CN106981671A - A kind of three-dimensional porous nitrogen-doped graphene and its preparation method and application - Google Patents
A kind of three-dimensional porous nitrogen-doped graphene and its preparation method and application Download PDFInfo
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- CN106981671A CN106981671A CN201710246261.5A CN201710246261A CN106981671A CN 106981671 A CN106981671 A CN 106981671A CN 201710246261 A CN201710246261 A CN 201710246261A CN 106981671 A CN106981671 A CN 106981671A
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Abstract
The invention provides a kind of preparation method of three-dimensional porous nitrogen-doped graphene, carbon source and nitrogen source are used as using amino acid small molecule simultaneously, utilize transition-metal catalyst, it is fired successively, grinding, pickling, deionization is washed, after absolute ethyl alcohol is washed and dried, obtain three-dimensional porous nitrogen-doped graphene, nitrogen source and pore-creating activator need not be added in preparation process, one-step method just can form porous nitrogen-doped graphene in situ, the three-dimensional porous nitrogen-doped graphene of different-shape can be obtained according to the species difference of transition-metal catalyst, this method is simple and convenient, it is with low cost, it is easy to large-scale production, and fuel cell can be widely applied to, the field such as lithium ion battery and ultracapacitor.
Description
Technical field
The present invention relates to new carbon technical field, more particularly to a kind of preparation side of three-dimensional porous nitrogen-doped graphene
Method and three-dimensional porous nitrogen-doped graphene and its application.
Background technology
Graphene is the two-dimensional material being made up of single layer of carbon atom, is by mechanically pulling off in 2004 by Britain professor Geim
Method has been surprisingly found that.Graphene has excellent electric conductivity, the mechanical strength of superelevation, huge specific surface area etc., Zi Congfa because of it
Just cause research boom since existing and be widely used in multiple fields.Graphene has weight in the negative electrode and anode of fuel cell
Apply.Numerous studies show that graphene can be directly as cathodic oxygen reduction catalyst, and shows higher activity；In addition
Graphene is alternatively arranged as the excellent carrier of catalyst, the consumption of noble metal is thus reduced, so as to reduce fuel cell cost.
In order to further lift the performance of graphene, people begin one's study the graphene with three-dimensional structure.Compared to two
Graphene is tieed up, three-dimensional grapheme has more electron propagation ducts, more excellent stability, and because it is unique porous
Structure cause three-dimensional grapheme have bigger specific surface area, be electrons/ions, gas and liquid transmission and storage it is more
Space.In addition, result of study shows, nitrogen atom doping is entered into graphene, electronics of the graphene at fermi level can be improved
Cloud density, so as to change the electric conductivity of graphene；On the other hand because nitrogen atom doping can be introduced suitably in graphene base body
Defect, these defects can further increase the active site and storage site of graphene.
Preparing the method for graphene at present mainly includes mechanical stripping method, oxidation-reduction method, chemical vapour deposition technique and table
Face epitaxial growth method.Generally require additionally to add nitrogen source for nitrogen atom doping is entered into graphene.In addition, preparing three-dimensional porous shape
Graphene when generally using masterplate method or add highly basic etc. and be used as pore creating material.It can thus be seen that tradition preparation is three-dimensional more
Pore structure nitrogen-doped graphene complex steps, preparation condition require higher, due to a large amount of chemical reagent particularly toxic reagent etc.
Polluted using to environment, synthesis cost is high, it is difficult to mass produce.
The content of the invention
In view of this, it is an object of the invention to provide a kind of preparation method of three-dimensional porous nitrogen-doped graphene, a step
Method just can be formed in situ porous nitrogen-doped graphene, simple and convenient, with low cost, be easy to large-scale production, while environmental protection,
The consumption of the energy is reduced, and the fields such as fuel cell, lithium ion battery and ultracapacitor can be widely applied to.
In order to realize foregoing invention purpose, the present invention provides following technical scheme：
The invention provides a kind of preparation method of three-dimensional porous nitrogen-doped graphene, comprise the following steps：
(1) amino acid is mixed with transition metal salt and water, obtains mixed solution；
(2) mixed solution for obtaining the step (1) heats removing moisture under agitation, obtains solid mixture；
(3) carry out calcination process after the solid mixture grinding obtained the step (2) and obtain N doping carbon dust；
(4) successively through pickling, deionization washing, absolute ethyl alcohol after the N doping carbon dust grinding obtained the step (3)
After washing and drying, three-dimensional porous nitrogen-doped graphene is obtained.
Preferably, amino acid includes glycine, alanine, glutamic acid, serine, arginine and relied in the step (1)
One or more of mixtures in propylhomoserin.
Preferably, it is one or more of in soluble-salt of the transition metal salt including Fe, Co and Ni in the step (1)
Mixture.
Preferably, transition metal salt includes FeCl in the step (1)2、FeCl3、Ni(NO3)2、NiCl2、Ni
(CH3COO)2、CoCl2With Co (NO3)2In one or more of mixtures.
Preferably, the mass ratio of amino acid and transition metal salt is 1 in the step (1):1~1:10.
Preferably, the time of mixing is 12~24h in the step (1).
Preferably, the rotating speed of stirring is 100~800rpm in the step (2)；The temperature of heating is in the step (2)
50~80 DEG C.
Preferably, calcination process is in the step (3)：In N2Under atmosphere, heated up with 2~10 DEG C/min heating rate
To 750~1050 DEG C, 60~180min is incubated, then room temperature is down to 2~10 DEG C/min rate of temperature fall.
It is described present invention also offers the three-dimensional porous nitrogen-doped graphene that preparation method described in above-mentioned technical proposal is obtained
Three-dimensional porous nitrogen-doped graphene has porous three-dimensional crosslinked network, the carbon hexatomic ring of the three-dimensional porous nitrogen-doped graphene
Carbon atom in structure is by pyridine nitrogen, pyrroles's nitrogen, graphitization nitrogen and nitrogen oxide substitution.
The three-dimensional porous nitrogen-doped graphene that is obtained present invention also offers preparation method described in above-mentioned technical proposal or on
Three-dimensional porous nitrogen-doped graphene described in technical scheme is stated as the application of fuel-cell catalyst or catalyst carrier.
The invention provides a kind of preparation method of three-dimensional porous nitrogen-doped graphene, using amino acid small molecule simultaneously as
Carbon source and nitrogen source, using transition-metal catalyst, fired successively, grinding, pickling, deionization washing, absolute ethyl alcohol washing and
After drying, three-dimensional porous nitrogen-doped graphene is obtained.The method that the present invention is provided is in preparation process without additionally adding nitrogen
Source and pore-creating activator, one-step method just can form porous nitrogen-doped graphene in situ；And adjustable transition-metal catalyst
Species, obtains the three-dimensional porous nitrogen-doped graphene of different-shape, when the transition-metal catalyst used is iron class, obtains
It is curling, the three-dimensional porous nitrogen-doped graphene of gauze-like, when the transition-metal catalyst used is cobalt class, what is obtained is
The three-dimensional porous nitrogen-doped graphene of " onion shape ", when the transition-metal catalyst used is nickel class, what is obtained is " honeycomb
The three-dimensional porous nitrogen-doped graphene of shape ".Preparation method that the present invention is provided is simple and convenient, with low cost, be easy to extensive life
Production, and the fields such as fuel cell, lithium ion battery and ultracapacitor can be widely applied to.
Three-dimensional porous nitrogen-doped graphene prepared by the present invention has three-dimensional cross-linked loose structure, three-dimensional cross-linked net
Network structure can provide good mechanical stability for graphene, and three-dimensional cross-linked graphene can be cloudy for fuel cell as catalyst
Pole oxygen reduction reaction provides more electric transmission paths, to accelerate the kinetic rate of reaction, three-dimensional porous N doping graphite
The porous of alkene can significantly improve the specific surface area of graphene, can increase the active sites of fuel battery negative pole oxygen reduction reaction
Point；Three-dimensional porous nitrogen-doped graphene prepared by the present invention has certain degree of graphitization, with higher electric conductivity and
Stability in electrochemical environment can promote Cathodic oxygen reduction process, and can carry as fuel-cell catalyst
The stability of high catalyst；Three-dimensional porous nitrogen-doped graphene prepared by the present invention introduces nitrogen atom doping, and nitrogen-atoms is mixed
In the carbon-coating of miscellaneous entrance graphene, the carbon atom in carbon six-membered ring structure is by pyridine nitrogen, and pyrroles's nitrogen, graphitization nitrogen and nitrogen oxide take
Generation, due to nitrogen-atoms and the difference of carbon atom electronegativity so that the carbon around nitrogen-atoms becomes the active sites of oxygen reduction reaction
Point, improves the electro catalytic activity of fuel-cell catalyst；Graphene prepared by the present invention has certain defect, the defect
Have a great impact for fuel-cell catalyst performance, because the active sites of the oxygen reduction catalytic activity of carbon material come from material
The defect of, defect itself is more, is more possible to construct more active sites, so as to improve the activity of catalyst.
Brief description of the drawings
The present invention is further detailed explanation with reference to the accompanying drawings and detailed description.
Fig. 1 is that the SEM figures and difference of three-dimensional porous nitrogen-doped graphene prepared by Example 1 and Example 2 of the present invention are put
Big multiple TEM photos, Fig. 1 a are the SEM figures of three-dimensional porous nitrogen-doped graphene -2 (NCFe-950) prepared by embodiment 1；Fig. 1 b
Scheme with Fig. 1 c for NCFe-950 TEM；Fig. 1 d, Fig. 1 e, Fig. 1 f are three-dimensional porous nitrogen-doped graphene -7 prepared by embodiment 2
(NCCo-950) the TEM figures of different amplification；
The three-dimensional porous nitrogen-doped graphene that Fig. 2 is NCFe-950 made from the embodiment of the present invention 1 and prepared by embodiment 2
Structure and composition figure, Fig. 2 a, Fig. 2 b, Fig. 2 c and Fig. 2 d are respectively both XRDs, Raman figure, nitrogen adsorption-desorption curve figure
With XPS-N1s figures；
Fig. 3 is three-dimensional porous nitrogen-doped graphene -7 prepared by NCFe-950 made from the embodiment of the present invention 1 and embodiment 2
As the performance characterization graph of fuel battery negative pole oxygen reduction catalyst, Fig. 3 a are two kinds of three-dimensional porous nitrogen-doped graphenes and business
Industry Pt/C catalyst in alkalescence (solution be 0.1M KOH, rotating speed is 1600rmp, and sweep speed is 10mV/s) linear scan
Comparison diagram；Fig. 3 b are the Tafel curve maps of two kinds of three-dimensional porous nitrogen-doped graphenes and business Pt/C catalyst；Two kind three of Fig. 3 c
Tie up the electron transfer number figure of porous nitrogen-doped graphene and business Pt/C catalyst under different voltages；Fig. 3 d are that NCFe-950 exists
The linear scan figure measured under 400~2500rmp different rotating speeds recycles the calculating of Koutecky-Levich (K-L) equation to be made
1/J-1With ω-1/2Curve map.
Embodiment
The invention provides a kind of preparation method of three-dimensional porous nitrogen-doped graphene, comprise the following steps：
(1) amino acid is mixed with transition metal salt and water, obtains mixed solution；
(2) mixed solution for obtaining the step (1) heats removing moisture under agitation, obtains solid mixture；
(3) carry out calcination process after the solid mixture grinding obtained the step (2) and obtain N doping carbon dust；
(4) successively through pickling, deionization washing, absolute ethyl alcohol after the N doping carbon dust grinding obtained the step (3)
After washing and drying, three-dimensional porous nitrogen-doped graphene is obtained.
The present invention mixes amino acid with transition metal salt and water, obtains mixed solution.
Source of the invention to the amino acid and transition metal salt is without any special restriction, using this area skill
Commercial goods known to art personnel.
In the present invention, the amino acid preferably includes glycine, alanine, glutamic acid, serine, arginine and bad ammonia
One or more of mixtures in acid；When the mixture preferably includes two kinds of amino acid, more preferably glycine and rely
The mixture of the mixture of propylhomoserin, lysine and serine, the present invention does not have to the mass ratio of each amino acid in the mixture
Limitation, those skilled in the art can select the mixture of the amino acid of any mass ratio according to actual needs.
In the present invention, the transition metal salt preferably includes one or more of in Fe, Co and Ni soluble-salt
Mixture, more preferably including FeCl2、FeCl3、Ni(NO3)2、NiCl2、Ni(CH3COO)2、CoCl2With Co (NO3)2In one
Plant or several mixtures；When the mixture preferably includes two kinds of transition metal salts, more preferably CoCl2And FeCl3It is mixed
Compound, CoCl2With Ni (NO3)2Mixture, the present invention do not limited the mass ratio of transition metal salt in the mixture, this
Art personnel can select the mixture of the transition metal salt of any mass ratio according to actual needs；In the embodiment of the present invention
In, the CoCl2And FeCl3、CoCl2With Ni (NO3)2Mass ratio be preferably 1:1~1:5, more preferably 1:1~1:3.
In the present invention, the mass ratio of the amino acid and transition metal salt is preferably 1:1~1:10, more preferably 1:2
~1:6.
In the present invention, the order by merging to the raw material does not have special limitation, is known using those skilled in the art
Order by merging；In embodiments of the present invention, preferably first amino acid and transition metal salt are mixed, adds water.
The present invention does not have any special restriction to the mode of the mixing, using mixing well known to those skilled in the art
Mode；The mode for being preferred to use stirring in embodiments of the present invention is carried out, and the time of the stirring is preferably 2~24h, more
Preferably 4~12h, most preferably 6~8, the speed of the stirring is preferably 100~800rpm, more preferably 200~
600rpm, most preferably 300~500rpm.
Obtain after mixed solution, obtained mixed solution is heated removing moisture by the present invention under agitation, obtain solid and mix
Compound.
In the present invention, the speed of the stirring is preferably 100~800rpm, more preferably 200~600rpm, most preferably
For 300~500rpm；The time of the stirring is preferably 2~24h, more preferably 4~12h, and most preferably 6~8.
In the present invention, the temperature of the heating is preferably 50~80 DEG C, more preferably 60~70 DEG C, the heating when
Between be preferably until mixed solution in moisture remove completely, obtain bulk powder solid.
Obtain after solid mixture, by the present invention will obtained solid mixture grind after carry out calcination process and obtain nitrogen and mix
Miscellaneous carbon dust.
The present invention does not have any special restriction to the mode of the grinding, using grinding well known to those skilled in the art
Mode；Preferably it is ground in embodiments of the present invention in agate mortar, the time of the grinding is preferably 1~5h,
More preferably 2~4h.
In the present invention, the calcination process is preferably：In N2Under atmosphere, heated up with 2~10 DEG C/min heating rate
To 750~1050 DEG C, 60~180min is incubated, then room temperature is down to 2~10 DEG C/min rate of temperature fall；In the present invention, institute
State heating rate and be more preferably 5~8 DEG C/min, the warming temperature is more preferably 850~950 DEG C, and the soaking time is preferred
For 80~160min, more preferably 100~120min；The rate of temperature fall is more preferably 5~8 DEG C/min.
The present invention does not have any special restriction to the device of the calcination process, using well known to those skilled in the art
Calcination process device, is preferably placed in quartz boat by grinding product in embodiments of the present invention, then in tube furnace
It is calcined.
Obtain after N doping carbon dust, the present invention obtained N doping carbon dust is ground after successively through acid, deionized water, anhydrous
After ethanol is washed and dried, three-dimensional porous nitrogen-doped graphene is obtained.
In the present invention, the acid is preferably hydrochloric acid, and the concentration of the hydrochloric acid is preferably 1~5M, more preferably 2~3M.
The present invention does not have any special restriction to the mode of the acid elution, is using mode of washing well known to those skilled in the art
Can, the mode that centrifugation is preferred to use in embodiments of the present invention is washed, and the rotating speed of the centrifugation is preferably 200~
1000rpm, more preferably 400~600rpm, the time of the centrifugation is preferably 1~10h, more preferably 2~4h.
In the present invention, the deionization washing can remove the transition metal salt not utilized.
In the present invention, the absolute ethyl alcohol, which is washed, can remove organic impurities that may be present.
The present invention does not have any special restriction to the mode of the drying, using drying well known to those skilled in the art
Mode, is preferred to use vacuum drying in embodiments of the present invention, and the vacuum drying temperature is preferably 60~90 DEG C, more
Preferably 70~80 DEG C, the vacuum drying time is preferably 1~24h, more preferably 2~10h.
It is described present invention also offers the three-dimensional porous nitrogen-doped graphene that preparation method described in above-mentioned technical proposal is obtained
Three-dimensional porous nitrogen-doped graphene has porous three-dimensional crosslinked network, the carbon hexatomic ring of the three-dimensional porous nitrogen-doped graphene
Carbon atom in structure is by pyridine nitrogen, pyrroles's nitrogen, graphitization nitrogen and nitrogen oxide substitution.
The three-dimensional porous nitrogen-doped graphene that is obtained present invention also offers preparation method described in above-mentioned technical proposal or on
Three-dimensional porous nitrogen-doped graphene described in technical scheme is stated as the application of fuel-cell catalyst or catalyst carrier.
In the present invention, when the three-dimensional porous nitrogen-doped graphene is applied in fuel cell cathode catalyst material, institute
State three-dimensional porous nitrogen-doped graphene and drip to rotation electrode surface in a form of slurry, fuel battery negative pole is obtained after drying.
In the present invention, the solid content of the slurry is preferably 10%~50%, and more preferably 20%~30%.
In the present invention, the solvent preferably ethanol that the slurry is used.
The present invention does not have any special restriction to the drying mode, using drying side well known to those skilled in the art
Formula is carried out；Preferably carried out in embodiments of the present invention in vacuum drying mode, the vacuum drying temperature is preferably
60~90 DEG C, more preferably 70~80 DEG C；The vacuum drying pressure is preferably -0.07~-0.01MPa, more preferably -
0.08~-0.09MPa.
The invention provides a kind of preparation method of three-dimensional porous nitrogen-doped graphene, using amino acid small molecule simultaneously as
Carbon source and nitrogen source, using transition-metal catalyst, fired successively, grinding, pickling, deionization washing, absolute ethyl alcohol washing and
After drying, three-dimensional porous nitrogen-doped graphene is obtained.The method that the present invention is provided is in preparation process without additionally adding nitrogen
Source and pore-creating activator, one-step method just can form porous nitrogen-doped graphene in situ；And adjustable transition-metal catalyst
Species, obtains the three-dimensional porous nitrogen-doped graphene of different-shape, when the transition-metal catalyst used is iron class, obtains
It is curling, the three-dimensional porous nitrogen-doped graphene of gauze-like, when the transition-metal catalyst used is cobalt class, what is obtained is
The three-dimensional porous nitrogen-doped graphene of " onion shape ", when the transition-metal catalyst used is nickel class, what is obtained is " honeycomb
The three-dimensional porous nitrogen-doped graphene of shape ".Preparation method that the present invention is provided is simple and convenient, with low cost, be easy to extensive life
Production, and the fields such as fuel cell, lithium ion battery and ultracapacitor can be widely applied to.
Three-dimensional porous nitrogen-doped graphene prepared by the present invention has three-dimensional cross-linked loose structure, three-dimensional cross-linked net
Network structure can provide good mechanical stability for graphene, and three-dimensional cross-linked graphene can be cloudy for fuel cell as catalyst
Pole oxygen reduction reaction provides more electric transmission paths, to accelerate the kinetic rate of reaction, three-dimensional porous N doping graphite
The porous of alkene can significantly improve the specific surface area of graphene, can increase the active sites of fuel battery negative pole oxygen reduction reaction
Point；Three-dimensional porous nitrogen-doped graphene prepared by the present invention has certain degree of graphitization, with higher electric conductivity and
Stability in electrochemical environment can promote Cathodic oxygen reduction process, and can carry as fuel-cell catalyst
The stability of high catalyst；Three-dimensional porous nitrogen-doped graphene prepared by the present invention introduces nitrogen atom doping, and nitrogen-atoms is mixed
In the carbon-coating of miscellaneous entrance graphene, the carbon atom in carbon six-membered ring structure is by pyridine nitrogen, and pyrroles's nitrogen, graphitization nitrogen and nitrogen oxide take
Generation, due to nitrogen-atoms and the difference of carbon atom electronegativity so that the carbon around nitrogen-atoms becomes the active sites of oxygen reduction reaction
Point, improves the electro catalytic activity of fuel-cell catalyst；Graphene prepared by the present invention has certain defect, the defect
Have a great impact for fuel-cell catalyst performance, because the active sites of the oxygen reduction catalytic activity of carbon material come from material
The defect of, defect itself is more, is more possible to construct more active sites, so as to improve the activity of catalyst.
Three-dimensional porous nitrogen-doped graphene provided with reference to embodiment the present invention and its preparation method and application enters
Row detailed description, but they can not be interpreted as limiting the scope of the present invention.
Embodiment 1
(1) by 1g glycine by transition metal salt FeCl respectively with different proportion3·6H2O is mixed, and respectively obtains mixing
(the glycine of thing 1：FeCl3·6H2O mass ratio is 1：1), (glycine of mixture 2：FeCl3·6H2O mass ratio is 1：2)
With (the glycine of mixture 3：FeCl3·6H2O mass ratio is 1：4)；(the glycine of mixture 4：FeCl3·6H2O mass ratio
For 1：6)；(the glycine of mixture 5：FeCl3·6H2O mass ratio is 1：8)；(the glycine of mixture 6：FeCl3·6H2O matter
Amount is than being 1：10)；
(2) 40mL deionized water is separately added into six kinds of mixtures of step (1), is stirred at room temperature；
(3) solution in step (2) is heated to 80 DEG C until evaporating water under agitation；
(4) quartz boat is put into by product is polished in step (3), be subsequently placed in tube furnace, in N2Under atmosphere, with 5
DEG C/min heating rate is warming up to 950 DEG C, is incubated 60min, then room temperature is down to 5 DEG C/min rate of temperature fall, obtain carbon dust；
(5) product obtained by step (4) is ground, through 1M HCl centrifuge washings, deionized water, absolute ethyl alcohol are washed till neutrality
To remove impurity, it is placed in being dried in vacuo in 60 DEG C of baking ovens.Six kinds of resulting products are designated as three-dimensional porous nitrogen and mixed successively respectively
Miscellaneous graphene 1-6.
Embodiment 2
(1) by 1g glycine and 2g transition metal salts CoCl2·6H2O is mixed；
(2) 40mL deionized water is added into the mixture of step (1), is stirred at room temperature；
(3) solution in step (2) is heated to 80 DEG C until evaporating water under agitation；
(4) quartz boat is put into by product is polished in step (3), be subsequently placed in tube furnace, in N2Under atmosphere, with 5
DEG C/min heating rate is warming up to 950 DEG C, is incubated 60min, then room temperature is down to 5 DEG C/min rate of temperature fall, obtain carbon dust；
(5) product obtained by step (4) is ground, through 1M HCl centrifuge washings, deionized water, absolute ethyl alcohol are washed till neutrality
To remove impurity, it is placed in being dried in vacuo in 60 DEG C of baking ovens.Products therefrom is designated as three-dimensional porous nitrogen-doped graphene -7.
The structural characterization of three-dimensional porous nitrogen-doped graphene prepared by Examples 1 and 2 is as shown in Fig. 1~2, and these materials are used
When fuel cell, its performance test results is as shown in figure 3, three-dimensional porous nitrogen-doped graphene is in fuel cell cathode catalyst material
Performance test conditions are in material：Using three-electrode system, working electrode is glass carbon rotating disc electrode, three-dimensional porous N doping graphite
Alkene drips to rotation electrode surface in a form of slurry, is tested after fully drying.Reference electrode is silver/silver chloride electrode, to electrode
For platinized platinum.Test is carried out in 0.1M KOH solutions, and temperature is 25 DEG C, is tested using U.S.'s PINE double potentiostats, electricity
Position scope is 0.2V~0.8V, and sweep speed is 10 millivolts per second, and electrode rotating speed is 400~2500rpm.
Fig. 1 a are the scanning electron microscope (SEM) photograph of the three-dimensional porous nitrogen-doped graphene -2 (NCFe-950) prepared by embodiment 1
(SEM).Presentation three-dimensional cross-linked network in the three-dimensional porous inside of nitrogen-doped graphene -2 can be clearly observed from Fig. 1 a porous
The transmission electron microscope picture (TEM) that structure, figure b and figure c are NCFe-950-2, it can be seen that NCFe-950 is presented typical from figure b
The curling of graphene, the pattern of gauze-like, figure c scheme for NCFe-950 high-resolution TEM, can be clearly observed graphited
Lattice fringe, and the number of plies of graphene is about 10 layers, illustrates that prepared three-dimensional porous nitrogen-doped graphene has certain stone
Blackization degree.Fig. 1 d and Fig. 1 e are the TEM figures of the three-dimensional porous nitrogen-doped graphene -7 (NCCo-950) prepared by embodiment 2,
As can be seen from the figure NCCo-950 by it is compact arranged it is porous constitute, in high-resolution TEM figure (Fig. 2 f) it is observed that this
Some holes, around constituting, forms the carbon of " onion shape ", pore size is about 15-20nm by graphited band.
Fig. 2 a are the XRD of two kinds of prepared three-dimensional porous nitrogen-doped graphenes, can substantially be observed from figure
26.5 ° or so appearance, one obvious peak, it corresponds to graphene (002) peak, and relative to NCCo-950, NCFe-950's
Degree of graphitization is higher.Fig. 2 b are the Raman spectrogram of two kinds of three-dimensional porous nitrogen-doped graphenes.
It was found from Fig. 2 b, two kinds of graphenes have an obvious D peak, G peaks and 2D peaks, and wherein D peaks are induced by disordering
Formed, illustrate that the three-dimensional porous nitrogen-doped graphene prepared by the present invention contains certain defect.Fig. 2 c are prepared two kinds
The nitrogen adsorption of three-dimensional porous nitrogen-doped graphene-desorption curve figure.As can be seen from the figure NCFe-950 and NCCo-950
Iv class nitrogen adsorption-desorption curve is showed, it is mesoporous material to illustrate the three-dimensional porous nitrogen-doped graphene prepared by the present invention
Material.Fig. 2 d are the XPS-N1s of two kinds of prepared three-dimensional porous nitrogen-doped graphenes, and the appearance at the peak illustrates N atoms successfully
Doping is entered among the matrix of graphene；In addition, carrying out swarming to N1s peaks, it can be seen that it is by four kinds of different types of nitrogen
Composition, is pyridine nitrogen (N1), pyrroles's nitrogen (N2), graphitization nitrogen (N3) and nitrogen oxide (N4) respectively, and wherein N3 is oxygen reduction reaction
Avtive spot.
Fig. 3 is pole of the three-dimensional porous nitrogen-doped graphene of the invention prepared as fuel battery negative pole oxygen reduction catalyst
Change curve.It was found from from Fig. 3 a, the present invention prepared by NCFe-950 there is good oxygen reduction activity, its take-off potential and
Limiting current density all reaches the level close with business Pt/C catalyst.Fig. 3 b are Tafel curve maps, as can be seen from the figure
NCFe-950, NCCo-950 and Pt/C catalyst are in the low overpotential Tafel slope different with the appearance of high overpotential.Wherein,
Tafel slopes of the NCFe-950 under two sections of current potentials is respectively 84.4mv/dec and 115.9mv/dec, all closely business
Pt/C catalyst, illustrates that the three-dimensional porous nitrogen-doped graphene prepared by invention has faster kinetic reaction speed.Fig. 3 c
The electron transfer number figure of two kinds of three-dimensional porous nitrogen-doped graphenes and business Pt/C catalyst under different voltages, can be with from figure
Find out NCFe-950 electron transfer number closely 4, the explanation hydrogen reduction process is four electron reaction mechanism.In Fig. 3 d
The electron transfer number of three-dimensional porous nitrogen-doped graphene catalyst is calculated by K-L curves, its catalysis is further demonstrated
Course of reaction is all four electron reaction processes.Three-dimensional porous nitrogen-doped graphene is completely without metal, more without noble metal, cost
It is relatively low.Reached and catalytic activity as precious metal in the case of so low cost, it was demonstrated that the three-dimensional that the present invention is obtained is more
Hole nitrogen-doped graphene has powerful some commercial potential.
Embodiment 3
(1) by 1g glycine and 2g transition metal salts NiCl2·6H2O is mixed；
(2) 40mL deionized water is added into the mixture of step (1), is stirred at room temperature；
(3) solution in step (2) is heated to 50 DEG C until evaporating water under agitation；
(4) quartz boat is put into by product is polished in step (3), be subsequently placed in tube furnace, in N2Under atmosphere, with 2
DEG C/min heating rate is warming up to 750 DEG C, is incubated 60min, then room temperature is down to 2 DEG C/min rate of temperature fall, obtain carbon dust；
(5) product obtained by step (4) is ground, through 2M HCl centrifuge washings, deionized water, absolute ethyl alcohol are washed till neutrality
To remove impurity, it is placed in being dried in vacuo in 90 DEG C of baking ovens.
Embodiment 4
(1) by 1g alanine and 2g transition metal salts NiCl2·6H2O is mixed；
(2) 40mL deionized water is added into the mixture of step (1), is stirred at room temperature；
(3) solution in step (2) is heated to 60 DEG C until evaporating water under agitation；
(4) quartz boat is put into by product is polished in step (3), be subsequently placed in tube furnace, in N2Under atmosphere, with 10
DEG C/min heating rate is warming up to 1050 DEG C, is incubated 180min, then room temperature is down to 10 DEG C/min rate of temperature fall, obtain carbon
Powder；
(5) product obtained by step (4) is ground, through 3M HCl centrifuge washings, deionized water, absolute ethyl alcohol are washed till neutrality
To remove impurity, it is placed in being dried in vacuo in 70 DEG C of baking ovens.
Embodiment 5
(1) by 1g glutamic acid and 2g transition metal salt Ni (NO3)2·6H2O) mix；
(2) 40mL deionized water is added into the mixture of step (1), is stirred at room temperature；
(3) solution in step (2) is heated to 70 DEG C until evaporating water under agitation；
(4) quartz boat is put into by product is polished in step (3), be subsequently placed in tube furnace, under n 2 atmosphere, with 8
DEG C/min heating rate is warming up to 850 DEG C, is incubated 80min, then room temperature is down to 8 DEG C/min rate of temperature fall, obtain carbon dust；
(5) product obtained by step (4) is ground, through 4M HCl centrifuge washings, deionized water, absolute ethyl alcohol are washed till neutrality
To remove impurity, it is placed in being dried in vacuo in 80 DEG C of baking ovens.
Embodiment 6
(1) by 1g arginine and 6g transition metal salt Ni (CH3COO)2·4H2O) mix；
(2) 40mL deionized water is added into the mixture of step (1), is stirred at room temperature；
(3) solution in step (2) is heated to 70 DEG C until evaporating water under agitation；
(4) quartz boat is put into by product is polished in step (3), be subsequently placed in tube furnace, under n 2 atmosphere, with 3
DEG C/min heating rate is warming up to 850 DEG C, is incubated 160min, then room temperature is down to 4 DEG C/min rate of temperature fall, obtain carbon
Powder；
(5) product obtained by step (4) is ground, through 5M HCl centrifuge washings, deionized water, absolute ethyl alcohol are washed till neutrality
To remove impurity, it is placed in being dried in vacuo in 70 DEG C of baking ovens
Embodiment 7
(1) by 1g serines and 2g transition metal salts FeCl3·6H2O、2g CoCl2·6H2O is mixed；
(2) 40mL deionized water is added into the mixture of step (1), is stirred at room temperature；
(3) solution in step (2) is heated to 60 DEG C until evaporating water under agitation；
(4) quartz boat is put into by product is polished in step (3), be subsequently placed in tube furnace, under n 2 atmosphere, with 7
DEG C/min heating rate is warming up to 950 DEG C, is incubated 120min, then room temperature is down to 3 DEG C/min rate of temperature fall, obtain carbon
Powder；
(5) product obtained by step (4) is ground, through 2M HCl centrifuge washings, deionized water, absolute ethyl alcohol are washed till neutrality
To remove impurity, it is placed in being dried in vacuo in 60 DEG C of baking ovens.
Embodiment 8
(1) by 1g lysines, 1g serines and 2g transition metal salts CoCl2·6H2O、5g Ni(NO3)2·6H2O is mixed；
(2) 60mL deionized water is added into the mixture of step (1), is stirred at room temperature；
(3) solution in step (2) is heated to 80 DEG C until evaporating water under agitation；
(4) quartz boat is put into by product is polished in step (3), be subsequently placed in tube furnace, under n 2 atmosphere, with 10
DEG C/min heating rate is warming up to 1050 DEG C, is incubated 100min, then room temperature is down to 10 DEG C/min rate of temperature fall, obtain carbon
Powder；
(5) product obtained by step (4) is ground, through 1M HCl centrifuge washings, deionized water, absolute ethyl alcohol are washed till neutrality
To remove impurity, it is placed in being dried in vacuo in 80 DEG C of baking ovens.
Three-dimensional porous nitrogen-doped graphene prepared by embodiment 3~8 has three-dimensional cross-linked loose structure and certain
Degree of graphitization, carbon atom in carbon six-membered ring structure is by pyridine nitrogen, pyrroles's nitrogen, graphitization nitrogen and nitrogen oxide substitution, simultaneously
Also there is certain defect, the defect has a great impact for fuel-cell catalyst performance, because the hydrogen reduction of carbon material
Defect of the active sites of catalytic activity from material, defect in itself is more, is more possible to construct more active sites, so as to improve
The activity of catalyst, with the stability in higher electric conductivity and electrochemical environment, can be used as fuel-cell catalyst.
Described above is only the preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of three-dimensional porous nitrogen-doped graphene, it is characterised in that comprise the following steps：
(1) amino acid is mixed with transition metal salt and water, obtains mixed solution；
(2) mixed solution for obtaining the step (1) heats removing moisture under agitation, obtains solid mixture；
(3) carry out calcination process after the solid mixture grinding obtained the step (2) and obtain N doping carbon dust；
(4) washed successively through pickling, deionization washing, absolute ethyl alcohol after the N doping carbon dust grinding obtained the step (3)
After drying, three-dimensional porous nitrogen-doped graphene is obtained.
2. preparation method according to claim 1, it is characterised in that amino acid includes glycine, third in the step (1)
One or more of mixtures in propylhomoserin, glutamic acid, serine, arginine and lysine.
3. preparation method according to claim 1, it is characterised in that transition metal salt includes Fe, Co in the step (1)
With one or more of mixtures in Ni soluble-salt.
4. preparation method according to claim 3, it is characterised in that transition metal salt includes FeCl in the step (1)2、
FeCl3、Ni(NO3)2、NiCl2、Ni(CH3COO)2、CoCl2With Co (NO3)2In one or more of mixtures.
5. preparation method according to claim 1, it is characterised in that amino acid and transition metal salt in the step (1)
Mass ratio be 1:1~1:10.
6. preparation method according to claim 1 or 5, it is characterised in that in the step (1) time of mixing for 12~
24h。
7. preparation method according to claim 1, it is characterised in that in the step (2) rotating speed of stirring for 100~
800rpm；The temperature of heating is 50~80 DEG C in the step (2).
8. preparation method according to claim 1, it is characterised in that calcination process is in the step (3)：In N2Atmosphere
Under, 750~1050 DEG C are warming up to 2~10 DEG C/min heating rate, 60~180min is incubated, then with 2~10 DEG C/min's
Rate of temperature fall is down to room temperature.
9. the three-dimensional porous nitrogen-doped graphene that preparation method described in claim 1~8 any one is obtained, it is characterised in that
The three-dimensional porous nitrogen-doped graphene has porous three-dimensional crosslinked network, the carbon six of the three-dimensional porous nitrogen-doped graphene
Carbon atom in ring structure is replaced by pyridine nitrogen, pyrroles's nitrogen, graphitization nitrogen and nitrogen oxide.
10. three-dimensional porous nitrogen-doped graphene described in claim 9 is used as the application of fuel-cell catalyst or catalyst carrier.
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