyclic voltammogram under speed.
Fig. 3 is that embodiment 1 obtains Heteroatom doping porous carbon materials in 1Ag-1Charge and discharge electrograph under current density.
Specific implementation mode
With reference to specific embodiment, the present invention is described in detail.Following embodiment will be helpful to the technology of this field
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that the ordinary skill of this field
For personnel, without departing from the inventive concept of the premise, various modifications and improvements can be made.These belong to the present invention
Protection domain.
Embodiment 1, the preparation of the compound N doped porous carbon materials of Co：
The Hericium erinaceus for weighing 4g, is immersed in 0.5molL-1Co(NO3)2Aqueous solution in 12h, by the Hericium erinaceus after immersion
Vacuum freezedrying is placed in tube furnace, under Ar atmosphere, with 5 DEG C of min-1Heating rate rise to 850 DEG C, constant temperature 60min,
Impurity is removed after cooling wash with distilled water, centrifugal drying obtains Heteroatom doping porous carbon materials.
Physicochemical property characterization, Fig. 1 are carried out to prepared Heteroatom doping porous carbon materials using scanning electron microscope
It has been shown that, prepared Heteroatom doping porous carbon materials be laminated structure, above load C o particles.Gained carbon material Fig. 3 shows,
It is carried out in 1Ag-1Charge-discharge test under current density, 1Ag-1Under discharge current density, specific capacity 200Fg-1。
Embodiment 2, the preparation of the compound N doped porous carbon materials of Ni：
The Hericium erinaceus for weighing 4g, is immersed in 0.5molL-1Ni(NO3)2Aqueous solution in 12h, by the Hericium erinaceus after immersion
Vacuum freezedrying is placed in tube furnace, under Ar atmosphere, with 5 DEG C of min-1Heating rate rise to 850 DEG C, constant temperature 60min,
Impurity is removed after cooling wash with distilled water, centrifugal drying obtains Heteroatom doping porous carbon materials.
Embodiment 3, the preparation of Co composite S doped porous carbon materials：
The Hericium erinaceus for weighing 4g, is immersed in 0.5molL-1CoSO4Aqueous solution in 12h, the Hericium erinaceus after immersion is cold
Freeze vacuum drying, is placed in tube furnace, under Ar atmosphere, with 5 DEG C of min-1Heating rate rise to 850 DEG C, constant temperature 60min is cold
But impurity is removed after wash with distilled water, centrifugal drying obtains Heteroatom doping porous carbon materials.
Embodiment 4, the preparation of Ni composite S doped porous carbon materials：
The Hericium erinaceus for weighing 4g, is immersed in 0.5molL-1NiSO4Aqueous solution in 12h, the Hericium erinaceus after immersion is cold
Freeze vacuum drying, is placed in tube furnace, under Ar atmosphere, with 5 DEG C of min-1Heating rate rise to 850 DEG C, constant temperature 60min is cold
But impurity is removed after wash with distilled water, centrifugal drying obtains Heteroatom doping porous carbon materials.
Claims (3)
1. a kind of method that dipping recrystallization carbonization biomass prepares the compound Heteroatom doping porous carbon materials of transition metal, special
Sign is：
Step 1：Biomass is immersed in the aqueous solution of metal salt, the method for the biomass economy vacuum freezedrying after immersion
So that metal salt recrystallizes to obtain product A in the hole of biomass；The biomass is Hericium erinaceus, agaric, stalk, soybean flour
End, rice hulls, sawdust or seaweed；The aqueous solution of the metal salt is the nitrate or sulfate of Fe, Co, Ni or Mn；
Step 2：High-temperature calcination will be carried out in product A merging tube furnaces, calcination temperature is 850 DEG C, makes biomass fermentation at high temperature
Raw carburizing reagent, while metal salt decomposition reaction occurs, obtains that transition metal is compound while the porous carbon materials of Heteroatom doping.
2. dipping recrystallization carbonization biomass according to claim 1 prepares the compound Heteroatom doping porous carbon of transition metal
The method of material, it is characterized in that：A concentration of 0.05~2molL of the aqueous solution of the metal salt-1。
3. it is more that dipping recrystallization carbonization biomass according to claim 1 or 2 prepares the compound Heteroatom doping of transition metal
The method of hole carbon material, it is characterized in that：The high-temperature calcination is to calcine 10~180 minutes in a vacuum or inert atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610265252.6A CN105923629B (en) | 2016-04-26 | 2016-04-26 | The method that dipping recrystallization carbonization biomass prepares the compound Heteroatom doping porous carbon materials of transition metal |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610265252.6A CN105923629B (en) | 2016-04-26 | 2016-04-26 | The method that dipping recrystallization carbonization biomass prepares the compound Heteroatom doping porous carbon materials of transition metal |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105923629A CN105923629A (en) | 2016-09-07 |
| CN105923629B true CN105923629B (en) | 2018-08-17 |
Family
ID=56836344
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610265252.6A Active CN105923629B (en) | 2016-04-26 | 2016-04-26 | The method that dipping recrystallization carbonization biomass prepares the compound Heteroatom doping porous carbon materials of transition metal |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105923629B (en) |
Families Citing this family (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106783213A (en) * | 2016-12-23 | 2017-05-31 | 宁海县浙工大海洋研究院 | Metal and the mesoporous carbon nano-composite material preparation method of metal oxide quantum dot |
| CN106914265B (en) * | 2017-03-06 | 2019-12-13 | 南京师范大学 | method for preparing nitrogen-doped porous nano carbon material by using biomass as carbon source through gel method |
| CN108963207B (en) * | 2018-06-19 | 2021-09-07 | 上海电力学院 | Porous metal-doped carbon composite material and preparation method and application thereof |
| CN109019554B (en) * | 2018-07-31 | 2020-10-27 | 湖南理工学院 | Nitrogen-phosphorus co-doped porous biomass carbon material, preparation method thereof and application thereof in supercapacitor |
| CN109301182A (en) * | 2018-09-05 | 2019-02-01 | 东华大学 | Static Spinning cobalt/N doping porous carbon nano-composite fiber and its preparation and application |
| CN109728284B (en) * | 2019-01-02 | 2022-04-19 | 齐鲁工业大学 | Preparation method of metal-modified three-dimensional carbon net loaded metal organic framework as lithium/sodium-sulfur battery positive electrode material |
| CN109650376B (en) * | 2019-01-23 | 2022-05-20 | 复旦大学 | Method for preparing carbon nanosheet containing multilevel structure by using biomass |
| CN109786723A (en) * | 2019-03-11 | 2019-05-21 | 上海电力学院 | A kind of preparation method of the carbon composite of three-dimensional porous low metal doping |
| CN111129531B (en) * | 2020-01-06 | 2023-03-21 | 西安航空职业技术学院 | Preparation method of cobalt-nitrogen co-doped biomass carbon zinc-air battery catalyst |
| CN111204732B (en) * | 2020-01-13 | 2021-07-23 | 吉林大学 | Transition metal doped porous carbon material and preparation method and application thereof |
| CN111613456B (en) * | 2020-06-04 | 2021-07-30 | 西南科技大学 | Microbial enrichment preparation method of hypha-based doped supercapacitor material |
| CN112209373A (en) * | 2020-08-31 | 2021-01-12 | 大连工业大学 | Method for preparing seaweed-based porous carbon material |
| CN113578314B (en) * | 2021-09-06 | 2023-07-25 | 葛浩然 | Method for preparing laccase-like catalyst |
| CN115015350A (en) * | 2022-05-25 | 2022-09-06 | 南通大学 | Pt-doped porous carbon modified glassy carbon electrode and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103332687A (en) * | 2013-07-11 | 2013-10-02 | 黑龙江大学 | Method for preparing boron and nitrogen codoped graphitized nano carbon by taking biomass as carbon source |
| WO2014025125A1 (en) * | 2012-08-10 | 2014-02-13 | 삼성정밀화학 주식회사 | Method for preparing lithium metal phosphor oxide |
| CN105293483A (en) * | 2015-12-08 | 2016-02-03 | 武汉理工大学 | In-situ preparation method of transition metal doped porous graphene |
| CN105314629A (en) * | 2015-11-27 | 2016-02-10 | 燕山大学 | Method for directly preparing co-doping three-dimensional graphene electrode material through biomass carbon sources |
| CN105480963A (en) * | 2016-02-25 | 2016-04-13 | 武汉工程大学 | Nitrogen-oxygen co-doped hierarchical porous carbon derived from polyaniline-sodium alga acid hydrogel and preparation method thereof |
-
2016
- 2016-04-26 CN CN201610265252.6A patent/CN105923629B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2014025125A1 (en) * | 2012-08-10 | 2014-02-13 | 삼성정밀화학 주식회사 | Method for preparing lithium metal phosphor oxide |
| CN103332687A (en) * | 2013-07-11 | 2013-10-02 | 黑龙江大学 | Method for preparing boron and nitrogen codoped graphitized nano carbon by taking biomass as carbon source |
| CN105314629A (en) * | 2015-11-27 | 2016-02-10 | 燕山大学 | Method for directly preparing co-doping three-dimensional graphene electrode material through biomass carbon sources |
| CN105293483A (en) * | 2015-12-08 | 2016-02-03 | 武汉理工大学 | In-situ preparation method of transition metal doped porous graphene |
| CN105480963A (en) * | 2016-02-25 | 2016-04-13 | 武汉工程大学 | Nitrogen-oxygen co-doped hierarchical porous carbon derived from polyaniline-sodium alga acid hydrogel and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105923629A (en) | 2016-09-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105923629B (en) | The method that dipping recrystallization carbonization biomass prepares the compound Heteroatom doping porous carbon materials of transition metal | |
| JP6550378B2 (en) | Method of manufacturing titanium oxide based supercapacitor electrode material | |
| CN106549163B (en) | A kind of preparation method and applications of cobalt, nitrogen co-doped ultrathin nanometer carbon plate | |
| NO20170575A1 (en) | Method for producing activated carbon | |
| CN106601490A (en) | Preparation method of biomass-based nitrogenous porous carbon, porous carbon prepared by method and use thereof | |
| CN112234206B (en) | Method for preparing thin-layer graphene/transition metal fluoride composite positive active material by using antibiotic fungi residues | |
| CN106299392A (en) | A kind of nanometer Mn with manganese defect3o4and preparation method thereof and application in electrocatalytic oxidation reduction reaction | |
| CN103632856A (en) | Production method and application of cobaltous oxide/carbon nanostructure array | |
| CN110565113B (en) | Preparation method of composite electrocatalytic material for alkaline electrocatalytic hydrogen evolution | |
| CN108455596A (en) | One step charring prepares the method and its application of high-specific surface area richness nitrogen multi-stage porous Carbon Materials | |
| Wang et al. | Vertically aligned ZnCo 2 O 4 nanoplates on Ti 3 C 2 for high-efficiency hybrid supercapacitors | |
| CN109243829B (en) | Dye-sensitized cell electrode, preparation method thereof and application of MIL-47 material | |
| CN109534412B (en) | Three-dimensional porous NiMn2O4Preparation method and application of the same in super capacitor anode material | |
| CN114538408B (en) | Method for preparing high-electrocatalytic active biochar by micro-oxygen pyrolysis | |
| Achour et al. | MnOx thin film based electrodes: Role of surface point defects and structure towards extreme enhancement in specific capacitance | |
| CN109920654B (en) | Preparation method of graphene/carbon nanosheet electrode | |
| CN111968863A (en) | Preparation method of rare earth composite biomass-based capacitance carbon material | |
| CN109449407B (en) | Preparation method of Fe7S8@ C nanorod material applicable to lithium ion battery | |
| CN106340625A (en) | Preparation method of titanous self-doped titanium dioxide/carbon composite cathode material | |
| CN104201009B (en) | A kind of preparation method of the polymer with nitrogen for electrode material for super capacitor | |
| CN110255561A (en) | A kind of N doping biomass porous carbon and preparation method thereof | |
| CN114291806B (en) | Multi-scale regulation and control method for graphitization degree of low-order coal-based porous carbon | |
| CN114394592B (en) | Method for modulating sludge-based hierarchical porous phosphorus-containing carbon by microwaves for super capacitor | |
| CN115547700A (en) | Derivative plant-based porous carbon and preparation method and application thereof | |
| CN114695861B (en) | Preparation method of sulfur and nitrogen co-doped porous carbon material, prepared carbon material and application thereof |
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 |