CN106744850B - The preparation of transition metal and nitrogen co-doped multistage pore canal three-dimensional grapheme - Google Patents
The preparation of transition metal and nitrogen co-doped multistage pore canal three-dimensional grapheme Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/18—Polybenzimidazoles
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2204/00—Structure or properties of graphene
- C01B2204/04—Specific amount of layers or specific thickness
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- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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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
A kind of preparation method for preparing transition metal and nitrogen co-doped multistage pore canal three-dimensional grapheme is invented.The polybenzimidazoles (PBI) of soluble full armaticity is carbon source and nitrogen source, transition metal salt and PBI solution reaction obtain the complex that PBI and transition metal ions are formed, nanometer calcium carbonate is added in mixed liquor and does template, it is uniformly mixed, is concentrated, making complex in template top finishing and regularly arranged, it is pyrolyzed, removes template agent removing, the three-dimensional grapheme of transition metal and nitrogen co-doped multi-stage artery structure is obtained, the duct of multistage perforation can strengthen mass transfer.PBI viscosity average molecular weigh is 2 ~ 40,000；The mass ratio of PBI and transition metal salt is 1:2 ~ 2:1；Template is calcium carbonate, 30 ~ 100 nm of partial size；PBI and template mass ratio are 2:1 ~ 1:4；Pyrolysis temperature is 800 DEG C ~ 1100 DEG C.Product can be used for redox reaction catalyst, fuel cell, metal-air battery oxygen reduction catalyst, electrolysis water oxygen and the fields such as catalyst, supercapacitor be precipitated.
Description
Technical field
Belong to field of nano material preparation, for the redox reaction catalyst in Chemical Manufacture, clean energy resource field
Fuel cell, metal-air battery cathod catalyst, electrolysis water catalyst, lithium ion battery material, super capacitor electrode
The fields such as pole material and electrochemical sensor.
Background technique
Although two-dimensional graphene has excellent performance and a variety of potential applications, however, pole again between two-dimensional graphene
Easy layer-layer is overlapped mutually to form graphite-structure, so that the performance for keeping its excellent is lost.Therefore, the preparation and property of three-dimensional grapheme
It can research hotspot of the research as current field of nanometer material technology.The study found that the graphene of N doping is due in graphene molecules
Polarity between C-N key makes the cloud density in graphene molecules change, therefore nitrogen-doped graphene catalytic oxidation-reduction etc.
Performance is better than graphene.
Facilitate the increase of active sites by doping metals, the synergistic effect of metal and nitrogen further improves its catalytic
Energy, enhancing catalytic activity and raising stability (Zhao Y, et al. J Am Chem Soc (American Chemical Society), 2012,
134:19528).Therefore metal-nitrogen-Spectra of Carbon Clusters (M-N-C) research is taken seriously, studies have shown that adulterated in graphene nitrogen and
After transition metal (such as iron, cobalt etc.), it will form more active sites, so that the catalysis of product catalytic oxidation-reduction can be further increased
Activity.The transition metal and nitrogen co-doped catalyst for especially forming three-dimensional structure, can preferably keep its two-dimensional slice knot
For structure without being superimposed and assembling, catalytic active site is more, and porous structure is conducive to the transmitting of fortification substance.Due to it
Unique advantage, such material are considered as most one of development potentiality oxygen reduction catalyst, are attracted widespread attention
(Jaouen F, et al. Energy Environ Sci (energy environment science), 2011,4,114 130).In M-N-C
In catalyst, metal-doped nitrogen can be Fe2O3 doping, and ((American Chemical Society-urges Lin L, et al. ACS Catal
Change), 2016,6:4449), cobalt doped ((grind Gao J, et al. Ind. Eng. Chem. Res by chemical industry and engineering
Study carefully), 2015,54:7984) and iron cobalt codope (Li S, et al. Electrochim. Acta (electrochemistry journal),
2010,55:7346) transition metal and nitrogen co-doped graphene have extensive use, can be used as oxygen reduction catalyst (Jiang
H L, et al. ACS Appl. Mater. Interfaces(American Chemical Society-application material and interface), 2015,7
(38): 21511).In the fields such as sensor, supercapacitor and lithium ion battery (Salavagione H J, et al. J.
Mater. Chem. A (materials chemistry magazine A), 2014,2:14289) application have document report.Metal, N doping
Graphene preparation method have very much: such as, high temperature pyrolysis transition macrocyclic complex (Osmieri L, et al. Int J
Hydrogen Energ (international Hydrogen Energy magazine), 2016,41:22570)；Heat treatment organic compounds containing nitrogen (such as ethylenediamine,
Pyridine etc.) with transition metal salt obtain M-N-C cluster (Lefe vre M, et al. Science (science) 2009,324:
71)；Fe-N-C cluster catalyst (Lai Q X, et al. is prepared by high temperature pyrolysis with melamine and etal molysite
ACS Appl. Mater. Interfaces (American Chemical Society-application material interface), 2015,7:18170), also useful
Polypyrrole and etal molysite pass through high temperature pyrolysis preparation Fe-N-C cluster catalyst (Zheng Y P, et al. Nano
Energy (the nanometer energy), 2016,30:433)；With heat treatment preparation one kind M/N/C catalysis of polyaniline combination iron and cobalt
Agent (Wu G, et al. Science (science), 2011,332:443) etc..
The present invention is a kind of prepares with the transition metal and nitrogen co-doped multistage pore canal three-dimensional graphite for strengthening mass transfer effect
The method of alkene.It is reacted with the polybenzimidazoles (PBI) of soluble full armaticity with molysite or cobalt salt solution, the cooperation of generation
Object, nanometer calcium carbonate template, reaction mixture are uniformly mixed with calcium carbonate template, are evaporated, and complex is on template surface
Regularly arranged, under inert gas shielding, pyrolysis, complex forms transition metal and nitrogen co-doped by dehydrogenation-cyclisation-carbonization
Three-dimensional grapheme, the carbon dioxide that Decomposition of Calcium Carbonate generates, which is discharged, to be formed aperture and mutually passes through with the macropore generated after removing template is removed
Logical, the product of preparation is the three-dimensional grapheme of transition metal and nitrogen co-doped multistage pore canal perforation；Product is used for redox
Catalyst, supercapacitor etc. is precipitated in catalysts, fuel cell, metal-air battery oxygen reduction catalyst, electrolysis water oxygen
Field.
Obtained transition metal and nitrogen co-doped multistage pore canal three-dimensional grapheme, due to transition metal and nitrogen co-doped and three
Porous structure is tieed up, so that its specific surface area increases, catalytic active site increases.Due to the big pi bond structure of graphene itself, iron or cobalt
For the polar bond formed with nitrogen inside graphene molecules, entire molecule forms big pi bond structure, and the delocalization energy of molecular orbit increases
Greatly, the energy level between HUMO track and LOMO track becomes smaller, so that the environment of its catalytic active center is especially as porphyrin, phthalocyanine are matched
The environment for closing object, can substantially reduce the overpotential of catalytic oxidation-reduction, the catalysis thermodynamic property of catalyst gets a promotion in this way；
Furthermore the three-dimensional porous structure of multistage pore canal perforation is conducive to strengthen mass transfer, so that electrode reaction dynamic performance is improved.
The present invention and simple itrogenous organic substance and transient metal complex or nitrogen containing polymer, such as pollopas, melamine
Polyimide resin etc. and metal-nitrogen-Spectra of Carbon Clusters difference of transition metal mixture pyrolysis preparation are that metal-nitrogen-Spectra of Carbon Clusters is not
It is graphene-structured, is not the codope of transition metal ions and nitrogen, the effect without big π, so catalytic performance is not high, metal
It is easy to be removed by acid, so durability is not good enough, especially because metal-nitrogen-Spectra of Carbon Clusters is not its mass transfer of porous structure effect
Fruit is bad, so, catalytic activity and durability are not good enough.Formation is pyrolyzed together with transition metal with polyaniline, polypyrrole
The difference of catalyst is, polyaniline and polypyrrole since it cannot be dissolved, so, can not cover with paint, lacquer, colour wash, etc. on template surface,
So its operating characteristics be deteriorated, and PBI be it is soluble, be very easy to cover with paint, lacquer, colour wash, etc. on template surface, operating performance is good.
Summary of the invention
The present invention is a kind of prepares with the transition metal and nitrogen co-doped multistage pore canal three-dimensional graphite for strengthening mass transfer effect
The method of alkene.It is reacted, is generated with transition metal salt solution with polybenzimidazoles (PBI) macromolecule of soluble full armaticity
PBI and transition metal ions complex, complex reaction mixture are uniformly mixed in nanometer calcium carbonate template, and complex is in mould
The arrangement of plate agent rule of surface, under inert gas shielding, pyrolysis, complex forms transition metal and nitrogen by dehydrogenation-cyclisation-carbonization
The graphene of codope, the carbon dioxide that Decomposition of Calcium Carbonate generates are discharged to form aperture and go the macropore generated after removing template mutual
Perforation prepares the three-dimensional grapheme of transition metal and nitrogen co-doped multistage pore canal perforation；The product is used for redox reaction
The fields such as catalyst, supercapacitor are precipitated in catalyst, fuel cell, metal-air battery oxygen reduction catalyst, electrolysis water oxygen.
Obtained transition metal and nitrogen co-doped multistage pore canal three-dimensional grapheme, due to the co-doped of transition metal and nitrogen
And three-dimensional porous structure, so that its specific surface area increases, catalytic active site increases.Due to the big pi bond structure of graphene itself, mistake
Metal is crossed with the polar bond of nitrogen formation inside graphene molecules, entire molecule forms big pi bond structure, the delocalization of molecular orbit
It can increase, the energy level between HUMO track and LOMO track becomes smaller, so that the environment of its catalytic active center is especially as porphyrin, phthalein
The environment of cyanines complex, can substantially reduce the overpotential of catalytic oxidation-reduction in this way, and the catalysis thermodynamic property of catalyst obtains
It is promoted；Furthermore the three-dimensional porous structure of multistage pore canal perforation is conducive to strengthen mass transfer, so that electrode reaction dynamic performance obtains
Improve.
The present invention and simple itrogenous organic substance and transient metal complex or nitrogen containing polymer, such as pollopas, melamine
Polyimide resin etc. and metal-nitrogen-Spectra of Carbon Clusters difference of transition metal mixture pyrolysis preparation are that metal-nitrogen-Spectra of Carbon Clusters is not
It is graphene-structured, rather than the codope of transition metal ions and nitrogen, the effect without big π, so catalytic performance is not high, gold
Belong to and be easy to be removed by acid, so durability is not good enough；Especially because metal-nitrogen-Spectra of Carbon Clusters is not its mass transfer of porous structure
Effect is bad, so, catalytic activity and durability are not good enough.It is pyrolyzed and to be formed together with transition metal with polyaniline, polypyrrole
The difference of catalyst be, polyaniline and polypyrrole since it cannot be dissolved, so, can not cover with paint, lacquer, colour wash, etc. in template table
Face, thus its operating characteristics be deteriorated, and PBI be it is soluble, be very easy to cover with paint, lacquer, colour wash, etc. on template surface, complex can advise
It then is arranged in template surface, only in this way, a series of heat chemistrys such as dehydrogenation-cyclisation-carbonization occur in pyrolytic process
Available nitrogen-doped graphene structure after variation.
Viscosity average molecular weigh being soluble between 20,000~40,000 of full armaticity PBI solid phase method or liquid phase method preparation
DMAc, DMF, DMSO, in N-Methyl pyrrolidone equal solvent.Molecular weight is too big, and the solubility property of PBI is deteriorated；Molecular weight is too small
Its viscosity is too small, cannot coated die plate agent well.
The method of the preparation of transition metal and nitrogen co-doped multistage pore canal three-dimensional grapheme are as follows: it is appropriate to prepare the degree of polymerization first
Full armaticity PBI, PBI dissolution form solution in a solvent, a certain amount of transition metal salt solution is added into solution,
It heats, be stirred to react 5 ~ 8 hours, obtain the complex reaction solution that PBI and transition metal ions are formed, be added into the reaction solution
Suitable partial size is the template calcium carbonate of 30 ~ 100 nm, and stirring mixes them thoroughly uniformly.Under stiring, it heats, at leisure
It steams solvent to do to close, is transferred in vacuum oven and is dried at 60 ~ 120 DEG C.It is finely ground in mortar, it is laid in porcelain boat bottom, is put
Enter in electric tube furnace, under protection of argon gas, at 800~1100 DEG C, is pyrolyzed 2 ~ 3h.It is cooled to room temperature, takes out to furnace temperature, use is dilute
Sour repeatedly washing filters to remove template agent removing, is washed with deionized water, dries to obtain product.
The present invention is in the reacting of PBI and transition metal salt, and the additional amount of transition metal salt is critically important, it determines preparation
Product in transition metal doping, also determine product as catalyst catalytic active site how much.Due to transition metal
Ion is coordinated with the imidazoles nitrogen in PBI macromolecule, guarantees that the corresponding transition metal ions of four imidazole rings is advisable, experiment hair
The mass ratio of existing PBI and transition metal salt between 1:2 ~ 2:1, determined by different types of transition metal salt by the variation of proportion
It is fixed.
In the present invention, template is nano-calcium carbonate particles.The nitrogen co-doped multistage pore canal of transition metal-can be prepared
Three-dimensional grapheme, the partial size and additional amount of template are crucial: the partial size of template determines the aperture of the material of preparation；Mould
The additional amount of plate agent determines the formation and performance of the number of plies of the graphene of preparation, aperture.Template additional amount is very little, can only obtain
To transition metal and nitrogen co-doped porous carbon materials, the material of multi-layer graphene structure cannot be obtained；It is added excessively, obtains
Transition metal and the nitrogen co-doped three-dimensional grapheme number of plies are very little, after removing template agent removing, are easy to collapse, and can only obtain broken broken
Piece.The granularity of template has a certain impact to the amount that template is added, and granularity is small, large specific surface area, the mould needed
The amount of plate agent is just few；, whereas if granularity is big, the amount of the template needed is just more；Consider that Decomposition of Calcium Carbonate can generate aperture,
The aperture of aperture in 2 ~ 5 nm, so, the partial size of calcium carbonate selects 30 ~ 100 nm；The dosage of template are as follows: PBI and template
Mass ratio be 2:1~1:4；Ratio variation is related with the granularity of template.Be pyrolyzed under inert gas protection, it is regularly arranged
The a series of thermal chemical reactions such as dehydrogenation-cyclisation-carbonization can occur for the complex on template surface, finally obtain product.Perforation
The formation of pore channels it is related with the decomposition when amount of nanometer calcium carbonate and pyrolysis, pyrolysis temperature is at 800 DEG C hereinafter, calcium carbonate
It does not decompose, the channel of aperture perforation cannot be formed.The aperture of aperture and the amount of calcium carbonate are related, the carbon dioxide that calcium carbonate generates
Amount it is big, then the aperture of the aperture that can be formed is just big, if the amount of the carbon dioxide of generation is small, the aperture formed is just
It is small.It is pyrolyzed under inert gas protection, pyrolysis temperature are as follows: 800~1100 DEG C；The formation of aperture and pore size are calcium carbonate point
What the carbon dioxide that solution generates generated, the factors such as amount and pyrolysis temperature of calcium carbonate determine aperture and the perforation performance of aperture.It should
The porous material of class multistage perforation has mass transfer to have invigoration effect electrode reaction.
Washing diluted acid after repeatedly template agent removing is removed in washing, is washed with deionized to neutrality and dries.
Pyrolysis temperature is critically important, and pyrolysis temperature range is 800~1100 DEG C.The too low PBI pyrolysis of temperature not exclusively, is produced
The electric conductivity of product is poor；At 800 DEG C hereinafter, calcium carbonate does not decompose, the channel of aperture perforation cannot be formed.Pyrolysis temperature reaches most
After good temperature, then to increase pyrolysis temperature its performance constant, still, oxidation reaction, institute can occur when inert gas shielding is insufficient
It is unsuitable excessively high with pyrolysis temperature.
The graphene characterizing method of the nitrogen co-doped multistage pore canal of 3-D transition metal are as follows: aperture, porosity, Kong Rong and ratio
For surface area with nitrogen adsorption instrument (BET), the Morphology analysis of product is micro- with scanning electron microscope (SEM) and projection electron
Mirror (TEM), graphene number of plies can be characterized by high power transmission electron microscope (HRTEM) and Raman spectrum.The stone of product
Blackization degree, graphene-structured and the number of plies can be characterized with X-ray powder diffraction (XRD), Raman spectrum.The element of product
Composition, valence state can be characterized with x-ray photoelectron spectroscopy (XPS), with rotating disk electrode (r.d.e) (RDE) come test product
Catalytic oxidation-reduction react (ORR) performance, water electrolysis oxygen evolution reaction (EOR), the capacitive property of evolving hydrogen reaction (EHR) and product
Test can be tested with cyclic voltammetric (CV), linear volt-ampere (LSV), Tafel curve and charge-discharge performance.Product is used as and urges
CV, LSV and chronoa mperometric plot (i-t) can be used in the durability test of agent.The catalytic performance of product finally needs to assemble
Metal-air battery, hydrogen-oxygen fuel cell, the electrolytic cell of electrolysis water, supercapacitor and sensor test its performance.
Specific embodiment
The preparation of [embodiment 1] mPBI: polyphosphoric acids is added in the three-necked flask equipped with electric stirring and nitrogen protection
(PPA) (100 g), the lower 160 DEG C of stirrings 1h of nitrogen protection is to remove extra moisture and air.By DABz (4 g, 18.7
Mmol) and M-phthalic acid (3.1 g, 18.7 mmol) is uniformly mixed, and is slowly added in three-necked flask.Control nitrogen
Gas velocity prevents DABz to be oxidized, while reaction temperature being promoted to 200 DEG C and continues to keep the temperature, is stirred to react 5-8 h.With
The increase in reaction time, polymerization system gradually become sticky.Stop reaction when viscosity is suitable, reaction mixture is slowly transferred to
It reels off raw silk from cocoons in a large amount of deionized waters, cleans, drying, crush, deionized water is repeatedly washed to remove polyphosphoric acids and unreacted reaction
Object is to get mPBI is arrived, with the molecular weight of determination of ubbelohde viscometer mPBI.
[embodiment 2] Solid phase synthesis mPBI: by DABz (4 g, 18.7 mmol) and M-phthalic acid (3.1
G, 18.7 mmol) it is uniformly mixed in being fully ground in mortar, be transferred to nitrogen protection, blender three-necked flask in.
Lead to 15 min of nitrogen to drain the air in flask.N2Protection, under stirring, 225 DEG C of oil bath heating keep 3h.It is taken out after cooling,
It is finely ground, N2Under protection, heating in electric furnace is warming up to 270-275 DEG C, keeps 3h.It is cooled to room temperature, product is taken out, is finely ground, i.e.,
MPBI is obtained, with the molecular weight of determination of ubbelohde viscometer mPBI.
The preparation method of [embodiment 3] ABPBI is similar with mPBI's, is only substituted with 3,4- diaminobenzoic acid (DABA)
DABz and M-phthalic acid.ABPBI only can be obtained with a kind of raw material.Other reaction conditions and the same embodiment of operating procedure
1 and embodiment 2.
[embodiment 4] is template with the calcium carbonate of partial size 30nm, uses ferric acetate；The mass ratio of ferric acetate and mPBI are 1:
2, by taking mPBI and calcium carbonate template mass ratio are 1:1 as an example: in the beaker of 250mL, the mPBI(viscosity average molecular weigh of 1g is added
2 ~ 3, ten thousand) with 20 mL DMAc, heat, stir to dissolve, the 20mL DMAc solution of 0.5 g ferric acetate is added under stiring,
It at 80 DEG C ~ 100 DEG C of heat preservation, is stirred to react 5 ~ 8 hours, is slowly added into the calcium carbonate granule for the nanometer that 1 g partial size is 30 nm, stirs
It mixes 4 ~ 6 hours, it is made to be uniformly dispersed.Obtained viscous liquid is heated to be concentrated under stiring and closely be done, in vacuum oven
Dry at 60 ~ 120 DEG C, solid is finely ground in mortar, is transferred in porcelain boat, under protection of argon gas, is pyrolyzed at 900 DEG C in electric furnace
2-3h is down to room temperature to furnace temperature, takes out, finely ground, obtains black powder solid, is transferred in 250 mL conical flasks, is added 70
The dilute hydrochloric acid of mL, heating, stirring for 24 hours, filter, in this way with dilute hydrochloric acid wash three times, be washed to neutrality, be dried to obtain black powder
0.72 g of shape solid product.BET test shows that its pore-size distribution is 30 nm, and 2 ~ 4 nm specific surface area of aperture is 1131 m2 g-1, the product that shows of SEM test be porous foam shape carbon material, TEM and HRTEM analysis shows, product is three-dimensional graphite
Alkene structure carbon material, aperture are 30 nm, and 2 ~ 4 nm graphene of aperture, which is drawn a bow to the full back, is shown to be 2 ~ 4 layers of graphene.XRD and Raman spectrum
Test shows that product is 2 ~ 4 layers of graphene-structured；XPS analysis shows product iron content 1.7%, nitrogen content 6.3%, and nitrogen
For pyridine type nitrogen and pyrroles's type nitrogen.Illustrate, product is the material of the nitrogen co-doped multistage pore canal three-dimensional grapheme structure of iron-.Its
Catalytic oxidation-reduction performance under 0.1 mol/L KOH, oxygen initial reduction current potential are 0.99 V vs RHE, and electron transfer number is
3.98, durability is good；Magnesium air battery performance is up to 103 mW/cm2.It is 584 mW/ for its peak power of hydrogen-oxygen fuel cell
cm2, it is 1.56 V vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L, and limiting current density reaches 100
mA/cm2.Supercapacitor specific capacitance is 348 F g-1, be recycled 10000 times still holding capacitor value 98%.
[embodiment 5] as described in Example 4, other conditions are identical, and only the quality of mPBI and calcium carbonate becomes 2:1,
It is similarly obtained the solid powder of black.BET test shows that its pore-size distribution is still 30nm, 2 ~ 4 nm of aperture, but its specific surface
It is long-pending then be reduced to 732 m2 g-1, SEM and TEM test show its it is internal be porous structure carbon material, surface is Multi-layer graphite
Alkene structure, XRD and Raman data show 7 ~ 8 layers of the number of plies of its graphene.XPS data are similar with the product of embodiment 4.It 0.1
Catalytic oxidation-reduction performance under mol/L KOH, oxygen initial reduction current potential are 0.83 V vs RHE, and electron transfer number 3.59 is resistance to
Long property is good；Magnesium air battery performance is up to 65 mW/cm2.It is 231 mW/cm for its peak power of hydrogen-oxygen fuel cell2, 0.5
It is 1.67 V vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of mol/L, and limiting current density reaches 40 mA/cm2.It is super
Grade capacitor specific capacitance is 192 F g-1, be recycled 10000 times still holding capacitor value 95%.
[embodiment 6] as described in Example 4, other conditions are identical, and only the quality of mPBI and calcium carbonate becomes 1:2,
It is similarly obtained the solid powder of black.BET test shows 10 ~ 30 nm of its pore size distribution range, 3 ~ 5 nm of aperture, but it compares
Surface area is then reduced to 812 m2 g-1, SEM and TEM test show its it is internal be porous structure carbon material, surface is multilayer
Graphene-structured, XRD and Raman data show 7 ~ 8 layers of the number of plies of its graphene.XPS data are similar with the product of embodiment 4.
Catalytic oxidation-reduction performance under its 0.1 mol/L KOH, oxygen initial reduction current potential are 0.84 V vs RHE, and electron transfer number is
3.65, durability is good；Magnesium air battery performance is up to 76 mW/cm2.It is 238 mW/ for its peak power of hydrogen-oxygen fuel cell
cm2, it is 1.65 V vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L, and limiting current density reaches 50
mA/cm2.Supercapacitor specific capacitance is 258 F g-1, be recycled 10000 times still holding capacitor value 95%.
[embodiment 7] as described in Example 4, other conditions are identical, and only pyrolysis temperature is respectively 700 DEG C.It obtains black
Powdered 0.72 g of solid product of color.BET test shows that its pore-size distribution is 30 nm, 2 ~ 4 nm of aperture, specific surface area 958
m2 g-1, the product that shows of SEM test be porous foam shape carbon material, TEM and HRTEM analysis shows, product is three-dimensional
Graphene structural carbon material, aperture are 30 nm, 2 ~ 4 nm of aperture, and graphene, which is drawn a bow to the full back, is shown to be 2 ~ 4 layers of graphene.XRD and Raman
Spectrum test shows that product is 2 ~ 4 layers of graphene-structured；XPS analysis shows product iron content 1.6%, nitrogen content 6.6%,
And nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Illustrate, product is the material of the three-dimensional grapheme structure of N doping.Its 0.1 mol/L
Catalytic oxidation-reduction performance under KOH, oxygen initial reduction current potential are 0.83 V vs RHE, and electron transfer number 3.54, durability is slightly
Difference is good；Magnesium air battery performance is up to 56 mW/cm2.It is 146 mW/cm for its peak power of hydrogen-oxygen fuel cell2, 0.5 mol/L
Sulfuric acid solution in oxygen take-off potential is precipitated is 1.69 V vs RHE, limiting current density reaches 30 mA/cm2.Super capacitor
Device specific capacitance is 236 F g-1, be recycled 10000 times still holding capacitor value 94%.
[embodiment 8] the other the same as in Example 4, only pyrolysis temperature is 1100 DEG C.Obtain black powder solid product
0.58 g.BET test shows that its pore-size distribution is 30 nm, and 2 ~ 4 nm of aperture, specific surface area is 786 m2 g-1, SEM test table
It is bright, obtained product be porous foam shape carbon material, TEM and HRTEM analysis shows, product be three-dimensional grapheme structure carbon materials
Material, aperture are 30 nm, 2 ~ 4 nm of aperture, and graphene, which is drawn a bow to the full back, is shown to be 2 ~ 4 layers of graphene.XRD and Raman spectrum test show
The graphene-structured that product is 2 ~ 4 layers；XPS analysis shows that product iron content 1.5%, nitrogen content 5.2%, and nitrogen are pyridine type
Nitrogen and pyrroles's type nitrogen.Illustrate, product is the material of the three-dimensional grapheme structure of N doping.Oxygen is catalyzed under its 0.1 mol/L KOH
Reducing property, oxygen initial reduction current potential are 0.95 V vs RHE, and electron transfer number 3.94, durability is good；Magnesium air electricity
Pond performance is up to 92 mW/cm2.It is 312 mW/cm for its peak power of hydrogen-oxygen fuel cell2, oxygen in the sulfuric acid solution of 0.5 mol/L
Precipitation take-off potential is 1.68 V vs RHE, and limiting current density reaches 70 mA/cm2.Supercapacitor specific capacitance is 247
F g-1, be recycled 10000 times still holding capacitor value 96%.
[embodiment 9] as described in Example 3, other conditions are identical, are only that 50 nm calcium carbonate granules are done with partial size
Template, at this moment, since the partial size of template becomes larger, surface area increases small, and the dosage of mPBI reduces, then mPBI and template
Mass ratio is changed to as 1:2, and obtained product is similar to Example 4, and only its pore-size distribution compares table in 50 nm, 4 ~ 5 nm of aperture
Area is 921 m2 g-1, it is 3 ~ 5 layers of three-dimensional nitrogen-doped graphene material, catalytic oxidation-reduction starting electricity under 0.1 mol/L KOH
Position is 0.93 V vs RHE, and electron transfer number 3.92, durability is good；Magnesium air battery performance is up to 86 mW/cm2.For
Its peak power of hydrogen-oxygen fuel cell is 279 mW/cm2, it is 1.64 V that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L
Vs RHE, limiting current density reach 70 mA/cm2.Supercapacitor specific capacitance is 298 F g-1, it is recycled 10000 times
Still the 97% of holding capacitor value.
[embodiment 10] as described in Example 4, other conditions are identical, are only 100 nm calcium carbonate granules with partial size
Template is done, at this moment since the partial size of template increases, surface area reduces, and the dosage of mPBI is reduced, then mPBI and template
Mass ratio be changed to as 1:4, obtained product is similar to Example 4, and only its pore-size distribution compares table in 100nm, 5 nm of aperture
Area is 784 m2 g-1, it is 3 ~ 5 layers of three-dimensional nitrogen-doped graphene material, catalytic oxidation-reduction take-off potential is 0.90 V vs
RHE, electron transfer number 3.91, durability is good；Magnesium air battery performance is up to 77 mW/cm2.For hydrogen-oxygen fuel cell its
Peak power is 266 mW/cm2, it is 1.65 V vs RHE, limit electricity that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L
Current density reaches 70 mA/cm2.Supercapacitor specific capacitance is 265 F g-1, it is recycled 10000 still holding capacitor values
95%。
[embodiment 11] uses calcium carbonate template, and partial size is 30 nanometers, and with citric acid cobalt, the mass ratio with ABPBI is
1:1.Other experiment conditions are the same as embodiment 4.The mass ratio of ABPBI and template is 1:1.Its result is similar to Example 4.Aperture
For 30 nm, aperture 2 ~ 4 nm, 1264 m2 g-1, it is 2 ~ 4 layers of graphene.Cobalt content 1.6%, nitrogen content 6.8%, and nitrogen are pyrrole
Pyridine type nitrogen and pyrroles's type nitrogen.Catalytic oxidation-reduction performance under its 0.1 mol/LKOH, oxygen initial reduction current potential are 0.99 V vs
RHE, electron transfer number 3.97, durability is good；Magnesium air battery performance is up to 93 mW/cm2.For hydrogen-oxygen fuel cell its
Peak power is 437 mW/cm2, it is 1.58 V vs RHE, limit electricity that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L
Current density reaches 80 mA/cm2.Supercapacitor specific capacitance is 389 F g-1, it is recycled 10000 still holding capacitor values
97%。
Other cobalt salts with the situation under the other mass ratioes of mPBI, operating procedure with embodiment 4, urge by obtained product
It is similar to change performance.
Other molysite, cobalt salt situation are similar to the above embodiments, only change the ratio of PBI and molysite or cobalt salt.
The case where product that the calcium carbonate of ABPBI and other partial sizes is mixed with, same to above-described embodiment, performance is slightly better than
The product of mPBI is used under similarity condition.
Claims (5)
1. a kind of complex formed with polybenzimidazoles (PBI) macromolecule and transition metal ions of soluble full armaticity
It covers with paint, lacquer, colour wash, etc. in nano template calcium carbonate surface, is pyrolyzed, removes removing template, prepare transition metal and nitrogen co-doped multistage pore canal perforation
Three-dimensional grapheme preparation method, it is characterised in that: PBI is the soluble of full armaticity, by PBI and transition metal salt
Mass ratio is that 2:1~1:2 hybrid reaction obtains complex, and it is the nanometer calcium carbonate of 30~100 nm as template that partial size, which is added,
Agent is 2:1~1:4 by the mass ratio of PBI and nano template calcium carbonate, is uniformly mixed, makes PBI and transition metal ions
The complex of formation is in template top finishing and regularly arranged, under inert gas argon gas or high pure nitrogen protection, 800~
It at 1100 DEG C, is pyrolyzed 2~3 hours, removes template agent removing, obtain the three-dimensional graphite of transition metal and the perforation of nitrogen co-doped multistage pore canal
Alkene；The transition metal and the three-dimensional grapheme of nitrogen co-doped multistage pore canal perforation are used for redox reaction catalyst, combustion
Catalyst, electrode material for super capacitor is precipitated in oxygen reduction catalyst in material battery, metal-air battery, electrolysis water oxygen.
2. a kind of polybenzimidazoles (PBI) macromolecule and transition with soluble full armaticity according to claim 1
The complex that metal ion is formed is covered with paint, lacquer, colour wash, etc. in nano template calcium carbonate surface, is pyrolyzed, is removed removing template, prepares transition metal and nitrogen
The preparation method of the three-dimensional grapheme of the multistage pore canal perforation of codope, it is characterised in that: the entire polymer of PBI of full armaticity
Molecule forms a big pi bond, and molecule belongs to rigidity, aroma type compound, for poly- (2,5- benzimidazole) (ABPBI) or poly- [2,
One of 2 '-(phenyl) -5,5 '-bibenzimidaz sigmales] (mPBI)；Polymer viscosity average molecular weigh is between 2~40,000；It can be molten
Solution is in dimethyl acetamide (DMAc), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), N-Methyl pyrrolidone or two
In any one solvent in toluene.
3. a kind of polybenzimidazoles (PBI) macromolecule and transition with soluble full armaticity according to claim 1
The complex that metal ion is formed is covered with paint, lacquer, colour wash, etc. in nano template calcium carbonate surface, is pyrolyzed, is removed removing template, prepares transition metal and nitrogen
The preparation method of the three-dimensional grapheme of the multistage pore canal perforation of codope, transition metal salt are as follows: acetate, the nitre of transition metal
One of hydrochlorate, hydrochloride, citrate, perchlorate or gluconate, it is characterised in that: divide in intensive polar solvent
The salt for dissipating or dissolving.
4. a kind of polybenzimidazoles (PBI) macromolecule and transition with soluble full armaticity according to claim 1
The complex that metal ion is formed is covered with paint, lacquer, colour wash, etc. in nano template calcium carbonate surface, is pyrolyzed, is removed removing template, prepares transition metal and nitrogen
The preparation method of the three-dimensional grapheme of the multistage pore canal perforation of codope, nano template are calcium carbonate, it is characterised in that: grain
Diameter is in 30~100 nm, for any one nano particle in spherical, cylindrical, cube or polygon prism.
5. a kind of polybenzimidazoles (PBI) macromolecule and transition with soluble full armaticity according to claim 1
The complex that metal ion is formed is covered with paint, lacquer, colour wash, etc. in nano template calcium carbonate surface, is pyrolyzed, removing template is gone to prepare transition metal and nitrogen
The preparation method of the three-dimensional grapheme of the multistage pore canal perforation of codope, the mass ratio of PBI and transition metal salt be 2:1~
1:2；It is 2:1~1:4 by the mass ratio of PBI and nano template calcium carbonate；Hybrid mode are as follows: PBI solution and transition metal salt
Solution mixing, heats, is stirred to react 5~8 hours, and PBI and transition metal ions form complex solution；Calcium carbonate template is added
Agent is uniformly mixed for stirring 4~6 hours, is stirred lower heating and is steamed solvent to close dry, vacuum drying is finely ground, under inert gas shielding
Pyrolysis, removes template agent removing with Diluted Acid Washing.
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