CN106517136A - Method for preparing iron/nitrogen-codoped ordered mesoporous carbon material - Google Patents
Method for preparing iron/nitrogen-codoped ordered mesoporous carbon material Download PDFInfo
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000000034 method Methods 0.000 title claims abstract description 15
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 28
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- 229920001568 phenolic resin Polymers 0.000 claims abstract description 21
- 239000005011 phenolic resin Substances 0.000 claims abstract description 21
- 239000000178 monomer Substances 0.000 claims abstract description 16
- 239000004202 carbamide Substances 0.000 claims abstract description 10
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 238000001338 self-assembly Methods 0.000 claims abstract description 7
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 238000005530 etching Methods 0.000 claims abstract description 6
- 238000003763 carbonization Methods 0.000 claims abstract description 4
- 239000000693 micelle Substances 0.000 claims abstract description 3
- 229920000428 triblock copolymer Polymers 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 32
- KAESVJOAVNADME-UHFFFAOYSA-N 1H-pyrrole Natural products C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 29
- 239000000243 solution Substances 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 17
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 15
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 12
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 11
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 235000013877 carbamide Nutrition 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 229960004756 ethanol Drugs 0.000 claims description 8
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical class CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- 238000006116 polymerization reaction Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 3
- 238000000935 solvent evaporation Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000009413 insulation Methods 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920003987 resole Polymers 0.000 claims description 2
- 238000005245 sintering Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 210000002700 urine Anatomy 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000005518 electrochemistry Effects 0.000 abstract description 3
- 230000002378 acidificating effect Effects 0.000 abstract 1
- 230000006698 induction Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 239000002131 composite material Substances 0.000 description 7
- 238000009826 distribution Methods 0.000 description 7
- 239000011148 porous material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000003990 capacitor Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- -1 polyoxyethylene Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 229910052605 nesosilicate Inorganic materials 0.000 description 2
- 150000004762 orthosilicates Chemical class 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 150000003233 pyrroles Chemical class 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005267 amalgamation Methods 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000002484 cyclic voltammetry Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000000802 evaporation-induced self-assembly Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 238000007634 remodeling Methods 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- 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
-
- 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
- C01P2006/12—Surface area
-
- 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
- C01P2006/14—Pore volume
-
- 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
Landscapes
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a method for preparing an iron/nitrogen-codoped ordered mesoporous carbon material. The method comprises the following steps: taking a triblock copolymer F127 as a template, under acidic condition, a silicon source-tetraethoxysilane, a carbon source-phenolic resin, a nitrogen source 1-urea, a nitrogen source 2-pyrroles monomer and an iron source-ferric trichloride are added, the micelle having a three-dimensional porous structure is synthesized with one step by a solvent volatilization induction self-assembly method, and the ordered mesoporous carbon material is obtained through high temperature carbonization and hydrofluoric acid etching. The method of the ordered mesoporous carbon material has the advantages of simple operation, low reaction temperature, and controllable condition, the prepared ordered mesoporous carbon material has the ordered three-dimensional tunnel structure, high specific surface area and excellent electrochemistry performance, and has good application prospect in the field of electrochemistry.
Description
Technical field
The invention belongs to meso-porous carbon material technical field, specifically, is related to a kind of ferrum/nitrogen co-doped order mesoporous carbon materials
The preparation method of material.
Background technology
Mesoporous carbon is a kind of new non-silicon-based mesoporous material, as there is larger surface area (may be up to 2500 for which
m2/ g), pore volume (2.25 cm3/ g) and good electric conductivity, have in fields such as catalyst carrier, hydrogen storage material, electrode materials
Good application prospect.Meso-porous carbon material can be used for the preparation of double layer capacitor, the electric charge of this double layer capacitor
Capacitance after the assembling of reserves, generally higher than metal oxide particle, also above the double electricity of metal-oxide common on market
Layer capacitance material.Higher specific surface area that simultaneously meso-porous carbon material has, specific aperture size, good electric conductivity and
High thermal stability so as to have huge application potential in terms of double layer capacitor development and application.
The modified purpose of ordered mesopore carbon be functional group required for introducing in order mesoporous carbon surface or skeleton with
Hetero atom, changes the surface nature of ordered mesopore carbon.It is ordered in order mesoporous carbon surface and skeleton introducing nitrogen heteroatom mesoporous
One of main method of modifying of carbon.Nitrogen-atoms are introduced in ordered mesopore carbon can be improved the wellability of material, bio-compatibility and lead
Electrically.N doping mesoporous carbon due to its excellent process based prediction model, in ultracapacitor, fuel cell, hydrogen storage, catalyst
The fields such as carrier have huge application prospect.Research impact and its mechanism of the N doping to mesoporous carbon form and chemical property
Great scientific value and and realistic meaning.
Amorphous carbon is mainly by ordered mesopore carbon prepared by carbon source of phenolic resin, electric conductivity is poor, and capacitance is low, and
There is good electric conductivity in the presence of being graphitized carbon when carbon in the form of graphite, so the graphitization of ordered mesopore carbon can be carried
High its electric conductivity, such that it is able to be used as electrode material.After research shows to load Fe on ordered mesoporous carbon material, can be relatively low
At a temperature of realize the graphitization of mesoporous carbon, so as to improve the electric conductivity of mesoporous carbon so that mesoporous carbon can preferably be applied to electricity
Chemical research.
However, the preparation method of existing meso-porous carbon material exist prepare template process complexity is tediously long, hard template removal
Process causes the amalgamation of cumbersome experimentation, presoma and template poor etc., thus needs a kind of easy to operate and condition badly
The preparation method of controllable meso-porous carbon material.
The content of the invention
It is an object of the present invention to provide a kind of preparation method of ferrum/nitrogen co-doped ordered mesoporous carbon material, the mesoporous carbon
Material has orderly three-dimensional open-framework and higher specific capacitance.
To solve above-mentioned technical problem, the present invention is employed the following technical solutions and is achieved：
A kind of preparation method of ferrum/nitrogen co-doped ordered mesoporous carbon material, its preparation process are as follows：With triblock copolymer F127
As template, silicon source-tetraethyl orthosilicate, carbon source-phenolic resin, nitrogen source 1- carbamide, nitrogen source 2- are added in acid condition
Pyrrole monomer and source of iron-ferric chloride, have three-dimensional porous structure using the method one-step synthesis of solvent evaporation induced self-assembly
Micelle, obtain ordered mesoporous carbon material Jing after high temperature cabonization, hf etching.
Alternatively, preparation process is specific as follows：
（1）The preparation of carbon source-phenolic resin：With formaldehyde, phenol is as Material synthesis resol, and is configured to phenolic resin
Ethanol solution；
（2）Ferrum/nitrogen co-doped：By 1.3 g-1.9 g template F127（Polyoxyethylene-poly-oxypropylene polyoxyethylene,
PEO106PPO70PEO106）It is dissolved in the dehydrated alcohol of 6 g-10 g, is slowly added dropwise appropriate hydrochloric acid solution, stirs, adds 0.1
G-0.3 g carbamide, 1 g-3 g tetraethyl orthosilicates（TEOS）, 3 g-7 g phenolic resin ethanol solution（15 wt%-
25 wt%）, after continuing stirring, by 0.5 ml-2 ml pyrrole monomers, 5 ml-15 ml liquor ferri trichloridis（0.289 M）Slowly
It is added drop-wise in mixed solution, after keeping temperature stirring a period of time, above-mentioned mixed solution is placed in surface plate, drying at room temperature；
（3）High temperature thermal polycondensation：Surface plate is placed in into baking oven high temperature hot polymerization；
（4）Carbonization etching：Sample is placed in tube furnace under nitrogen atmosphere after high-temperature calcination, after soaking in a solution of hydrofluoric acid, from
The heart is washed, and is dried, is obtained ordered mesoporous carbon material.
The step（1）In, phenolic resin used is in the case where reaction temperature is for 65-75 DEG C, by phenol with formaldehyde in alkali
Under the conditions of property obtained in polycondensation.
Wherein reaction temperature is preferably 70 DEG C, and the mass fraction of the ethanol solution of phenolic resin is 15 wt%-25
Wt%, preferably 20 wt%.
Step（2）In, whipping temp is 38-50 DEG C, preferably 40 DEG C.
Step（2）In, the quality of F127 is preferably 1.6 g, and anhydrous alcohol solution quality is preferably 8 g.
Step（2）In, carbamide as nitrogen source 1, its quality be preferably 0.2 g, tetraethyl orthosilicate as silicon source, its quality
Preferably 2.08 g.Pyrrole monomer is used as nitrogen source 2, FeCl3As source of iron, after addition mixing time be 1 h-3 h, preferably 2
h。
Step（2）Middle pyrrole monomer and FeCl3Mol ratio be 10:1-5, mol ratio are preferably 10:1、10:2、10:3.
Step（3）In, the temperature of high temperature thermal polycondensation is 90-110 DEG C, and preferably 100 DEG C, the hot polymerization time is 16-32h,
Preferably 24 h.
Step（4）In, sample is placed in tube furnace roasting under nitrogen atmosphere, and sintering temperature is 850 DEG C, and heating rate is
3 DEG C/min of room temperature rises to 450 DEG C, 90 min of roasting, then rises to 850 DEG C of 120 min of insulation with 2 DEG C/min speed,
Room temperature is cooled under nitrogen protection.
Step（4）In, the mass fraction of hydrofluoric acid solution is 5 %-20 %, preferably 10 %；Soak time is 10 h-20
H, preferably 12 h.
The preparation method of the ferrum/nitrogen co-doped ordered mesopore carbon of the present invention, using the method for solvent evaporation induced self-assembly,
By template F127, tetraethyl orthosilicate, carbon source phenolic resin, the collaboration self assembly effect between carbamide, polypyrrole, a step
Ordered mesoporous carbon material of the synthesis with three-dimensional open-framework.Prepared meso-porous carbon material pore-size distribution is orderly, pore size
It is homogeneous.
The present invention ferrum/nitrogen co-doped ordered mesopore carbon preparation method, F127 as block copolymer, in catalyst
（HCl, NaOH, H2SO4）In the presence of, the mesoscopic structure of high-sequential is obtained with carbon source etc. by organic-organic self assembly, can be obtained
The pore size for arriving is generally 2-15 nm.Compared with hard template, the ordered aggregation that F127 is formed, shape are typically all easy to
Construct, it is not necessary to complicated equipment, therefore the method experimental implementation is simple, experimental cost is cheap.Therefore, F127 is template and phenol
The self assemblies such as urea formaldehyde are very desirable selections.
The preparation method of the ferrum/nitrogen co-doped ordered mesopore carbon of the present invention, phenolic resin used are reaction temperatures 65
At DEG C -75 DEG C, by phenol with obtained in formaldehyde in the basic conditions polycondensation, obtained phenolic resin is first rank phenolic aldehyde tree
Fat.
The preparation method of the ferrum/nitrogen co-doped ordered mesopore carbon of the present invention, the homogeneous pore-size distribution of composite is logical
Cross the formation of evaporation induced self-assembly effect.
The preparation method of the ferrum/nitrogen co-doped ordered mesopore carbon of the present invention, FeCl3Both as required for pyrrole monomer polymerization
Oxidant, and introduce ferrum element as source of iron, the presence of ferrum element has beneficial to the graphitization journey for improving ordered mesoporous carbon material
Degree, so as to affect the pattern and chemical property of ordered mesoporous carbon material.
The preparation method of the ferrum/nitrogen co-doped ordered mesopore carbon of the present invention, pyrrole monomer, the mol ratio of ferric chloride are
10:1-5, the pore-size distribution of gained composite are preferable.
The preparation method of the ferrum/nitrogen co-doped ordered mesopore carbon of the present invention, introduces dinitrogen source.Nitrogen source wherein in carbamide
The wellability of ordered mesoporous carbon material can be improved, so as to improve chemical property；The introducing of the pyrroles's nitrogen in polypyrrole can be improved
The capacitance of ordered mesoporous carbon material.
Compared with prior art, advantages of the present invention and good effect are：
The method that the present invention is adopted, one-step synthesis ferrum/nitrogen co-doped ordered mesoporous carbon material, experimentation are easy, with low cost,
And yield is higher, products pure, prepared composite pore-size distribution is orderly, pore size is homogeneous.
The preparation method of the ferrum/nitrogen co-doped ordered mesoporous carbon material of the present invention, using F127 as template, positive silicic acid four
, used as silicon source, used as carbon source, used as nitrogen source 1, pyrroles is used as nitrogen source 2, FeCl for carbamide for carbon source phenolic resin for ethyl ester3As source of iron,
Hydrochloric acid solution provides acid condition, and one-step synthesis ordered mesoporous carbon material can be by adjusting F127 and carbon source, Bi Kayu
FeCl3Mol ratio the pore radiuses and distribution of composite is finely adjusted.Prepared composite pore-size distribution in order,
Pore size is homogeneous.
Dinitrogen source and the introducing of ferrum, effectively improve the chemical property of material, therefore the composite wood in electro-chemical test
With higher specific capacitance, Jing tests are that specific capacitance can reach 155.8 F/g under 0.1 A/g in electric current density to material.
The method of ferrum of the present invention/nitrogen co-doped ordered mesoporous carbon material, with easy to operate, reaction temperature is low, and condition can
The advantage of control, and prepared composite has orderly three-dimensional open-framework, higher specific surface area and excellent electrification
Performance is learned, has good application prospect in electrochemical field.
A series of concept of reduced forms is introduced in Summary, this will enter in specific embodiment part
One step is described in detail.The key that present invention part is not meant to attempt to limit technical scheme required for protection is special
Seek peace essential features, more do not mean that the protection domain for attempting to determine technical scheme required for protection.
Below in conjunction with accompanying drawing, advantages and features of the invention are described in detail.
Description of the drawings
Below in conjunction with drawings and Examples, the invention will be further described, in accompanying drawing：
Fig. 1 be pyrrole monomer, ferric chloride mol ratio be 10:The TEM photos of the material under the conditions of 3；
Fig. 2 be pyrrole monomer, ferric chloride mol ratio be 10:Under the conditions of 3, in KOH（2 M）In electrolyte solution, test
Cyclic voltammetric (CV) curve；
Fig. 3 be pyrrole monomer, ferric chloride mol ratio be 10:Under the conditions of 3, KOH（2 M）Make electrolyte solution, electric current density
For 0.1 A/g when, constant current charge-discharge (CP) curve of test.
It will be seen from figure 1 that the mol ratio in pyrrole monomer, ferric chloride is 10:Under the conditions of 3, resulting material tool
Orderly duct, and pore distribution is more uniform；As can be seen that resulting material has good electrochemistry from Fig. 2 and Fig. 3
Performance, shows as that cyclic voltammetry curve (CV) is approximate rectangular, constant current charge-discharge (CP) curve longer discharge time, with larger
Specific capacitance.
Specific embodiment
In order that the objects, technical solutions and advantages of the present invention become more apparent, below in conjunction with drawings and Examples pair
The present invention is described in further detail.It should be appreciated that embodiment described herein is only to explain the present invention, and without
It is of the invention in limiting.
In the following description, a large amount of concrete details are given to provide more thorough understanding of the invention.So
And, it will be apparent to one skilled in the art that the present invention can be able to without the need for one or more of these details
Implement.In other examples, in order to avoid obscuring with the present invention, for some technical characteristics well known in the art do not enter
Row description.
In order to thoroughly understand the present invention, detailed structure will be proposed in following description.Obviously, execution of the invention is simultaneously
It is not limited to the specific details is familiar with by those skilled in the art.Presently preferred embodiments of the present invention is described in detail as follows, but
In addition to these detailed descriptions, the present invention can also have other embodiment.
Embodiments of the invention are described in detail below in conjunction with accompanying drawing.
Embodiment 1
（1）The preparation of carbon source-phenolic resin：Weigh 8 g phenol and be placed in 41 DEG C of meltings in beaker, be added dropwise over the NaOH of 1.7 g
Aqueous solution（20 wt%）, 10 min are stirred, are added dropwise over, the formalin of 14.16 g（37%）, 70 DEG C of 1 h of reaction are warming up to,
The hydrochloric acid solution of 0.6 mol/L balances pH to neutrality, and 45 DEG C of 1 h of revolving obtain phenolic resin, are configured to the phenolic aldehyde tree of 20 wt%
The ethanol solution of fat；
（2）1.6 g surfactant F127 are dissolved in 8 g dehydrated alcohol, 1 g hydrochloric acid solutions are slowly added dropwise（0.2 M）, 40
DEG C stirring 1 h, add 0.2 g carbamide, 2.08 g tetraethyl orthosilicates（TEOS）, 5 g phenolic resin ethanol solution
（20 wt%）, continue 30 min of stirring, by 1 ml pyrrole monomers（Density 0.967g/ml）, 15 ml liquor ferri trichloridi（It is dense
Spend 0.289 M）It is slowly dropped in mixed solution, keeping temperature stirring 2h.Above-mentioned mixed solution is placed in surface plate, room temperature
It is dried；
（3）High temperature thermal polycondensation：Surface plate is placed in into 100 DEG C of 24 h of hot polymerization in baking oven；
（4）Carbonization etching：After sample is placed in tube furnace 850 DEG C of high-temperature calcinations in a nitrogen atmosphere, in the Fluohydric acid. of 10 wt%
12 h of middle immersion, centrifuge washing 5 times, 40 DEG C of dryings obtain ferrum/nitrogen co-doped ordered mesoporous carbon material.
The above, is only presently preferred embodiments of the present invention, is not the restriction for making other forms to the present invention, is appointed
What those skilled in the art possibly also with the disclosure above technology contents changed or be modified as equivalent variations etc.
Effect embodiment.But it is every without departing from technical solution of the present invention content, according to the technical spirit of the present invention to above example institute
Any simple modification, equivalent variations and the remodeling made, still falls within the protection domain of technical solution of the present invention.
Claims (10)
1. the preparation method of a kind of ferrum/nitrogen co-doped ordered mesoporous carbon material, it is characterised in that preparation process is as follows：With three block
Copolymer F127 adds silicon source-tetraethyl orthosilicate, carbon source-phenolic resin, nitrogen source 1- urine in acid condition as template
Element, nitrogen source 2- pyrrole monomer and source of iron-ferric chloride, have three-dimensional using the method one-step synthesis of solvent evaporation induced self-assembly
The micelle of loose structure, obtains ordered mesoporous carbon material Jing after high temperature cabonization, hf etching.
2. the preparation method of ordered mesoporous carbon material according to claim 1, it is characterised in that preparation process is specific as follows：
（1）The preparation of carbon source-phenolic resin：With formaldehyde, phenol is as Material synthesis resol, and is configured to phenolic resin
Ethanol solution；
（2）Ferrum/nitrogen co-doped：1.3 g-1.9 g template F127 are dissolved in the dehydrated alcohol of 6 g-10 g, are slowly added dropwise suitable
Amount hydrochloric acid solution, stirs, and adds 0.1 g-0.3 g carbamide, 1 g-3 g tetraethyl orthosilicates, 3 g-7 g steps（1）System
The ethanol solution of the phenolic resin for obtaining, after continuing stirring, by 0.5 ml-2 ml pyrrole monomers, 5 ml-15 ml tri-chlorinations
Ferrous solution is slowly dropped in mixed solution, after keeping temperature stirring a period of time, above-mentioned mixed solution is placed in surface plate,
Drying at room temperature；
（3）High temperature thermal polycondensation：Surface plate is placed in into baking oven high temperature hot polymerization；
（4）Carbonization etching：Sample is placed in tube furnace under nitrogen atmosphere after high-temperature calcination, after soaking in a solution of hydrofluoric acid, from
The heart is washed, and is dried, is obtained ordered mesoporous carbon material.
3. the preparation method of ordered mesoporous carbon material according to claim 2, it is characterised in that：The step（1）In, institute
It is that, at reaction temperature 65-75 DEG C, by phenol, polycondensation is obtained in the basic conditions with formaldehyde to state phenolic resin.
4. the preparation method of ordered mesoporous carbon material according to claim 2, it is characterised in that：The nothing of the phenolic resin
The mass percent of hydrous ethanol solution is 15 %-25 %.
5. the preparation method of ordered mesoporous carbon material according to claim 2, it is characterised in that：Step（2）In, stirring temperature
Spend for 38-50 DEG C.
6. the preparation method of ordered mesoporous carbon material according to claim 2, it is characterised in that：Step（2）In, carbamide is made
For nitrogen source 1, used as silicon source, pyrrole monomer is used as nitrogen source 2, FeCl for tetraethyl orthosilicate3Used as source of iron, after addition, mixing time is
1 h-3 h。
7. the preparation method of ordered mesoporous carbon material according to claim 2, it is characterised in that：Step（2）Middle pyrrole monomer
With FeCl3Mol ratio be 10:1-5.
8. the preparation method of ordered mesoporous carbon material according to claim 2, it is characterised in that：Step（3）In, high warm
The temperature of polycondensation is 90-110 DEG C, and the hot polymerization time is 16-32h.
9. the preparation method of ordered mesoporous carbon material according to claim 2, it is characterised in that：Step（4）In, sample is put
The roasting under nitrogen atmosphere in tube furnace, sintering temperature are 850 DEG C, and heating rate rises to 450 DEG C for 3 DEG C/min of room temperature, roasting
90 min are burnt, 850 DEG C of 120 min of insulation are risen to 2 DEG C/min speed then, room temperature is then cooled under nitrogen protection.
10. the preparation method of ordered mesoporous carbon material according to claim 2, it is characterised in that：Step（4）In, Fluohydric acid.
The mass fraction of solution is 5 wt%-20 wt%, and soak time is 10 h-20 h.
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