CN106744850A - 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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- 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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- 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 of soluble full armaticity（PBI）It is carbon source and nitrogen source, transition metal salt obtains the complex that PBI is formed with transition metal ions with PBI solution reactions, nano-calcium carbonate is added to do template in mixed liquor, it is well mixed, concentrates, makes 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 insertion can strengthen mass transfer.PBI viscosity average molecular weighs are 2 ~ 40,000；PBI is 1 with the mass ratio of transition metal salt:2~2:1；Template is calcium carbonate, the nm of particle diameter 30 ~ 100；PBI is 2 with template mass ratio: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 separate out the fields such as catalyst, ultracapacitor.
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
Although two-dimensional graphene has excellent performance and various potential applications, however, pole again between two-dimensional graphene
Easy layer-layer is overlapped mutually to form graphite-structure, so that its excellent performance is lost.Therefore, the preparation of three-dimensional grapheme and property
Can study hotspot of the research as current field of nanometer material technology.Research finds that the Graphene of N doping is due in graphene molecules
Polarity between C-N keys, makes the cloud density in graphene molecules change, therefore nitrogen-doped graphene catalytic oxidation-reduction etc.
Performance is better than Graphene.
Contribute to the increase of active sites by doping metals, metal further increases its catalytic with the synergy of nitrogen
Can, strengthen catalysis activity and improve stability（Zhao Y, et al. J Am Chem Soc (JACS), 2012,
134: 19528）.Therefore metal-nitrogen-Spectra of Carbon Clusters（M-N-C）Research is taken seriously, and research shows, in Graphene adulterate nitrogen and
Transition metal（Such as iron, cobalt etc.）Afterwards, more avtive spots can be formed, so as to the catalysis of product catalytic oxidation-reduction can be improved further
Activity.The transition metal and nitrogen co-doped catalyst of three-dimensional structure are particularly formed, its two-dimensional slice knot can be preferably kept
, without superposition occurring and assembling, its catalytic active site is more, and loose structure is conducive to the transmission of fortification substance for structure.Due to it
Unique advantage, such material is considered as most one of development potentiality oxygen reduction catalyst, is 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（Lin L, et al. ACS Catal (American Chemical Societies-urge
Change), 2016,6: 4449）, cobalt doped（Gao J, et al. Ind. Eng. Chem. Res (grind by chemical industry and engineering
Study carefully), 2015,54: 7984）With 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 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）Application have document report.Metal, N doping
Graphene preparation method have a lot：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（As ethylenediamine,
Pyridine etc.）M-N-C clusters are obtained with transition metal salt（Lefe vre M, et al. Science (science) 2009,324:
71）；With melamine and etal molysite Fe-N-C cluster catalysts are prepared by high temperature pyrolysis（Lai Q X, et al.
ACS Appl. Mater. Interfaces (American Chemical Society-application material interface), 2015,7: 18170）, it is also useful
Polypyrrole and etal molysite prepare Fe-N-C cluster catalysts by high temperature pyrolysis（Zheng Y P, et al. Nano
Energy (the nanometer energy), 2016,30: 433）；A class M/N/C is prepared with the heat treatment of polyaniline combination iron and cobalt to be catalyzed
Agent (Wu G, et al. Science (science), 2011,332:443) etc..
The present invention is a kind of preparation with the transition metal and nitrogen co-doped multistage pore canal three-dimensional graphite for strengthening mass transfer effect
The method of alkene.With the polybenzimidazoles of soluble full armaticity（PBI）Reacted with molysite or cobalt salt solution, the cooperation of generation
Thing, nano-calcium carbonate template, reaction mixture is well mixed with calcium carbonate template, is 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 of Decomposition of Calcium Carbonate generation is discharged and to form aperture and mutually passed through with the macropore for going to generate after removing template
Logical, the product of preparation is transition metal and the three-dimensional grapheme of nitrogen co-doped multistage pore canal insertion；Product is used for redox
Catalysts, fuel cell, metal-air battery oxygen reduction catalyst, electrolysis water oxygen separate out catalyst, ultracapacitor etc.
Field.
The transition metal and nitrogen co-doped multistage pore canal three-dimensional grapheme for obtaining, due to transition metal and nitrogen co-doped and three
Dimension loose structure so that the increase of its specific surface area, catalytic active site increase.Due to Graphene big π bond structures in itself, iron or cobalt
Inside graphene molecules, whole molecule forms big π bond structures to the polar bond formed with nitrogen, and the delocalization energy of its molecular orbit increases
Greatly, the energy level between HUMO tracks and LOMO tracks diminishes so that the environment of its catalytic active center is especially as porphyrin, phthalocyanine are matched somebody with somebody
The environment of compound, can so substantially reduce the overpotential of catalytic oxidation-reduction, and the catalysis thermodynamic property of catalyst gets a promotion；
Furthermore, the three-dimensional porous structure of multistage pore canal insertion is conducive to strengthening mass transfer so that electrode reaction dynamic performance is improved.
It is of the invention with simple itrogenous organic substance and transient metal complex or nitrogen containing polymer, such as pollopas, melamine
Metal-nitrogen-Spectra of Carbon Clusters difference that polyimide resin etc. is prepared with transition metal mixture pyrolysis is 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, its metal
Easily removed by acid, so durability is not good enough, especially because metal-nitrogen-Spectra of Carbon Clusters is not loose structure its mass transfer effect
It is really bad, so, its catalysis activity and durability are not good enough.Formation is pyrolyzed together with transition metal with polyaniline, polypyrrole
The difference of catalyst is, polyaniline with polypyrrole because it can not be dissolved, so, it cannot be covered with paint, lacquer, colour wash, etc. on template surface,
So its operating characteristics is deteriorated, and PBI is soluble, and its very easy covering with paint is on template surface, and its operating performance is good.
The content of the invention
The present invention is a kind of preparation with the transition metal and nitrogen co-doped multistage pore canal three-dimensional graphite for strengthening mass transfer effect
The method of alkene.With the polybenzimidazoles of soluble full armaticity（PBI）Macromolecule reacts with transition metal salt solution, generation
PBI and transition metal ions complex, complex reaction mixture are well mixed in nano-calcium carbonate template, and complex is in mould
Plate agent rule of surface is arranged, and under inert gas shielding, pyrolysis, complex forms transition metal and nitrogen by dehydrogenation-cyclisation-carbonization
The Graphene of codope, the carbon dioxide of Decomposition of Calcium Carbonate generation discharges that to form aperture mutual with the macropore for going to generate after removing template
Insertion, prepares the three-dimensional grapheme of transition metal and nitrogen co-doped multistage pore canal insertion；The product is used for redox reaction
Catalyst, fuel cell, metal-air battery oxygen reduction catalyst, electrolysis water oxygen separate out the fields such as catalyst, ultracapacitor.
The transition metal and nitrogen co-doped multistage pore canal three-dimensional grapheme for obtaining, due to transition metal and the co-doped of nitrogen
And three-dimensional porous structure so that the increase of its specific surface area, catalytic active site increase.Due to Graphene big π bond structures in itself, mistake
Metal is crossed with the polar bond of nitrogen formation inside graphene molecules, whole molecule forms big π bond structures, the delocalization of its molecular orbit
Can increase, the energy level between HUMO tracks and LOMO tracks diminishes so that the environment of its catalytic active center is especially as porphyrin, phthalein
The environment of cyanines complex, can so substantially reduce the overpotential of catalytic oxidation-reduction, and the catalysis thermodynamic property of catalyst is obtained
Lifting；Furthermore, the three-dimensional porous structure of multistage pore canal insertion is conducive to strengthening mass transfer so that electrode reaction dynamic performance is obtained
Improve.
It is of the invention with simple itrogenous organic substance and transient metal complex or nitrogen containing polymer, such as pollopas, melamine
Metal-nitrogen-Spectra of Carbon Clusters difference that polyimide resin etc. is prepared with transition metal mixture pyrolysis is that metal-nitrogen-Spectra of Carbon Clusters is not
It is graphene-structured, rather than transition metal ions and the codope of nitrogen, the effect without big π, so catalytic performance is not high, its gold
Category is easily removed by acid, 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, so, its catalysis activity and durability are not good enough.It is pyrolyzed together with transition metal and is formed with polyaniline, polypyrrole
The difference of catalyst be, polyaniline with polypyrrole because it can not be dissolved, so, it cannot be covered with paint, lacquer, colour wash, etc. in template table
Face, so its operating characteristics is deteriorated, and PBI is soluble, and on template surface, complex can be advised for its very easy covering with paint
Template surface then is arranged in, only in this way, a series of heat chemistrys such as dehydrogenation-cyclisation-carbonization occurs in pyrolytic process
Nitrogen-doped graphene structure can be obtained after change.
Viscosity average molecular weigh being soluble between 20,000~40,000 prepared by full armaticity PBI solid phase methods 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 small
Its viscosity is too small, it is impossible to coated die plate agent well.
The method of the preparation of transition metal and nitrogen co-doped multistage pore canal three-dimensional grapheme is：It is appropriate that the degree of polymerization is prepared first
Full armaticity PBI, PBI dissolvings are formed solution in a solvent, to adding a certain amount of transition metal salt solution in solution,
Heating, stirring reaction 5 ~ 8 hours, obtain the complex reaction solution that PBI is formed with transition metal ions, are added in the reaction solution
Appropriate particle diameter is the template calcium carbonate of 30 ~ 100 nm, and stirring makes it be sufficiently mixed uniformly.Under agitation, heat, at leisure
Solvent is steamed near dry, is transferred in vacuum drying chamber and is dried at 60 ~ 120 DEG C.It is finely ground in mortar, porcelain boat bottom is laid in, put
Enter in electric tube furnace, under argon gas protection, at 800~1100 DEG C, be pyrolyzed 2 ~ 3h.Treat that furnace temperature is cooled to room temperature, take out, with dilute
Sour repeatedly washing dries to obtain product to go template agent removing, suction filtration to be washed with deionized water only.
In the reaction of PBI and transition metal salt, the addition of transition metal salt is critically important, and it determines preparation for the present invention
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 macromolecules, it is ensured that four imidazole ring one transition metal ions of correspondence are advisable, experiment hair
Existing PBI is 1 with the mass ratio of transition metal salt:2~2:Between 1, the change of its proportioning is determined by different types of transition metal salt
It is fixed.
In the present invention, template is nano-calcium carbonate particles.Transition metal-nitrogen co-doped multistage pore canal can be prepared
Three-dimensional grapheme, the particle diameter and addition of template are crucial：The particle diameter of template determines the aperture of the material of preparation；Mould
The addition of plate agent determines the number of plies of the Graphene of preparation, the formation of aperture and performance.Template addition very little, can only be obtained
To transition metal and nitrogen co-doped porous carbon materials, it is impossible to obtain the material of multi-layer graphene structure；Add excessively, obtain
Transition metal and the nitrogen co-doped three-dimensional grapheme number of plies very little, after removing template agent removing, are easily collapsed, and be can only obtain broken broken
Piece.The granularity of template has a certain impact to the amount for adding template, and granularity is small, its specific surface area it is big, it is necessary to mould
The amount of plate agent is just few；, whereas if granularity it is big, it is necessary to template amount it is just many；Consider that Decomposition of Calcium Carbonate can produce aperture,
The aperture of aperture in 2 ~ 5 nm, so, the particle diameter of calcium carbonate selects 30 ~ 100 nm；The consumption of template is：PBI and template
Mass ratio be 2:1~1:4；Ratio change is relevant with the granularity of template.Under inert gas shielding be pyrolyzed, it is regularly arranged
The complex on template surface can occur a series of thermal chemical reactions such as dehydrogenation-cyclisation-carbonization, finally give product.Insertion
The formation of pore channels and the amount of nano-calcium carbonate and decomposition during pyrolysis it is relevant, pyrolysis temperature below 800 DEG C, calcium carbonate
Do not decompose, it is impossible to form the passage of aperture insertion.The aperture of aperture is relevant with the amount of calcium carbonate, the carbon dioxide that calcium carbonate is produced
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 for being formed is just
It is small.It is pyrolyzed under inert gas shielding, pyrolysis temperature is：800~1100 DEG C；The formation of aperture and pore size are calcium carbonate point
The carbon dioxide generation of generation is solved, the factor such as amount and pyrolysis temperature of calcium carbonate determines aperture and the insertion performance of aperture.Should
The porous material of class multistage insertion has the mass transfer to have invigoration effect to 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 is incomplete, is produced
The electric conductivity of product is poor；Below 800 DEG C, calcium carbonate is not decomposed, it is impossible to form the passage of aperture insertion.Pyrolysis temperature is reached most
After good temperature, then to raise pyrolysis temperature its performance constant, but, oxidation reaction, institute can occur when inert gas shielding is insufficient
It is unsuitable too high with pyrolysis temperature.
The Graphene characterizing method of the nitrogen co-doped multistage pore canal of 3-D transition metal is：Aperture, porosity, pore volume and ratio
Surface area nitrogen adsorption instrument（BET）, the Morphology analysis SEM of product（SEM）It is micro- with projection electron
Mirror（TEM）, the Graphene number of plies can be by high power transmission electron microscope（HRTEM）Characterized with Raman spectrum.The stone of product
Blackization degree, graphene-structured and the number of plies can use X-ray powder diffraction（XRD）, Raman spectrum characterizes.The element of product
Composition, valence state can use x-ray photoelectron spectroscopy（XPS）Characterized, used rotating disk electrode (r.d.e)（RDE）Carry out test product
Catalytic oxidation-reduction reaction（ORR）Performance, water electrolysis oxygen evolution reaction（EOR）, evolving hydrogen reaction（EHR）With the capacitive property of product
Test can use cyclic voltammetric（CV）, linear volt-ampere（LSV）, Tafel curve and charge-discharge performance test.Product is used as urging
The durability test of agent can use CV, LSV and chronoa mperometric plot（i-t）.The catalytic performance of product finally needs assembling
Metal-air battery, hydrogen-oxygen fuel cell, the electrolytic cell of electrolysis water, ultracapacitor and sensor test 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) (100 g), lower 160 DEG C of nitrogen protection stirs 1h to remove unnecessary moisture and air.By DABz (4 g, 18.7
Mmol) and M-phthalic acid (3.1 g, 18.7 mmol) is well mixed, it is slowly added in there-necked flask.Control nitrogen
Gas velocity, prevents DABz to be oxidized, while reaction temperature being lifted to 200 DEG C and continuing insulation, stirring reaction 5-8 h.With
The increase in reaction time, polymerization system gradually becomes sticky.Stop reaction when viscosity is suitable, reaction mixture is slowly transferred to
Reeled off raw silk from cocoons in a large amount of deionized waters, clean, dry, crushed, deionized water repeatedly with removing polyphosphoric acids and unreacted reacted by washing
Thing, that is, obtain mPBI, 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 well mixed in mortar, being fully ground, it is transferred to in nitrogen protection, the there-necked flask of agitator.
Lead to the min of nitrogen 15 to drain the air in flask.N2Protection, under stirring, 225 DEG C of heating of oil bath keep 3h.Taken out after cooling,
It is finely ground, N2Under protection, heating in electric furnace is warmed up to 270-275 DEG C, keeps 3h.Be cooled to room temperature, by product take out, it 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, simply with 3,4- diaminobenzoic acids（DABA）Substitute
DABz and M-phthalic acid.Only it is that can obtain ABPBI 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 particle diameter 30nm, uses ferric acetate；Ferric acetate is 1 with the mass ratio of mPBI:
2, it is 1 with mPBI and calcium carbonate template mass ratio:As a example by 1：In the beaker of 250mL, the mPBI of 1g is added（Viscosity average molecular weigh
2 ~ 30,000）With 20 mL DMAc, heating, stirring dissolve it, the 20mL DMAc solution of 0.5 g ferric acetates is added under agitation,
At 80 DEG C ~ 100 DEG C of insulation, stirring reaction 5 ~ 8 hours is slowly added into the calcium carbonate granule of the nanometer that 1 g particle diameters are 30 nm, stirs
Mix 4 ~ 6 hours, it is uniformly dispersed.The viscous liquid for obtaining is heated to be concentrated under agitation and closely done, in vacuum drying chamber
Dried at 60 ~ 120 DEG C, solid is finely ground in mortar, be transferred in porcelain boat, under argon gas protection, be pyrolyzed at 900 DEG C in the electric furnace
2-3h, treats that furnace temperature is down to room temperature, takes out, finely ground, obtains black powder solid, is transferred in 250 mL conical flasks, adds 70
The watery hydrochloric acid of mL, heating, stirring 24h, suction filtration is so washed three times with watery hydrochloric acid, is washed to neutrality, is dried to obtain black powder
The g of shape solid product 0.72.BET tests show that its pore-size distribution is 30 nm, and the nm specific surface areas of aperture 2 ~ 4 are 1131 m2 g-1, SEM test show, the product for obtaining be porous foam shape carbon material, TEM and HRTEM analysis shows, product is three-dimensional graphite
Alkene structure carbon material, aperture is 30 nm, and the nm Graphenes of aperture 2 ~ 4 are drawn a bow to the full back and are shown to be 2 ~ 4 layer graphenes.XRD and Raman spectrum
Test shows that product is 2 ~ 4 layers of graphene-structured；XPS analysis show that product iron content 1.7%, nitrogen content is 6.3%, and nitrogen
It is pyridine type nitrogen and pyrroles's type nitrogen.Illustrate, product is the material of the multistage pore canal three-dimensional grapheme structure of iron-nitrogen co-doped.Its
Catalytic oxidation-reduction performance under 0.1 mol/L KOH, oxygen initial reduction current potential is 0.99 V vs RHE, and electron transfer number is
3.98, durability is good；Magnesium air cell performance is up to 103 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 584 mW/
cm2, it is 1.56 V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L, and limiting current density reaches 100
mA/cm2.Ultracapacitor 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 simply mPBI is changed into 2 with the quality of calcium carbonate：1,
It is similarly obtained the solid powder of black.BET tests show that its pore-size distribution is still 30nm, the nm of aperture 2 ~ 4, but its specific surface
It is long-pending then be reduced to 732 m2 g-1, its SEM and TEM tests show, are the carbon material of loose structure inside it, and 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 is 0.83 V vs RHE, and electron transfer number is 3.59, resistance to
Long property is good；Magnesium air cell performance is up to 65 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 231 mW/cm2, 0.5
It is 1.67 V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of mol/L, and limiting current density reaches 40 mA/cm2.It is super
Level 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 simply mPBI is changed into 1 with the quality of calcium carbonate：2,
It is similarly obtained the solid powder of black.BET is tested and shown, its pore size distribution range 10 ~ 30 nm, the nm of aperture 3 ~ 5, but it compares
Surface area is then reduced to 812 m2 g-1, its SEM and TEM tests show, are the carbon material of loose structure inside it, and 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 is 0.84 V vs RHE, and electron transfer number is
3.65, durability is good；Magnesium air cell performance is up to 76 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 238 mW/
cm2, it is 1.65 V vs RHE that oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L, and limiting current density reaches 50
mA/cm2.Ultracapacitor 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 simply pyrolysis temperature is respectively 700 DEG C.Obtain black
The powdered g of solid product 0.72 of color.BET tests show that its pore-size distribution is 30 nm, the nm of aperture 2 ~ 4, and specific surface area is 958
m2 g-1, SEM test show, the product for obtaining be porous foam shape carbon material, TEM and HRTEM analysis shows, product for three-dimensional
Graphene structural carbon material, aperture is 30 nm, and the nm of aperture 2 ~ 4, Graphene is drawn a bow to the full back and is shown to be 2 ~ 4 layer graphenes.XRD and Raman
Spectrum test shows that product is 2 ~ 4 layers of graphene-structured；XPS analysis show that product iron content 1.6%, nitrogen content is 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 is 0.83 V vs RHE, and electron transfer number is 3.54, and durability is slightly
Differ from；Magnesium air cell performance is up to 56 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 146 mW/cm2, 0.5 mol/L
Sulfuric acid solution in oxygen to separate out take-off potential be 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, simply pyrolysis temperature is 1100 DEG C.Obtain black powder solid product
0.58 g.BET tests show that its pore-size distribution is 30 nm, and the nm of aperture 2 ~ 4, specific surface area is 786 m2 g-1, SEM test tables
Bright, the product for obtaining is porous foam shape carbon material, TEM and HRTEM analysis shows, product is three-dimensional grapheme structure carbon materials
Material, aperture is 30 nm, and the nm of aperture 2 ~ 4, Graphene is drawn a bow to the full back and is shown to be 2 ~ 4 layer graphenes.XRD and Raman spectrum are tested and shown,
Product is 2 ~ 4 layers of graphene-structured；XPS analysis show that product iron content 1.5%, nitrogen content is 5.2%, 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.Oxygen is catalyzed under its 0.1 mol/L KOH
Reducing property, oxygen initial reduction current potential is 0.95 V vs RHE, and electron transfer number is 3.94, and durability is good；Magnesium air electricity
Pond performance is up to 92 mW/cm2.For hydrogen-oxygen fuel cell, its peak power is 312 mW/cm2, 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.Ultracapacitor 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, simply with particle diameter for 50 nm calcium carbonate granules do
Template, at this moment, because the particle diameter of template becomes big, its surface area increases small, the consumption reduction of mPBI, then mPBI and template
Mass ratio is changed to be 1:2, the product for obtaining is similar to Example 4, and simply its pore-size distribution compares table in 50 nm, the nm of aperture 4 ~ 5
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 is 3.92, and durability is good；Magnesium air cell 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 oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L
Vs RHE, limiting current density reaches 70 mA/cm2.Ultracapacitor 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 simply 100 nm calcium carbonate granules with particle diameter
Template is done, at this moment because the particle diameter of template increases, its surface area reduces, and the consumption of mPBI is reduced, then mPBI and template
Mass ratio be changed to be 1:4, the product for obtaining is similar to Example 4, and simply in 100nm, the nm of aperture 5 compares table to its pore-size distribution
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 is 3.91, and durability is good；Magnesium air cell 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 oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L
Current density reaches 70 mA/cm2.Ultracapacitor specific capacitance is 265 F g-1, it is recycled 10000 still holding capacitor values
95%。
[embodiment 11] uses calcium carbonate template, and particle diameter is 30 nanometers, uses citric acid cobalt, and it is with the mass ratio of ABPBI
1:1.Other experiment conditions are with embodiment 4.ABPBI is 1 with the mass ratio of template:1.Its result is similar to Example 4.Aperture
It is 30 nm, aperture 2 ~ 4 nm, 1264 m2 g-1, it is 2 ~ 4 layer graphenes.Cobalt content 1.6%, nitrogen content is 6.8%, and nitrogen is pyrrole
Pyridine type nitrogen and pyrroles's type nitrogen.Catalytic oxidation-reduction performance under its 0.1 mol/LKOH, oxygen initial reduction current potential is 0.99 V vs
RHE, electron transfer number is 3.97, and durability is good；Magnesium air cell 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 oxygen separates out take-off potential in the sulfuric acid solution of 0.5 mol/L
Current density reaches 80 mA/cm2.Ultracapacitor specific capacitance is 389 F g-1, it is recycled 10000 still holding capacitor values
97%。
Other cobalt salts with mPBI other mass ratioes under situation, its operating procedure with embodiment 4, urge by the product for obtaining
Change performance to be similar to.
Other molysite, cobalt salt situation are similar to the above embodiments, simply change the ratio of PBI and molysite or cobalt salt.
The situation of the product that ABPBI is mixed with the calcium carbonate of other particle diameters, same to above-described embodiment, its performance is slightly better than
With the product of mPBI under similarity condition.
Claims (6)
1. a kind of polybenzimidazoles with soluble full armaticity（PBI）The complex that macromolecule is formed with transition metal ions
Cover with paint, lacquer, colour wash, etc. in nano template calcium carbonate surface, be pyrolyzed, go the techniques such as removing template to prepare transition metal and nitrogen co-doped multi-stage porous
The preparation method of the three-dimensional grapheme of road insertion, it is characterised in that：PBI is the soluble of full armaticity, PBI solution and transition
Slaine hybrid reaction obtains complex, adds nano-calcium carbonate template, is uniformly mixed, make PBI and transition metal from
There is dehydrogenation-cyclisation-carbon in template top finishing and regularly arranged, pyrolysis under inert gas shielding in the complex that son is formed
The thermochemical process such as change, remove template agent removing, obtain the three-dimensional grapheme of transition metal and nitrogen co-doped multistage pore canal insertion；It is described
Transition metal and nitrogen co-doped multistage pore canal insertion three-dimensional grapheme be used for redox reaction catalyst, fuel cell,
Metal-air battery oxygen reduction catalyst, electrolysis water oxygen separate out catalyst, 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.；Its structural formula is as follows：
The structural formula of the structural formula mPBI of ABPBI
Polymer viscosity average molecular weigh is between 2~40,000；It is soluble in dimethylacetylamide（DMAc）, dimethylformamide
（DMF）, dimethyl sulfoxide (DMSO)（DMSO）, 1-METHYLPYRROLIDONE, in the organic solvent such as dimethylbenzene.
3. transition metal salt according to claim 1, is acetate, nitrate, hydrochloride, the citric acid of transition metal
Salt, perchlorate or gluconate etc., it is characterised in that can disperse or dissolve salt in intensive polar solvent, preferably molysite or
Cobalt salt.
4. nano template according to claim 1 is calcium carbonate, it is characterised in that particle diameter is in 30~100 nm, Ke Yishi
The nano particle of the shape such as spherical, cylindrical, cube or polygon prism.
5. PBI according to claim 1 is with the mass ratio of transition metal salt: 2:1~1:2；With nano template carbonic acid
The mass ratio of calcium is 2:1~1:4；Hybrid mode is：PBI solution and transition metal salt solution, heating, stirring reaction 5 ~ 8 are small
When, PBI forms complex solution with transition metal ions；Calcium carbonate template, stirring is added to be well mixed for 4 ~ 6 hours, stirring
Lower heating steams solvent near dry, vacuum drying, finely ground, is pyrolyzed under inert gas shielding, with Diluted Acid Washing removing template agent removing.
6. inert gas according to claim 1 is argon gas or high pure nitrogen, and pyrolysis temperature is 800~1100 DEG C.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108059145A (en) * | 2017-12-14 | 2018-05-22 | 同济大学 | A kind of preparation method of multi-stage porous N doping porous carbon |
| CN108940336A (en) * | 2018-07-03 | 2018-12-07 | 山西大学 | A kind of cobalt-based carbon nanocatalyst and its preparation method and application containing N doping |
| CN110364705A (en) * | 2019-06-20 | 2019-10-22 | 华南理工大学 | A kind of transition metals cobalt is monatomic/cluster insertion nitrogen-doped carbon framework material and its preparation method and application |
| CN111729684A (en) * | 2020-07-21 | 2020-10-02 | 南京大学 | Hierarchical porous Co-N-C type catalyst and preparation method and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5618615A (en) * | 1994-07-06 | 1997-04-08 | Matsushita Electric Industrial Co., Ltd. | Graphite layer material |
| 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 |
| CN104475172A (en) * | 2014-11-21 | 2015-04-01 | 东华大学 | Preparation method and application of three-dimensional porous heteroatom-doped graphene |
-
2016
- 2016-12-28 CN CN201611236544.3A patent/CN106744850B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5618615A (en) * | 1994-07-06 | 1997-04-08 | Matsushita Electric Industrial Co., Ltd. | Graphite layer material |
| 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 |
| CN104475172A (en) * | 2014-11-21 | 2015-04-01 | 东华大学 | Preparation method and application of three-dimensional porous heteroatom-doped graphene |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108059145A (en) * | 2017-12-14 | 2018-05-22 | 同济大学 | A kind of preparation method of multi-stage porous N doping porous carbon |
| CN108940336A (en) * | 2018-07-03 | 2018-12-07 | 山西大学 | A kind of cobalt-based carbon nanocatalyst and its preparation method and application containing N doping |
| CN108940336B (en) * | 2018-07-03 | 2020-06-12 | 山西大学 | Nitrogen-doped cobalt-based carbon nano catalyst and preparation method and application thereof |
| CN110364705A (en) * | 2019-06-20 | 2019-10-22 | 华南理工大学 | A kind of transition metals cobalt is monatomic/cluster insertion nitrogen-doped carbon framework material and its preparation method and application |
| CN111729684A (en) * | 2020-07-21 | 2020-10-02 | 南京大学 | Hierarchical porous Co-N-C type catalyst and preparation method and application thereof |
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