CN106622330A - Preparation of Fe-Co-N three-element co-doping three-dimensional graphene with catalytic synergistic effect - Google Patents
Preparation of Fe-Co-N three-element co-doping three-dimensional graphene with catalytic synergistic effect Download PDFInfo
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to a simple preparation method of Fe (ferrous), Co (cobalt) and N (nitrogen) three-element co-doping three-dimensional graphene with catalytic synergistic effect. The preparation method comprises the following steps of enabling soluble fully-aromatic PBI (polybenzimidazole) to react with a ferrous salt and cobalt salt mixing solution; firstly, preparing a complex of PBI, ferrous ions and cobalt ions; adding a nanometer template agent into the reaction mixing liquid; regularly arranging the complex at the surface of the template agent; pyrolyzing, removing a template, and the like, so as to prepare the Fe-Co-N three-element co-doping three-dimensional graphene. The PBI is selected from fully-aromatic macromolecules, such as ABPBI and mPBI, and the viscosity average molecular weigh is 20,000 to 40,000; the molar ratio of ferrous salt and cobalt salt is 1:2 to 2:1; the mass ratio of PBI and ferrous salt and cobalt salt mixture is 1:2 to 2:1; the template agent is selected from nanometer magnesium oxide, ferric oxide and ferric hydroxide nanoparticles; the particle size of the template agent is 5 to 50nm; the mass ratio of PBI and template agent is 3:1 to 1:3; the pyrolysis temperature is 700 to 1000 DEG C; the Fe-Co-N three-element co-doping three-dimensional graphene can be applied to the fields of redox reaction catalysts, fuel batteries, metal air battery redox catalysts, water electrolysis separation catalysts, supercapacitors and the like.
Description
Technical field
Belong to field of nano material preparation, for the redox reaction catalyst in Chemical Manufacture, clean energy resource field
Fuel cell, the cathod catalyst of metal-air battery, electrolysis water catalyst, lithium ion battery material, super capacitor electrode
The field such as pole material and electrochemical sensor.
Background technology
Graphene is the nano material of the lattice structure of the regular hexagon extension being made up of carbon atom, due to its performance
It is excellent and with various potential applications, become current wide concerned study hotspot (Kim K S, et al. Nature (from
So), 2009,457: 706).However, again easily layer-layer is overlapped mutually to form stone between macrocosm, two-dimensional graphene
Ink structure, so that its excellent performance is lost.Therefore, the preparation of three-dimensional grapheme and performance study become current nano material
Field study hotspot (Biener J, et al. Adv Mater (advanced material), 2012,24: 5083).Three-dimensional graphite
Alkene serves many purposes：Such as, for oxygen reduction catalyst or catalyst carrier, for energy such as fuel cell, metal-air batteries
The important materials of source conversion, are also the important materials in the fields such as lithium ion battery, ultracapacitor, electrochemical sensor and electrolysis
(Dai L. Acc Chem Res (chemical research commentary), 2013,46 (1): 31).Research discovery, the Graphene of N doping
Due to the polarity in graphene molecules between C-N keys, the cloud density in graphene molecules is set to change, therefore N doping stone
The performances such as black alkene catalytic oxidation-reduction are better than Graphene.
If nitrogen-containing group forms M-N-C activated centres with metal-complexing, metal is further improved with the synergy of nitrogen
Its catalytic performance.Research shows that adulterate nitrogen and transition metal in Graphene（Such as iron, cobalt etc.）Afterwards, more activity can be formed
Site, so as to can further improve product catalytic oxidation-reduction catalysis activity.Particularly form the transition metal and nitrogen of three-dimensional structure
The catalyst of codope, can preferably keep its two-dimensional slice structure and not be superimposed and assemble, and its catalytic active site is more,
And loose structure is conducive to the transmission of fortification substance.Due to its unique advantage, such material is considered as most to develop to dive
One of power oxygen reduction catalyst, attracts widespread attention (Zitolo A, et al. Nature materials (natures
Material), 2015,14 (9): 937-942).Transition metal and nitrogen co-doped Graphene have extensive use, can be used as oxygen also
Raw catalyst（Jiang H L, et al. ACS Appl. Mater. Interfaces（American Chemical Society is using surface and boundary
Face）, 2015, 7 (38): 21511）Or hydrogen separates out catalyst（Morozan A, et al. J. Electrochem.
(U.S.'s electrochemistry meeting will), Soc. 2015,162: H719）；In fields such as sensor, ultracapacitor and lithium ion batteries
（Salavagione H J, et al. J. Mater. Chem. A (materials chemistry magazine A), 2014,2: 14289）'s
Using there is document report.Metal, the graphene preparation method of N doping have a lot：Such as, high temperature pyrolysis transition macrocyclic complex
(Ji Y F, et al. Int J Hydrogen Energy (international Hydrogen Energy magazine), 2010,35: 8117)；Heat treatment contains
Nitrogen organic compound（Such as ethylenediamine, pyridine）M-N-C clusters are obtained with transition metal salt（Lefèvre M, et al.
Science (science) 2009,324,71）；The heat treatment for combining iron and cobalt with polyaniline prepares a class M/N/C catalyst (Wu
G, et al. Science (science), 2011,332: 443) ；Polypyrrole prepares oxygen reduction catalyst with cobalt salt pyrolysis
（Bashyam R & Zelenay P. Nature（It is natural）, 2006, 433(7): 63）Etc..
The present invention is the side of a kind of iron cobalt prepared with synergic catalytic effect and nitrogen ternary codope three-dimensional grapheme
Method.With the polybenzimidazoles of soluble full armaticity（PBI）The mixed liquor reaction of macromolecule and molysite and cobalt salt, generation is matched somebody with somebody
Compound, complex reaction mixture is well mixed in nano template, is evaporated, finely ground, and pyrolysis under inert gas shielding prepares iron
The three-dimensional grapheme of cobalt and nitrogen ternary codope.The PBI solution of full armaticity obtains PBI and iron with molysite and cobalt salt hybrid reaction
The complex that ion and cobalt ions are formed, adds nano particle as template, is uniformly mixed, and makes complex in template
Top finishing is simultaneously arranged in template rule of surface, under inert gas shielding, pyrolysis, dehydrogenation-cyclisation-carbonization, so as to form iron
The multi-layer graphene structure of cobalt and nitrogen ternary codope, goes template agent removing to obtain iron cobalt and nitrogen ternary codope three-dimensional grapheme.
Such material is due to iron cobalt and the co-doped and three-dimensional porous structure of nitrogen so that its specific surface area increase, catalytic active site increase
Plus.Because iron or cobalt and the polar bond of nitrogen formation are inside graphene molecules, the big π bond structures of Graphene itself, its molecule rail
The delocalization energy increase in road, the energy level between HUMO tracks and LOMO tracks diminishes so that the environment of its catalytic active center is special
As porphyrin, the environment of phthalocyanine complex, the overpotential of catalytic oxidation-reduction, the catalysis thermodynamics of catalyst can be so substantially reduced
Performance gets a promotion；In addition, the iron in product is different from the extranuclear strucure of cobalt, its electron outside nucleus cloud can influence each other, from
And produce catalyzing cooperation effect；Furthermore, three-dimensional porous structure is conducive to strengthening mass transfer so that electrode reaction dynamic performance increases
Plus.It is of the invention with simple itrogenous organic substance and transient metal complex or nitrogen containing polymer, such as pollopas, melmac
It is that metal-nitrogen-Spectra of Carbon Clusters is not graphite Deng the metal-nitrogen-Spectra of Carbon Clusters difference prepared with transition metal mixture pyrolysis
Alkene structure, the effect without big π, so catalytic performance is not high, its metal is easily by acid removing, so durability is not good enough, especially
It is because metal-nitrogen-Spectra of Carbon Clusters is not that loose structure its mass transfer effect is bad.With polyaniline, polypyrrole and transition metal one
Playing the difference of catalyst that pyrolysis formed is, polyaniline with polypyrrole because it can not be dissolved, so, it cannot be covered with paint, lacquer, colour wash, etc.
Template surface, so its operating characteristics is deteriorated, and PBI is soluble, and on template surface, it can for its very easy covering with paint
Good operation performance.
The content of the invention
The present invention is a kind of polybenzimidazoles of soluble full armaticity（PBI）Macromolecule is formed with molysite and cobalt salt
Complex pyrolysis under nano template effect prepares the preparation method of cobalt and nitrogen co-doped three-dimensional grapheme.Full armaticity
PBI solution obtains complex with molysite and cobalt salt hybrid reaction, adds nano particle as template, is uniformly mixed, and makes
The complex that PBI is formed with iron ion and cobalt ions is arranged in template top finishing and in template rule of surface, in inertia
Under gas shield, pyrolysis, dehydrogenation-cyclisation-carbonization, so as to form the multi-layer graphene structure of iron cobalt and nitrogen ternary codope, is gone
Template agent removing obtains iron cobalt and nitrogen ternary codope three-dimensional grapheme.Such material is due to iron cobalt and the co-doped and three-dimensional of nitrogen
Loose structure so that its specific surface area increase, catalytic active site increase.Because iron or cobalt and the polar bond of nitrogen formation are in Graphene
Intramolecule, the big π bond structures of Graphene itself cause its MO delocalization energy increase, HUMO tracks and LOMO tracks it
Between energy level difference diminish so that the environment of its catalytic active center can be with especially as porphyrin, the environment of cobaltphthalocyanines, so
The overpotential of catalytic oxidation-reduction is substantially reduced, catalysis thermodynamic property gets a promotion；In addition, the core dispatch from foreign news agency of the iron and cobalt in product
Minor structure is different, and its electron outside nucleus cloud can influence each other, so as to produce catalyzing cooperation effect；Furthermore, three-dimensional porous structure is favourable
In reinforcing mass transfer so that electrode reaction dynamic performance increases.It is of the invention with simple itrogenous organic substance and transient metal complex
Or nitrogen containing polymer, metal-nitrogen that such as prepared by the pyrolysis of pollopas, melmac and transition metal mixture-carbon original
Submanifold difference is, metal-nitrogen-Spectra of Carbon Clusters is not graphene-structured, the effect without big π, so catalytic performance is not high, its gold
Category is easily by acid removing, so durability is not good enough, especially because metal-nitrogen-Spectra of Carbon Clusters is not its mass transfer of loose structure
Effect is bad.The difference of catalyst formed with polyaniline, polypyrrole and transition metal salt mixture pyrolysis is, polyaniline with
Polypyrrole can not be dissolved due to it, so, it cannot be covered with paint, lacquer, colour wash, etc. on template surface, it is impossible to use template pore-creating；And PBI be can
Dissolubility, its very easy covering with paint is on template surface, and its operating performance is good.
Viscosity average molecular weigh being soluble between 20,000～40,000 prepared by full armaticity PBI solid phase method or liquid phase method
DMAc, DMF, DMSO, in 1-METHYLPYRROLIDONE equal solvent.Molecular weight is too big, and the solubility property of PBI is deteriorated；Molecular weight is too little
Its viscosity is too little, it is impossible to coated die plate agent well.In PBI families, the example with full armaticity, such as ABPBI and mPBI,
Their structural formula is respectively：
The structural formula of the structural formula mPBI of ABPBI
The method of the preparation of the Graphene of three-dimensional iron cobalt and nitrogen ternary codope is：The appropriate PBI of the degree of polymerization is prepared first,
PBI dissolvings form in a solvent solution, and the mixed liquor of a certain amount of molysite and cobalt salt, heating, stirring reaction 5 are added in solution
~ 8 hours, the complex reactant liquor that PBI and iron ion and cobalt ions are formed is obtained, add the appropriate particle diameter to be in the reactant liquor
Template is done in the nanoparticle template agent of 5 ~ 50 nm, and stirring makes it be sufficiently mixed uniformly.Under agitation, heat, steam at leisure molten
Agent is proceeded in vacuum drying chamber and dried at 60 ~ 120 DEG C near dry.It is finely ground in mortar, porcelain boat bottom is laid in, it is put into tubular type
In electric furnace, under argon gas protection, at 700～1100 DEG C, 2 ~ 3h is pyrolyzed.Treat that furnace temperature is cooled to room temperature, take out, it is multiple with diluted acid
Washing dries to obtain product to go template agent removing, suction filtration, deionized water to clean.
In the reaction of PBI and molysite and cobalt salt, molysite is 1 with the mol ratio of cobalt salt to the present invention:2~2:1；Salt-mixture
Addition is critically important, and it determines the doping of iron and cobalt in the product of preparation, also determines product as the catalysis of catalyst
Active sites are how many.Because iron ion and cobalt ions are coordinated with the imidazoles nitrogen in PBI macromolecules, it is ensured that four imidazole ring correspondences one
Individual iron ion or a cobalt ions are advisable, and experiment finds that PBI is 1 with the mass ratio of molysite and cobalt salt mixture:2~2:Between 1,
The change of its proportioning is determined by different types of molysite and cobalt salt.
In the present invention, template can be various nano-scale oxides or hydroxide particles.Three-dimensional can be prepared
Iron-cobalt-nitrogen co-doped Graphene, the particle diameter and addition of template are crucial：The particle diameter of template determines the material of preparation
Aperture；The shape of template determines the shape to form hole；The addition of template determines the number of plies of the Graphene of preparation and property
Can, addition very little, can only obtain iron cobalt and nitrogen co-doped porous carbon materials, add excessively, and the iron cobalt for obtaining and nitrogen are co-doped with
The miscellaneous three-dimensional grapheme number of plies very little, after removing template agent removing, is easily subsided, and can only obtain broken fragment.The particle of template
Spend the amount to adding template to have a certain impact, granularity is little, its specific surface area is big, the amount of the template of needs is just few；Instead
It, if granularity is big, the amount of the template of needs is just more.The consumption of template is：PBI is 3 with the mass ratio of template:1
～1:3；Ratio change is relevant with the granularity of template.Granularity is from 5 ~ 50 nm.It is pyrolyzed under inert gas shielding, pyrolysis temperature
Spend and be：700～1100 DEG C；Washing diluted acid, repeatedly washing is gone after template agent removing, is washed with deionized to neutral drying i.e.
Can.
Pyrolysis temperature is critically important, and pyrolysis temperature range is 700～1100 DEG C.The too low PBI pyrolysis of temperature is incomplete, is produced
The electric conductivity of product is poor；Pyrolysis temperature is reached after optimum temperature, then to raise pyrolysis temperature its performance constant, but, inert gas
Oxidation reaction can occur, so pyrolysis temperature is unsuitable too high when protecting insufficient.
The Graphene characterizing method of three-dimensional iron cobalt nitrogen ternary codope is：Aperture, porosity, pore volume and specific surface area nitrogen
Gas adsorption instrument（BET）, the Morphology analysis SEM of product（SEM）And projection electron microscope（TEM）, stone
The black alkene number of plies can pass through high power transmission electron microscope（HRTEM）Characterize with Raman spectrum.The degree of graphitization of product, stone
Black alkene structure and the number of plies can use X-ray powder diffraction（XRD）, Raman spectrum to be characterizing.The element composition of product, valence state can
With with x-ray photoelectron spectroscopy（XPS）Characterized, used rotating disk electrode (r.d.e)（RDE）Carry out the catalytic oxidation-reduction of test product
Reaction（ORR）Performance, water electrolysis oxygen evolution reaction（EOR）, evolving hydrogen reaction（EHR）Can be with following with the test of the capacitive property of product
Ring volt-ampere（CV）, linear volt-ampere（LSV）, Tafel curve and charge-discharge performance to be testing.Durability of the product as catalyst
Test can be using CV, LSV and chronoa mperometric plot（i-t）.The catalytic performance of product finally need assemble metal-air battery,
Hydrogen-oxygen fuel cell, the electrolytic cell of electrolysis water, ultracapacitor and sensor are testing its performance.
Specific embodiment
The preparation of [embodiment 1] mPBI：Polyphosphoric acids is added in the there-necked flask protected equipped with electric stirring and nitrogen
(PPA) (100g), lower 160 DEG C of nitrogen protection stirs 1h to remove unnecessary moisture and air.By DABz (4g, 18.7
Mmol) and M-phthalic acid (3.1g, 18.7 mmol) is well mixed, in being slowly added to there-necked flask.Control nitrogen
Flow velocity, prevents DABz to be oxidized, while lifting to 200 DEG C and continuing insulation, stirring reaction 5-8h by reaction temperature.With reaction
The increase of time, polymerization system gradually becomes sticky.Stop reaction when viscosity is suitable, reaction mixture is slowly transferred in a large number
Reel off raw silk from cocoons in deionized water, clean, dry, crush, deionized water is repeatedly washed to remove polyphosphoric acids and unreacted reactant, i.e.,
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) in mortar, are fully ground and are well mixed, and are transferred to three mouthfuls of burnings with nitrogen protection, agitator
In bottle.Logical nitrogen 15min is draining the air in flask.N2Protection, under stirring, 225 DEG C of heating of oil bath keep 3h.After cooling
Take out, finely ground, N2Under protection, heating in electric furnace is warmed up to 270-275 DEG C, keeps 3h.Room temperature is cooled to, product is taken out, ground
Carefully, that is, mPBI is obtained, with the molecular weight of determination of ubbelohde viscometer mPBI.
The preparation method of ABPBI is similar with mPBI, simply with 3,4- diaminobenzoic acids（DABA）Substitute DABz and
Phthalic acid.Only ABPBI is obtained with a kind of raw material.Other reaction conditions and operating procedure are with embodiment 1 and enforcement
Example 2.
[embodiment 3] is template with the MgO of particle diameter 30nm, and molysite and cobalt salt use acetate, mol ratio 1:1；Two kinds
With the mass ratio of PBI it is 1 after salt mixing:2, PBI with mPBI, with mPBI and MgO templates mass ratio as 1:As a example by 1：In 250mL
Beaker in, add 1g mPBI（Viscosity average molecular weigh 2 ~ 30,000）With 20mL DMAc, heating, stirring dissolve it, under agitation
Add the mixture of 0.5 g cobalt acetates and ferric acetate（Two kinds of salt are according to mol ratio 1:1 mixing）20mL DMAc solution, insulation
At 80 DEG C ~ 100 DEG C, stirring reaction 5 ~ 8 hours is slowly added into the MgO particles of the nanometer that 1g particle diameters are 30nm, stirs 4 ~ 6 hours,
It is set be uniformly dispersed.The viscous liquid for obtaining heat under agitation be concentrated into it is near dry, 120 DEG C in the vacuum drying chamber at do
Dry, solid is finely ground in mortar, is transferred in porcelain boat, under argon gas protection, 900 DEG C in the electric furnace at be pyrolyzed 2-3h, treat furnace temperature
Room temperature is down to, is taken out, it is finely ground, black powder solid is obtained, in being transferred to 250mL conical flasks, the watery hydrochloric acid of 70mL is added, plus
Heat, stirring 24h, suction filtration is so washed three times with watery hydrochloric acid, is washed to neutrality, is dried to obtain black powder solid product
0.73g.BET tests show that its pore-size distribution is 30nm, and specific surface area is 1123 m2 g-1, SEM test show, the product for obtaining
Product are porous foam shape material with carbon element, TEM and HRTEM analysis shows, product is three-dimensional grapheme structure material with carbon element, and aperture is 30
Nm, Graphene is drawn a bow to the full back and is shown to be 2 ~ 4 layer graphenes.XRD and Raman spectrum test show that product is 2 ~ 4 layers of graphene-structured；
XPS analysis show that product iron content 0.8%, cobalt content is 0.9%, and nitrogen content is 7.6%, and nitrogen is pyridine type nitrogen and pyrroles's type
Nitrogen.Illustrate, product is the material of the three-dimensional grapheme structure of iron-cobalt-nitrogen co-doped.Catalytic oxidation-reduction under its 0.1mol/L KOH
Performance, oxygen initial reduction current potential is 0.98 V vs RHE, and electron transfer number is 3.98, and durability is good；Magnesium air cell
Can be up to 97 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 556 mW/cm2, oxygen is separated out in the sulfuric acid solution of 0.5 mol/L
Take-off potential is 1.54V vs RHE, and limiting current density reaches 120mA/cm2.Ultracapacitor specific capacitance is 456F g-1,
10000 times capable of circulation still holding capacitor value 98%.
[embodiment 4] as described in Example 3, other conditions are identical, and simply the quality of mPBI and MgO is changed into 2：1, together
Sample obtains the pressed powder of black.BET tests show that its pore-size distribution is still 30nm, but its specific surface area is then reduced to 756
m2 g-1, its SEM and TEM tests show, its internal material with carbon element for loose structure, and surface is multi-layer graphene structure, XRD and
Raman data shows, 7 ~ 8 layers of the number of plies of its Graphene.XPS data are similar with the product of embodiment 3.Under its 0.1mol/L KOH
Catalytic oxidation-reduction performance, oxygen initial reduction current potential is 0.82V vs RHE, and electron transfer number is 3.61, and durability is good；Magnesium
Air cell performance reaches 66mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 252 mW/cm2, the sulfuric acid solution of 0.5mol/L
It is 1.68V vs RHE that middle oxygen separates out take-off potential, and limiting current density reaches 40mA/cm2.Ultracapacitor specific capacitance is
217F g-1, 10000 times capable of circulation still holding capacitor value 95%.
[embodiment 5] as described in Example 3, other conditions are identical, and simply the quality of mPBI and MgO is changed into 1：2, together
Sample obtains the pressed powder of black.BET is tested and shown, 10 ~ 30nm of its pore size distribution range, but its specific surface area is then reduced to
829 m2 g-1, its SEM and TEM tests show, are material with carbon element of loose structure inside it, and surface is multi-layer graphene 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 0.1mol/L
Catalytic oxidation-reduction performance under KOH, oxygen initial reduction current potential is 0.84V vs RHE, and electron transfer number is 3.73, and durability is good
It is good；Magnesium air cell performance reaches 79mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 346mW/cm2, the sulfuric acid of 0.5mol/L
It is 1.59V vs RHE that oxygen separates out take-off potential in solution, and limiting current density reaches 50mA/cm2.Ultracapacitor specific capacitance
For 318F g-1, 10000 times capable of circulation still holding capacitor value 95%.
[embodiment 6] as described in Example 3, other conditions are identical, and simply pyrolysis temperature is respectively 700 DEG C.Obtain black
Color powder solid product 0.78g.BET tests show that its pore-size distribution is 30nm, and specific surface area is 935 m2 g-1, SEM surveys
Take temperature bright, the product for obtaining is porous foam shape material with carbon element, TEM and HRTEM analysis shows, product is three-dimensional grapheme structural carbon
Material, aperture is 30nm, and Graphene is drawn a bow to the full back and is shown to be 2 ~ 4 layer graphenes.XRD and Raman spectrum test show that product is 2 ~ 4 layers
Graphene-structured；XPS analysis show that product iron content 0.8%, cobalt content is 0.8%, and nitrogen content is 7.6%, 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.Oxygen is catalyzed under its 0.1mol/L KOH
Reducing property, oxygen initial reduction current potential is 0.77 V vs RHE, and electron transfer number is 3.57, and durability is slightly worse good；Magnesium air
Battery performance is up to 62 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 241 mW/cm2, in the sulfuric acid solution of 0.5 mol/L
It is 1.69V vs RHE that oxygen separates out take-off potential, and limiting current density reaches 40mA/cm2.Ultracapacitor specific capacitance is 225
F g-1, 10000 times capable of circulation still holding capacitor value 94%.
[embodiment 7] the other the same as in Example 3, simply pyrolysis temperature is 1100 DEG C.Obtain black powder solid product
0.56g.BET tests show that its pore-size distribution is 30nm, and specific surface area is 856 m2 g-1, SEM test show, the product for obtaining
For porous foam shape material with carbon element, TEM and HRTEM analysis shows, product is three-dimensional grapheme structure material with carbon element, and aperture is 30nm,
Graphene is drawn a bow to the full back and is shown to be 2 ~ 4 layer graphenes.XRD and Raman spectrum test show that product is 2 ~ 4 layers of graphene-structured；XPS
Analysis shows, product iron content 0.7%, cobalt content is 0.6%, and nitrogen content is 6.5%, and nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Say
Bright, product is the material of the three-dimensional grapheme structure of N doping.Catalytic oxidation-reduction performance under its 0.1mol/L KOH, oxygen starting
Reduction potential is 0.95 V vs RHE, and electron transfer number is 3.93, and durability is good；Magnesium air cell performance is up to 95 mW/
cm2.For hydrogen-oxygen fuel cell, its peak power is 437 mW/cm2, oxygen precipitation take-off potential is in the sulfuric acid solution of 0.5 mol/L
1.58V vs RHE, limiting current density reaches 80mA/cm2.Ultracapacitor specific capacitance is 327 F g-1, it is capable of circulation
10000 times still holding capacitor value 96%.
[embodiment 8] as described in Example 3, other conditions are identical, simply do template for 5 nm MgO particles with particle diameter
Agent, at this moment, because the particle diameter of template diminishes, its surface area increase, the consumption of mPBI increases, then the quality of mPBI and template
Than being changed to as 3:1, the product for obtaining is similar to Example 3, and simply in 5 ~ 10nm, specific surface area is 1487 m to its pore-size distribution2
g-1, it is 3 ~ 5 layers of three-dimensional nitrogen-doped graphene material, catalytic oxidation-reduction take-off potential is 0.96V vs under 0.1mol/L KOH
RHE, electron transfer number is 3.96, and durability is good；Magnesium air cell performance is up to 94 mW/cm2.For hydrogen-oxygen fuel cell its
Peak power is 467 mW/cm2, it is 1.64V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L, and the limit is electric
Current density reaches 100 mA/cm2.Ultracapacitor specific capacitance is 433F g-1, capable of circulation 10000 times still holding capacitor values
97%。
[embodiment 9] as described in Example 3, other conditions are identical, simply do mould for 50 nm MgO particles with particle diameter
Plate agent, at this moment because the particle diameter of template increases, its surface area reduces, and the consumption of mPBI is reduced, then the matter of mPBI and template
Amount ratio is changed to as 1:3, the product for obtaining is similar to Example 3, and simply in 50nm, specific surface area is 757 m to its pore-size distribution2 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, and electron transfer number is
3.92, durability is good；Magnesium air cell performance is up to 85 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 318 mW/
cm2, it is 1.66V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5mol/L, and limiting current density reaches 80mA/
cm2.Ultracapacitor specific capacitance is 283F g-1, 10000 times capable of circulation still holding capacitor value 95%.
[embodiment 10] uses MgO templates, and particle diameter is 30 nanometers, molysite and cobalt salt citrate, its matter with ABPBI
Amount is than being 2:1.Other experiment conditions are with embodiment 3.ABPBI is 1 with the mass ratio of template:1.Its result and the class of embodiment 3
Seemingly.Aperture is 30nm, 1018 m2 g-1, it is 2 ~ 4 layer graphenes.Iron content 0.7%, cobalt content 0.8%, nitrogen content is 7.6%, and
Nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Catalytic oxidation-reduction performance under its 0.1mol/LKOH, oxygen initial reduction current potential is 0.96V
Vs RHE, electron transfer number is 3.96, and durability is good；Magnesium air cell performance is up to 98 mW/cm2.For hydrogen-oxygen fuel cell
Its peak power is 432 mW/cm2, oxygen separates out take-off potential for 1.59V vs RHE in the sulfuric acid solution of 0.5 mol/L, the limit
Current density reaches 110mA/cm2.Ultracapacitor specific capacitance is 454F g-1, capable of circulation 10000 times still holding capacitor values
97%。
Other molysite, cobalt salt situation are similar to the above embodiments, simply change the ratio of PBI and molysite and cobalt salt mixture
.
Mole such as the 1 of other molysite, cobalt salt:2 or 2:1, other operating procedures with embodiment 3, urge by the product for obtaining
Change performance and be not so good as 1:1 it is good.
[embodiment 11] uses Fe2O3Or iron hydroxide nano particle is template, particle diameter is 30 nanometers, PBI ABPBI；Iron
Salt and cobalt salt cobalt nitrate and ABPBI mass ratioes are 1:1.Other experiment conditions are with embodiment 3.The quality of ABPBI and template
Than for 1:1.Its result is similar to Example 3.Product is three-dimensional grapheme structure material with carbon element, and aperture is 30nm, 927 m2 g-1,
For 2 ~ 4 layer graphenes.Iron content 0.9%, cobalt content 0.8%, nitrogen content is 8.6%, and nitrogen is pyridine type nitrogen and pyrroles's type nitrogen.Say
Bright, product is the material of the three-dimensional grapheme structure of N doping.Catalytic oxidation-reduction performance under its 0.1mol/LKOH, oxygen starting
Reduction potential is 0.97V vs RHE, and electron transfer number is 3.97, and durability is good；Magnesium air cell performance reaches 102mW/cm2。
For hydrogen-oxygen fuel cell, its peak power is 573 mW/cm2, oxygen precipitation take-off potential is in the sulfuric acid solution of 0.5 mol/L
1.58V vs RHE, limiting current density reaches 110 mA/cm2.Ultracapacitor specific capacitance is 449F g-1, it is capable of circulation
10000 times still holding capacitor value 97%.
Product prepared by the iron oxide of other particle diameters is similar with above-described embodiment result.
It is that template is also similar with above-described embodiment result with iron hydroxide nano particle.
Can generate with the nitrogen-atoms in PBI molecules because nanoparticle carbon monoxide, iron hydroxide receive the iron ion on surface
Coordinate bond, can play a part of fixed nitrogen, improve nitrogen content in product.
Other templates are similar with above example as the situation of template.
Claims (6)
1. a kind of method for preparing the iron cobalt with catalyzing cooperation effect and nitrogen ternary codope three-dimensional grapheme, its feature exists
In with the polybenzimidazoles of soluble full armaticity（PBI）React with molysite and cobalt salt mixed solution, prepare first PBI with
The complex of iron ion and cobalt ions, adds nano template in reaction mixture, complex is arranged in template rule of surface
Row, are pyrolyzed under inert gas shielding, go the techniques such as template agent removing to obtain iron cobalt and nitrogen ternary codope three-dimensional grapheme；Product
Can be used for redox reaction catalyst, fuel cell, metal-air battery oxygen reduction catalyst, electrolysis water oxygen and separate out catalysis
Agent, ultracapacitor etc..
2. the PBI of full armaticity according to claim 1, it is characterised in that：Whole polymer molecule forms a big π
Key, molecule belongs to rigidity, aroma type compound, such as poly-（2,5- benzimidazoles）（ABPBI）, it is poly- [2,2 '-(phenyl) -5,
5 '-bibenzimidaz sigmale] (mPBI) etc.；Polymer viscosity average molecular weigh is between 2～40,000；It is soluble in dimethyl acetamide
（DMAc）, dimethylformamide（DMF）, dimethyl sulfoxide (DMSO)（DMSO）, 1-METHYLPYRROLIDONE, in the organic solvent such as dimethylbenzene.
3. molysite according to claim 1 and cobalt salt, it is characterised in that can disperse or dissolve in intensive polar solvent
Salt；Can select, acetate, citrate, nitrate, hydrochloride, perchlorate, gluconate etc.；Molysite and cobalt salt
Mol ratio be 1:2~2:1；Molysite and cobalt salt are preferred：Acetate, citrate, nitrate, hydrochloride.
4. nano template according to claim 1 is：Nano level magnesia, Fe2O3With Fe (OH)3Deng template, its
Nano-particle diameter is characterised by 5～50nm, can be the shapes such as spherical, cylindrical, cube or polygon prism.
5. PBI according to claim 1 is with the mass ratio of molysite and cobalt salt mixture: 2:1~1:2；PBI and nanometer mould
The mass ratio of plate agent is 3:1～1:3；Hybrid mode is：PBI solution mixes with the mixed liquor of molysite and cobalt salt, heating, stirring
Reaction 5 ~ 8 hours, PBI forms complex solution with iron ion and cobalt ions；Template, stirring is added to be well mixed for 4 ~ 6 hours,
The lower heating of stirring steams solvent near dry, and vacuum drying is finely ground, is pyrolyzed under inert gas shielding, with Diluted Acid Washing removing removing template
Agent.
6. inert gas according to claim 1 is argon gas or high pure nitrogen, and pyrolysis temperature is 700～1100 DEG C.
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| CN107732248A (en) * | 2017-11-21 | 2018-02-23 | 盐城工学院 | The MOF materials of negative electrode of lithium ion battery and its application |
| CN108336374A (en) * | 2018-01-24 | 2018-07-27 | 桂林电子科技大学 | Nitrogenous carbon material of a kind of high-performance ternary Fe-Co-Ni codopes and its preparation method and application |
| CN108682872A (en) * | 2018-05-22 | 2018-10-19 | 江苏理工学院 | A kind of preparation method of the nitrogen co-doped grading-hole carbon nanosheet oxygen reduction catalyst of iron cobalt |
| CN111729680A (en) * | 2020-06-18 | 2020-10-02 | 同济大学 | High-efficiency bifunctional oxygen electrocatalyst with heterostructure and preparation and application thereof |
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| CN104108708A (en) * | 2014-07-25 | 2014-10-22 | 深圳新宙邦科技股份有限公司 | Nitrogen-doped graphene and preparation method thereof |
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| CN107732248A (en) * | 2017-11-21 | 2018-02-23 | 盐城工学院 | The MOF materials of negative electrode of lithium ion battery and its application |
| CN107732248B (en) * | 2017-11-21 | 2020-11-06 | 盐城工学院 | MOF material of lithium ion battery cathode and application thereof |
| CN108336374A (en) * | 2018-01-24 | 2018-07-27 | 桂林电子科技大学 | Nitrogenous carbon material of a kind of high-performance ternary Fe-Co-Ni codopes and its preparation method and application |
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| CN108682872A (en) * | 2018-05-22 | 2018-10-19 | 江苏理工学院 | A kind of preparation method of the nitrogen co-doped grading-hole carbon nanosheet oxygen reduction catalyst of iron cobalt |
| CN111729680A (en) * | 2020-06-18 | 2020-10-02 | 同济大学 | High-efficiency bifunctional oxygen electrocatalyst with heterostructure and preparation and application thereof |
| CN112086652A (en) * | 2020-09-15 | 2020-12-15 | 香港科技大学深圳研究院 | Hollow carbon sphere/graphene bifunctional catalyst and preparation method and application thereof |
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