CN106744848B - The preparation of the three-dimensional grapheme of the iron cobalt and nitrogen ternary codope of multistage pore canal - Google Patents
The preparation of the three-dimensional grapheme of the iron cobalt and nitrogen ternary codope of multistage pore canal Download PDFInfo
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Abstract
The preparation method of the three-dimensional grapheme of iron cobalt and nitrogen ternary codope multistage pore canal with catalyzing cooperation effect is invented.The complex of PBI Yu iron ion and cobalt ions are prepared with the polybenzimidazoles (PBI) and molysite and cobalt salt of soluble full armaticity, addition nanometer calcium carbonate is template, pyrolysis, the carbon dioxide that Decomposition of Calcium Carbonate generates, which is discharged, to be formed aperture and is mutually communicated with the macropore generated after removing template is removed, and the three-dimensional grapheme that the multistage pore canal of iron cobalt and nitrogen ternary codope penetrates through is prepared.PBI preferably uses the macromolecule of the full armaticity such as ABPBI, mPBI, and viscosity average molecular weigh is 2 ~ 40,000；The molar ratio of molysite and cobalt salt is 1:2 ~ 2:1；The mass ratio of PBI and molysite cobalt salt mixture is 1:2 ~ 2:1；30 ~ 100 nm of partial size of template calcium carbonate；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
Graphene is the nano material of the lattice structure for the regular hexagon extension being made of carbon atom, due to its performance
Excellent and have a variety of potential applications, however, in macrocosm, easily layer-layer is overlapped mutually shape again between two-dimensional graphene
At graphite-structure, so that the performance for keeping its excellent is lost.Therefore, the preparation of three-dimensional grapheme and performance study become current nanometer
The research hotspot (Biener J, et al. Adv Mater (advanced material), 2012,24:5083) of Material Field.Research
It was found that the graphene of N doping due to the polarity between C-N key in graphene molecules sends out, the cloud density in graphene molecules
Changing, therefore the performances such as nitrogen-doped graphene catalytic oxidation-reduction are better than graphene.
Facilitate the generation of active sites by doping metals, if nitrogen-containing group and metal are coordinated to be formed in M-N-C activity
The synergistic effect of the heart, metal and nitrogen further improves its catalytic performance, enhancing catalytic activity and raising stability (Peng H
L, et al. Science (science), 2013,3:2045).Studies have shown that adulterated in graphene nitrogen and transition metal (such as iron,
Cobalt etc.) after, it will form more active sites, so that product catalytic oxidation-reduction catalytic activity can be further increased.Especially shape
At the transition metal and nitrogen co-doped catalyst of three-dimensional structure, its two-dimentional lamellar structure can be preferably kept without being superimposed
And aggregation, catalytic active site is more, and porous structure is conducive to the transmitting of fortification substance.It, should due to its unique advantage
Class material is considered as most one of development potentiality oxygen reduction catalyst, attracts widespread attention (Zitolo A, et
Al. Nature materials (nature material), 2015,14 (9): 937).Transition metal and nitrogen co-doped graphene tool
There is 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) or catalyst (Morozan A, et is precipitated in hydrogen
Al. J. Electrochem. Soc. (U.S.'s electrochemistry meeting will), 2015,162:H719)；In sensor, supercapacitor
With the fields such as lithium ion battery (Salavagione H J, et al. J. Mater. Chem. A (materials chemistry magazine A),
Application 2014,2:14289) has document report.Metal, N doping graphene preparation method have very much: such as, Gao Wenre
Solution transition macrocyclic complex (Beck F J, et al. Appl. Electrochem. (Applied Electrochemistry magazine), 1977,
7: 239)；Heat treatment organic compounds containing nitrogen (such as ethylenediamine, pyridine) and transition metal salt obtain M-N-C cluster (Lefe
Vre M, et al. Science (science) 2009,324:71)；Pass through high temperature pyrolysis system with melamine and etal molysite
Standby Fe-N-C cluster catalyst (Jiang W J, et al. J. Am. Chem. Soc (American Chemical Society) 2016,
138:3570), 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 the heat treatment system of polyaniline combination iron and cobalt
Standby one kind M/N/C catalyst (Wu G, et al. Science (science), 2011,332:443) etc..
The present invention is that a kind of prepare has the iron cobalt and nitrogen ternary codope of strengthening mass transfer effect and synergic catalytic effect more
The method of grade duct three-dimensional grapheme.With polybenzimidazoles (PBI) macromolecule and molysite and cobalt salt of soluble full armaticity
Mixed liquor reaction, the complex of generation, complex reaction mixture nanometer calcium carbonate template be uniformly mixed, complex exists
The arrangement of template rule of surface, under inert gas shielding, pyrolysis, complex forms iron cobalt and nitrogen three by dehydrogenation-cyclisation-carbonization
The graphene of first codope, the carbon dioxide that Decomposition of Calcium Carbonate generates are discharged to form aperture and go the macropore phase generated after removing template
Mutually perforation prepares the three-dimensional grapheme of the multistage pore canal perforation of iron cobalt and nitrogen ternary codope；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 iron cobalt and nitrogen ternary codope multistage pore canal three-dimensional grapheme, due to the co-doped and three of iron cobalt and nitrogen
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；
In addition, the iron in product is different from the extranuclear strucure of cobalt, electron outside nucleus cloud can influence each other, to generate catalyzing cooperation
Effect can be such that the catalytic activity of catalyst and stability increases；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, the effect without big π, so catalytic performance is not high, metal is easy to be removed by acid, so durability is inadequate
It is good, especially because metal-nitrogen-Spectra of Carbon Clusters is not that porous structure its mass transfer effect is bad, so, catalytic activity and durable
Property is not good enough.It is polyaniline and poly- pyrrole with the difference that polyaniline, polypyrrole are pyrolyzed the catalyst of formation together with transition metal
It coughs up since it cannot be dissolved, so, it can not cover with paint, lacquer, colour wash, etc. on template surface, so its operating characteristics is deteriorated, and PBI is solvable
Property, it is 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 that a kind of prepare has the iron cobalt and nitrogen ternary codope of strengthening mass transfer effect and synergic catalytic effect more
The method of grade duct three-dimensional grapheme.With polybenzimidazoles (PBI) macromolecule and molysite and cobalt salt of soluble full armaticity
Mixed liquor reaction, the complex of generation, complex reaction mixture nanometer calcium carbonate template be uniformly mixed, complex exists
The arrangement of template rule of surface, under inert gas shielding, pyrolysis, complex forms iron cobalt and nitrogen three by dehydrogenation-cyclisation-carbonization
The graphene of first codope, the carbon dioxide that Decomposition of Calcium Carbonate generates are discharged to form aperture and go the macropore phase generated after removing template
Mutually perforation prepares the three-dimensional grapheme of the multistage pore canal perforation of iron cobalt and nitrogen ternary codope；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 iron cobalt and nitrogen ternary codope multistage pore canal three-dimensional grapheme, due to the co-doped and three of iron cobalt and nitrogen
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；
In addition, the iron in product is different from the extranuclear strucure of cobalt, electron outside nucleus cloud can influence each other, to generate catalyzing cooperation
Effect can be such that the catalytic activity of catalyst and stability increases；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, the effect without big π, so catalytic performance is not high, metal is easy to be removed by acid, so durability is inadequate
It is good, especially because metal-nitrogen-Spectra of Carbon Clusters is not that porous structure its mass transfer effect is bad, so, catalytic activity and durable
Property is not good enough.It is polyaniline and poly- pyrrole with the difference that polyaniline, polypyrrole are pyrolyzed the catalyst of formation together with transition metal
It coughs up since it cannot be dissolved, so, it can not cover with paint, lacquer, colour wash, etc. on template surface, so its operating characteristics is deteriorated, and PBI is solvable
Property, it is very easy to cover with paint, lacquer, colour wash, etc. on template surface, operating performance is good.
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 the duct three-dimensional grapheme of iron cobalt and nitrogen ternary multistage codope are as follows: it is suitable to prepare the degree of polymerization first
When PBI, PBI dissolution form solution in a solvent, the mixed liquor of a certain amount of molysite and cobalt salt is added into solution, adds
Heat is stirred to react 5 ~ 8 hours, is obtained the complex reaction solution that PBI and iron ion and cobalt ions are formed, is 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.
For the present invention in the reacting of PBI and molysite and cobalt salt, the molar ratio of molysite and cobalt salt is 1:2 ~ 2:1；Salt-mixture
Additional amount is critically important, it determines the doping of iron and cobalt in the product of preparation, also determines catalysis of the product as catalyst
How much is active sites.Since iron ion and cobalt ions are coordinated with the imidazoles nitrogen in PBI macromolecule, guarantee four imidazole rings corresponding one
A iron ion or a cobalt ions are advisable, and test the mass ratio for finding PBI and molysite and cobalt salt mixture between 1:2 ~ 2:1,
Its variation matched is determined by different types of molysite and cobalt salt.
In the present invention, template is nano-calcium carbonate particles.The nitrogen co-doped multistage pore canal of tapping-cobalt-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；Template
The additional amount of agent determines the formation and performance of the number of plies of the graphene of preparation, aperture.Additional amount is very little, can only obtain iron cobalt and
Nitrogen co-doped porous carbon materials cannot obtain the material of multi-layer graphene structure；It is added excessively, obtained iron cobalt and nitrogen is co-doped with
The miscellaneous three-dimensional grapheme number of plies is very little, after removing template agent removing, is easy to collapse, can only obtain broken fragment.The particle of template
It spends and has a certain impact to the amount that template is added, granularity is small, large specific surface area, and the amount of the template needed is just few；Instead
It, 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 2 ~
5nm, so, the partial size of calcium carbonate selects 30 ~ 100nm；The dosage of template are as follows: the mass ratio of PBI and template is 2:1~1:
4；Ratio variation is related with the granularity of template.It is pyrolyzed under inert gas protection, the regularly arranged cooperation on template surface
The a series of heat chemistry variation such as dehydrogenation-cyclisation-carbonization can occur for object, finally obtain product.The formation of the pore channels of perforation
Related with the decomposition when amount of nanometer calcium carbonate and pyrolysis, pyrolysis temperature hereinafter, calcium carbonate does not decompose, cannot be formed at 800 DEG C
The channel of aperture perforation.The aperture of aperture and the amount of calcium carbonate are related, and the amount for the carbon dioxide that calcium carbonate generates is big, then can be with shape
At aperture aperture it is just big, if the amount of the carbon dioxide of generation is small, the aperture formed is with regard to small.In inert gas shielding
Lower pyrolysis, pyrolysis temperature are as follows: 800~1100 DEG C；The formation of aperture and pore size are the carbon dioxide that Decomposition of Calcium Carbonate generates
It generates, the factors such as amount and pyrolysis temperature of calcium carbonate determine aperture and the perforation performance of aperture.Such multistage penetrates through porous
Material has invigoration effect to the mass transfer of 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 multistage pore canal of three-dimensional iron cobalt nitrogen ternary codope 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) (100g), the lower 160 DEG C of stirrings 1h of nitrogen protection is to remove extra moisture and air.By DABz (4g, 18.7
Mmol) and M-phthalic acid (3.1g, 18.7 mmol) is uniformly mixed, and is slowly added in three-necked flask.Control nitrogen
Flow 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 5-8h.With reaction
The increase of time, polymerization system gradually become sticky.Stop reaction when viscosity is suitable, reaction mixture is slowly transferred to largely
It reels off raw silk from cocoons in deionized water, cleans, drying, crush, to remove polyphosphoric acids and unreacted reactant, i.e., deionized water is repeatedly washed
MPBI is obtained, with the molecular weight of determination of ubbelohde viscometer mPBI.
[embodiment 2] Solid phase synthesis mPBI: by DABz (4g, 18.7 mmol) and M-phthalic acid
(3.1g, 18.7 mmol) are uniformly mixed in being fully ground in mortar, are transferred to nitrogen protection, three mouthfuls of burnings of blender
In bottle.Lead to nitrogen 15min to drain the air in flask.N2Protection, under stirring, 225 DEG C of oil bath heating keep 3h.After cooling
It takes out, 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 ground
Carefully to get mPBI is arrived, with the molecular weight of determination of ubbelohde viscometer mPBI.
The preparation method of ABPBI is similar with mPBI's, only with 3,4- diaminobenzoic acid (DABA) substitute DABz and
Phthalic acid.ABPBI only can be obtained with a kind of raw material.Other reaction conditions and operating procedure with embodiment 1 and are implemented
Example 2.
[embodiment 3] is template with the calcium carbonate of partial size 30nm, and molysite and cobalt salt use acetate, molar ratio 1:1；Two
It with the mass ratio of mPBI is 1:2 after the mixing of kind of salt, by taking mPBI and calcium carbonate template mass ratio are 1:1 as an example: in the burning of 250mL
In cup, the mPBI(viscosity average molecular weigh 2 ~ 3 of 1g is added ten thousand) with 20mL DMAc, heats, stir to dissolve, be added under stiring
The 20mL DMAc solution of 0.5 g cobalt acetate and the mixture (two kinds of salt are mixed according to molar ratio 1:1) of ferric acetate, 80 DEG C of heat preservation ~
It at 100 DEG C, is stirred to react 5 ~ 8 hours, is slowly added into the calcium carbonate granule for the nanometer that 1g partial size is 30nm, stirs 4 ~ 6 hours, make
It is uniformly dispersed.Obtained viscous liquid is heated to be concentrated under stiring and closely be done, and is done at 60 ~ 120 DEG C in vacuum oven
Dry, solid is finely ground in mortar, is transferred in porcelain boat, under protection of argon gas, 2-3h is pyrolyzed at 900 DEG C in electric furnace, to furnace temperature
It is down to room temperature, is taken out, it is finely ground, black powder solid is obtained, is transferred in 250 mL conical flasks, the dilute hydrochloric acid of 70 mL is added,
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 solid product
0.75g.BET test shows that its pore-size distribution is 30 nm, and 2 ~ 4 nm specific surface area of aperture is 1331 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, 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 show to produce
The graphene-structured that product are 2 ~ 4 layers；XPS analysis shows product iron content 0.7%, cobalt content 0.8%, nitrogen content 6.8%, and
Nitrogen is 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-cobalt-
Material.Catalytic oxidation-reduction performance under its 0.1 mol/L KOH, oxygen initial reduction current potential are 1.01 V vs RHE, electron transfer number
It is 3.99, durability is good；Magnesium air battery performance is up to 127 mW/cm2.It is 674 for its peak power of hydrogen-oxygen fuel cell
mW/cm2, it is 1.46 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
140 mA/cm2.Supercapacitor specific capacitance is 523 F g-1, be recycled 10000 times still holding capacitor value 98%.
[embodiment 4] as described in Example 3, 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.It is 30 nm, 2 ~ 4 nm of aperture that BET test, which shows its pore-size distribution still, but it compares table
Area is then reduced to 747 m2 g-1, SEM and TEM test show its it is internal be porous structure carbon material, surface is multilayer stone
Black 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 3.Its
Catalytic oxidation-reduction performance under 0.1 mol/L KOH, oxygen initial reduction current potential are 0.86 V vs RHE, and electron transfer number is
3.69, durability is good；Magnesium air battery performance is up to 78 mW/cm2.It is 376 mW/ for its peak power of hydrogen-oxygen fuel cell
cm2, it is 1.57 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 60
mA/cm2.Supercapacitor specific capacitance is 238 F g-1, be recycled 10000 times still holding capacitor value 95%.
[embodiment 5] as described in Example 3, 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 868 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 3.
Catalytic oxidation-reduction performance under its 0.1 mol/L KOH, oxygen initial reduction current potential are 0.88 V vs RHE, and electron transfer number is
3.76, durability is good；Magnesium air battery performance is up to 84 mW/cm2.It is 368 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 70
mA/cm2.Supercapacitor specific capacitance is 364 F g-1, be recycled 10000 times still holding capacitor value 95%.
[embodiment 6] as described in Example 3, other conditions are identical, and only pyrolysis temperature is respectively 700 DEG C.It obtains black
Powdered 0.79 g of solid product of color.BET test shows that its pore-size distribution is 30 nm, 2 ~ 4 nm of aperture, and specific surface area is
1098 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 grapheme structure 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 that product iron content 0.7%, cobalt content are
0.7%, nitrogen content 6.8%, and nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Illustrate, product is the three-dimensional grapheme structure of N doping
Material.Catalytic oxidation-reduction performance under its 0.1mol/L KOH, oxygen initial reduction current potential are 0.87 V vs RHE, and electronics turns
Moving number is 3.74, and durability is slightly worse good；Magnesium air battery performance is up to 69 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is
281 mW/cm2, it is 1.66 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
To 50 mA/cm2.Supercapacitor specific capacitance is 274 F g-1, be recycled 10000 times still holding capacitor value 94%.
[embodiment 7] the other the same as in Example 3, only pyrolysis temperature is 1100 DEG C.Obtain black powder solid product
0.59 g.BET test shows that its pore-size distribution is 30 nm, and 3 ~ 4 nm of aperture, specific surface area is 865 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, 3 ~ 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 product iron content 0.6%, cobalt content 0.5%, nitrogen content 6.2%,
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 0.96 V vs RHE, and electron transfer number 3.95, durability is good
It is good；Magnesium air battery performance is up to 88 mW/cm2.It is 454 mW/cm for its peak power of hydrogen-oxygen fuel cell2, 0.5 mol/L's
It is 1.59 V vs RHE that take-off potential, which is precipitated, in oxygen in sulfuric acid solution, and limiting current density reaches 80 mA/cm2.Super capacitor
Device specific capacitance is 357 F g-1, be recycled 10000 times still holding capacitor value 96%.
[embodiment 8] 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 3, and only its pore-size distribution compares table in 50 nm, 4 ~ 5 nm of aperture
Area is 1181 m2 g-1, it is 3 ~ 5 layers of three-dimensional nitrogen-doped graphene material, catalytic oxidation-reduction originates under 0.1 mol/L KOH
Current potential is 0.96V vs RHE, and electron transfer number 3.96, durability is good；Magnesium air battery performance is up to 106 mW/cm2.With
In its peak power of hydrogen-oxygen fuel cell be 452 mW/cm2, it is 1.55 that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5 mol/L
V vs RHE, limiting current density reach 110 mA/cm2.Supercapacitor specific capacitance is 321F g-1, it is recycled 10000
The 97% of secondary still holding capacitor value.
[embodiment 9] as described in Example 3, other conditions are identical, are only that 100 nm calcium carbonate granules are done with partial size
Template, 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 is changed to as 1:4, and obtained product is similar to Example 3, and only its pore-size distribution is in 100 nm, 5 nm specific surface of aperture
Product is 867 m2 g-1, it is 3 ~ 5 layers of three-dimensional nitrogen-doped graphene material, catalytic oxidation-reduction take-off potential is 0.94V vs RHE,
Electron transfer number is 3.90, and durability is good；Magnesium air battery performance is up to 81 mW/cm2.For its peak function of hydrogen-oxygen fuel cell
Rate is 338 mW/cm2, it is 1.58 V vs RHE that take-off potential, which is precipitated, in oxygen in the sulfuric acid solution of 0.5mol/L, and carrying current is close
Degree reaches 70 mA/cm2.Supercapacitor specific capacitance is 221 F g-1, be recycled 10000 times still holding capacitor value 95%.
[embodiment 10] uses calcium carbonate template, and partial size is 30 nanometers, molysite and cobalt salt citrate, with ABPBI
Mass ratio be 2:1.Other experiment conditions are the same as embodiment 3.The mass ratio of ABPBI and template is 1:1.Its result and embodiment
3 is similar.Aperture is 30 nm, aperture 2 ~ 4 nm, 1315 m2 g-1, it is 2 ~ 4 layers of graphene.Iron content 0.8%, cobalt content 0.8%,
Nitrogen content is 6.7%, and nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Catalytic oxidation-reduction performance under its 0.1 mol/L KOH, oxygen rise
Beginning reduction potential is 1.02 V vs RHE, and electron transfer number 3.99, durability is good；Magnesium air battery performance is up to 118 mW/
cm2.It is 618 mW/cm for its peak power of hydrogen-oxygen fuel cell2, oxygen is precipitated take-off potential and is in the sulfuric acid solution of 0.5 mol/L
1.54 V vs RHE, limiting current density reach 110 mA/cm2.Supercapacitor specific capacitance is 549 F g-1, it is recycled
10000 times still holding capacitor value 97%.
[embodiment 11] other molysite, cobalt salt situation are similar to the above embodiments, only change PBI and molysite and cobalt salt is mixed
Close the ratio of object.
The case where product that the calcium carbonate of [embodiment 12] ABPBI and other partial sizes is mixed with, same to above-described embodiment,
Performance is better than using the product of mPBI under similarity condition.
Mole such as 1:2 or 2:1 of [embodiment 13] other molysite, cobalt salt, other operating procedures are obtained with embodiment 3
Product catalytic performance it is good not as good as 1:1.
Claims (5)
1. a kind of preparation method of the three-dimensional grapheme of iron cobalt and nitrogen ternary codope multistage pore canal with catalyzing cooperation effect,
It is characterized by: with polybenzimidazoles (PBI) and molysite and cobalt salt the preparation PBI and iron ion and cobalt of soluble full armaticity
The complex of ion, addition nanometer calcium carbonate are template, are uniformly mixed, are evaporated, and complex is arranged in template rule of surface,
Under inert gas shielding, pyrolysis, complex forms the graphene of iron cobalt and nitrogen ternary codope, carbon by dehydrogenation-cyclisation-carbonization
Sour calcium decompose the carbon dioxide generated be discharged to be formed micropore with go to generate after removing template it is mesoporous be mutually communicated, iron cobalt is prepared
The three-dimensional grapheme penetrated through with the multistage pore canal of nitrogen ternary codope；Its concrete operation step are as follows: the molar ratio of molysite and cobalt salt
For 1:2~2:1；The mass ratio of PBI and molysite and cobalt salt mixture is 2:1~1:2；Nano template is partial size 30~100
The calcium carbonate of nm；PBI and the mass ratio of nano template are 2:1~1:4；It is protected in inert gas argon gas or high pure nitrogen, 800
At~1100 DEG C, it is pyrolyzed 2~3 hours；The three-dimensional graphite of the multistage pore canal perforation of the iron cobalt and nitrogen ternary codope of above-mentioned preparation
Alkene is used for redox reaction catalyst, fuel cell, metal-air battery oxygen reduction catalyst, and catalysis is precipitated in electrolysis water oxygen
Agent, electrode material for super capacitor.
2. the three of a kind of iron cobalt and nitrogen ternary codope multistage pore canal with catalyzing cooperation effect according to claim 1
Tie up the preparation method of graphene, it is characterised in that: the entire polymer molecule of PBI of full armaticity forms a big pi bond, molecule category
In rigidity, aroma type compound, poly- (2,5- benzimidazole) (ABPBI), poly- [2,2 '-(phenyl) -5,5 '-biphenyl are selected
One of and imidazoles] (mPBI)；Polymer viscosity average molecular weigh is between 2~40,000；Dimethyl acetamide can be dissolved in
(DMAc), dimethylformamide (DMF), dimethyl sulfoxide (DMSO), any one in N-Methyl pyrrolidone or dimethylbenzene
In solvent.
3. the three of a kind of iron cobalt and nitrogen ternary codope multistage pore canal with catalyzing cooperation effect according to claim 1
Tie up the preparation method of graphene, it is characterised in that: molysite and cobalt salt are the salt that can be dispersed or dissolved in intensive polar solvent；
It selects, one of acetate, citrate, nitrate, hydrochloride, perchlorate, gluconate；Molysite and cobalt salt rub
You are than being 1:2~2:1.
4. the three of a kind of iron cobalt and nitrogen ternary codope multistage pore canal with catalyzing cooperation effect according to claim 1
Tie up the preparation method of graphene, nano template is nanoscale calcium carbonate, it is characterised in that: nano-particle diameter 30~
100 nm；800 DEG C of the nano particle starts to decompose；It is any one nano particle of spherical shape, cube, cylinder or polygon prism.
5. the three of a kind of iron cobalt and nitrogen ternary codope multistage pore canal with catalyzing cooperation effect according to claim 1
Tie up the preparation method of graphene, it is characterised in that: the mass ratio of PBI and molysite and cobalt salt mixture are as follows: 2:1~1:2；PBI with
The mass ratio of nano template is 2:1~1:4；Hybrid mode are as follows: PBI solution is mixed with the mixed liquor of molysite and cobalt salt, is added
Heat is stirred to react 5 ~ 8 hours, and PBI and iron ion and cobalt ions form complex solution；Template, stirring 4~6 hours is added
It is uniformly mixed, it stirs lower heating and steams solvent to closely doing, 60~120 DEG C of vacuum drying are finely ground, it is pyrolyzed under inert gas shielding,
With Diluted Acid Washing to remove template agent removing.
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