CN110148762A - The carbon material and one of a kind of nitrogen, fluorine and transition metal codope graphene-structured walk carbonization manufacture method - Google Patents
The carbon material and one of a kind of nitrogen, fluorine and transition metal codope graphene-structured walk carbonization manufacture method Download PDFInfo
- Publication number
- CN110148762A CN110148762A CN201910482806.1A CN201910482806A CN110148762A CN 110148762 A CN110148762 A CN 110148762A CN 201910482806 A CN201910482806 A CN 201910482806A CN 110148762 A CN110148762 A CN 110148762A
- Authority
- CN
- China
- Prior art keywords
- nitrogen
- fluorine
- transition metal
- carbon material
- graphene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- 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
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The present invention provides the carbon material of a kind of nitrogen, fluorine and transition metal codope graphene-structured, using melamine, polytetrafluoroethylene (PTFE), metal salt as raw material, after being mixed, being ground uniformly, nitrogen, fluorine and transition metal codope carbon material are prepared using one step carbonization；Graphene or class graphene-structured is presented in gained carbon material；Nitrogen, fluorine and distributions of metallic elements are uniform, and there is excellent hydrogen reduction and oxygen performance is precipitated.One walks carbonization manufacture method the following steps are included: the 1) mixing of raw material；2) one step carbonization.There is the present invention excellent hydrogen reduction and oxygen performance is precipitated.It is also possible to which performance is precipitated in the hydrogen reduction and oxygen for improving such material by adjusting the synergistic effect between nitrogen, fluorine and transition metal.One step carbonization of the present invention is reproducible, simple process, easy to operate.It has broad application prospects in fuel cell and metal-air battery electrode catalyst field and function carbon material direction.
Description
Technical field
The present invention relates to functional carbon Material Fields, and in particular to a kind of nitrogen, fluorine and transition metal codope graphene-structured
Carbon material preparation method.
Background technique
Currently, fossil fuel remains as the energy of our most mainstreams, traditional energy utilization patterns, there are low efficiency and
Pollute big two big disadvantages.These disadvantages generate very big negative effect to Global Ecological, environment.In order to adapt to the development of the new period
Demand, the epoch, there is an urgent need to the novel energy and new energy utilization patterns.Hydrogen Energy is as a kind of ideal clean energy resource, in recent years
To obtain the extensive concern in the whole world.Hydrogen-oxygen fuel cell directly can convert electric energy for Hydrogen Energy by electrochemical reaction, produce
Object only has water；It is not restricted by Carnot cycle, the advantage with energy conversion efficiency height and the no pollution to environment.These are excellent
Point makes hydrogen energy source and fuel cell technology become the outstanding person in new energy and new energy technology.Although fuel cell technology is close
It achieves significant progress year a bit, and starts gradually to be commercialized.But the fuel-cell catalyst of current business contains largely
Noble metal platinum, platinum scarcity of resources, expensive, these disadvantages will hinder the further sustainable development of fuel cell.Therefore, it makes
The low platinum or non-platinum catalyst of standby high activity, for reducing fuel cell cost, realization fuel cell is commercialized on a large scale to be had
Important meaning.The carbon material of hetero atom and transition metal codope is made due to the synergistic effect between hetero atom and transition metal
There is such material good hydrogen reduction (ORR)/oxygen (OER) performance is precipitated, and become that business platinum based catalyst is most potential to be replaced
Dai Zhe.Such non-precious metal catalyst has become the research hotspot in current fuel-cell catalyst field.
There are many research of hetero atom and the carbon material of transition metal codope, and Chinese patent 201710280405.9 discloses
A kind of oxygen reduction catalyst containing fluorine, nitrogen and carbon, for the catalyst using melamine as nitrogen source, formaldehyde is crosslinking agent, is drawn
Enter hexafluoro bisphenol-a as carbon source and Fluorine source, the oxygen reduction catalyst of fluorine, nitrogen, carbon is had both using solvent structure, it should
The half wave potential of catalyst is 0.79V or so.Chinese patent 201510568447.3 discloses a kind of using freeze-drying legal system
The standby Eutectic molten salt with 3 D stereo macroporous structure adulterates nitrogen, the catalyst of iron, this is urged then using Eutectic molten salt as template
Agent shows good oxygen reduction catalytic activity, and the half wave potential of the Fe-Mn cycle and transference catalyst is 0.83V.Chinese patent
201810332317.3 disclose one kind using riboflavin, cobalt acetate, sodium chloride as raw material, are then freeze-dried, carbonization obtains
Cobalt, nitrogen co-doped porous carbon materials, the material have given full play to the hydrogen reduction catalytic performance of carbon material, the half-wave electricity of the catalyst
Position is 0.8V.Chinese patent 201810496378.3 discloses one kind using ZnO nano piece as template and zinc source, 2-methylimidazole
For organic ligand, praseodynium iron is source of iron, and cobalt salt is cobalt source, and the carbon nanosheet of core-shell structure has been made using solvent-thermal method
Oxygen reduction catalyst, the catalyst activity site are abundant, show good catalytic activity, which cobalt, nitrogen co-doped urges
The half wave potential of agent is 0.81V.The non-precious metal catalyst of above method preparation all has good oxygen reduction catalytic activity,
But also exist following insufficient: preparation process is complicated, and preparation environmental requirement is high, and required equipment is more complex, these factors are brought into
The defects of this height, unsuitable heavy industrialization.
Above-mentioned patent has nitrogen, fluorin-doped carbon material；There is the carbon material of nitrogen or fluorine and transition metal codope.But
By nitrogen, two kinds of strong electronegativity hetero atoms of fluorine and transition metal codope, and the carbon material of graphene-structured is prepared in step carbonization,
Until not yet retrieving relevant report at present.The main reason is that nitrogen, fluorine hetero atom and transition metal codope graphene system
It is standby difficult；It is more difficult if wanting a step to be carbonized into the carbon material with graphene-structured.
Compare fortunately, this patent has selected suitable presoma, is prepared for nitrogen, fluorine hetero atom and mistake by one-step method
Metal co-doped graphene is crossed, a kind of excellent bifunctional catalyst has been obtained.Catalysis material obtained by this patent in hydrogen reduction and
Aspect, which is precipitated, in oxygen outstanding performance, hence it is evident that better than the performance of business platinum carbon catalyst and above-mentioned associated catalysts；And it prepares
In a step carbonization synthesis, simple process is controllable, and required equipment is simple, is conducive to large-scale industrial production.
Summary of the invention
The object of the present invention is to provide a kind of nitrogen, fluorine and transition metal codope graphene structural carbon material one step carbonizations
The method of preparation.Nitrogen, fluorine and transition metal are introduced into carbon material with cheap cost, and the material is made both topographically to show stone
The structure of black alkene or class graphene；On electrocatalysis characteristic, it is one which, which has excellent hydrogen reduction/oxygen separating out,
The excellent bifunctional catalyst of kind.Have in fuel cell, metal-air battery electrode material field and functional carbon Material Field
Broad application prospect.
Basic principle of the invention is the distribution of charges of nitrogen, the adjustable carbon material surface of Fluorin doped carbon material, nitrogen, fluorine
Strong electronegativity can lead to the polarization of adjacent carbon atom, to make to show a large amount of positive charge on adjacent carbon atom；Oxygen
(O2) molecule contains lone pair electrons, which is easy to be attracted by positively charged carbon, is conducive to O in this way2On the carbon material
Absorption, meanwhile, play the role of weakening O=O key, is conducive to the fracture of oxygen-oxygen bond, oxygen is made to be easy to happen reduction reaction.In addition,
Transition metal has a large amount of d unoccupied orbitals, these unoccupied orbitals can regulate and control the electron cloud in carbon material, equally also can effectively enhance oxygen
The absorption of gas and its reducing power.The reduction and precipitation of oxygen are reversible processes, therefore, the association between hetero atom and transition metal
Same-action can effectively enhance ORR the and OER performance of catalyst.
In order to achieve the above-mentioned object of the invention, the technical solution adopted by the present invention are as follows:
The carbon material of a kind of nitrogen, fluorine and transition metal codope graphene-structured, with melamine, polytetrafluoroethylene (PTFE), metal salt
Nitrogen, fluorine and transition metal codope carbon material are prepared using one step carbonization after being mixed, being ground uniformly for raw material；Institute
It obtains carbon material and graphene or class graphene-structured is presented；Nitrogen, fluorine and distributions of metallic elements are uniform；The transition metal be titanium, manganese,
Iron, cobalt, nickel, copper, zinc, zirconium, molybdenum, ruthenium element it is one or more.
An a kind of step carbonization manufacture method for the carbon material of nitrogen, fluorine and transition metal codope graphene-structured, including with
Lower step:
Step 1, the mixing of raw material is met by the mass ratio of metal in melamine powder, polytetrafluorethylepowder powder and metal salt
1:(0.25-4.0): (0.00001-0.2) is weighed, and metal salt is configured to certain density metal salt solution, by melamine
Powder and polytetrafluorethylepowder powder are added metal salt solution and are mixed, and through hand-ground or mechanical ball mill 0.5-2.0 hour, grind
Uniformly mixed powder sample is obtained after dry；
Step 2, one step carbonization, by step 1 gained powder sample, under an inert atmosphere, with heating rate for 3-10 DEG C/minute
Clock is started to warm up from room temperature between 600 DEG C -1200 DEG C, then keeps the temperature carbonization 0.5-3 hours, is carbonized, be can be obtained by a step
The carbon material of nitrogen, fluorine and transition metal codope.
The detection of this material property and characterization situation are as follows:
Test is precipitated in electrochemical oxygen reduction and oxygen: the class testing is used to characterize the hydrogen reduction of material and performance, and and English is precipitated in oxygen
40 wt % of state Jonhson-Matthey business Pt/C(Pt) platinum carbon catalyst compares, illustrate the excellent degree of its performance.
Oxygen reduction reaction (ORR) test: catalyst is applied in rotating disk electrode (r.d.e), wherein the catalysis of doping carbon material
The carrying capacity of agent is 0.51 milli gram per centimeter2；The carrying capacity of business Pt/C catalyst platinum is 0.51 micro- gram per centimeter2.Mercury/mercuric oxide electrode
For reference electrode, platinum filament is to electrode, and it is electrolyte that oxygen, which is saturated 0.1 mol/L potassium hydroxide aqueous solution, tests sweep speed
For the hydrogen reduction linear scan curve under the conditions of 5 mv ss.
Oxygen evolution reaction (OER) test: catalyst is applied in rotating disk electrode (r.d.e), wherein the catalysis of doping carbon material
The carrying capacity of agent is 0.51 milli gram per centimeter2；The carrying capacity of business Pt/C catalyst platinum is 0.51 micro- gram per centimeter2.Mercury/mercuric oxide electrode
For reference electrode, platinum filament is to electrode, and it is electrolyte that oxygen, which is saturated 0.1 mol/L potassium hydroxide aqueous solution, tests sweep speed
Linear scan curve is precipitated for the oxygen under the conditions of 5 mv ss.
Transmission electron microscope (TEM) characterization: by transmission electron microscope map, the shape characteristic of resulting materials is characterized.
X-ray photoelectron spectroscopy (EDX) characterization: by EDX energy spectrum diagram, characterization has proved nitrogen, fluorine and transition metal
Through being evenly distributed in resulting materials.
Creativeness of the invention is embodied in:
1) present invention be prepared for nitrogen, fluorine and transition metal codope have graphene/class graphene structural carbon material；
2) graphene/class grapheme material of nitrogen, fluorine and transition metal codope only needs one step carbonization in the present invention
It obtains.
The present invention compared with the existing technology, has following advantages:
1) design technology process of the present invention is simple, easily operated, is easy to industrialization realization；
2) industry polytetrafluorethylepowder powder, melamine raw material used in the present invention and common transition metal salt, raw material are easy to get,
It is cheap；
3) present invention is as fuel battery cathod catalyst in use, its hydrogen reduction performance is apparently higher than business platinum carbon catalyst
With the similar associated catalysts in relation to reporting；
4) present invention is used as metal-air battery catalyst in use, performance, which is precipitated, in its oxygen is substantially better than the catalysis of business platinum carbon
Agent.
Detailed description of the invention
Fig. 1 is hydrogen reduction linear scan curve of the catalyst obtained by embodiment 1,2 and comparative example in rotating disk electrode (r.d.e)；
Fig. 2 is the transmission electron microscope map of embodiment 1；
Fig. 3 is the EDX energy spectrum diagram of embodiment 1；
Fig. 4 is 40 wt % of the resulting catalyst of embodiment 1,3,4 and Britain Jonhson-Matthey business Pt/C(Pt) catalysis
Hydrogen reduction linear scan curve of the agent in rotating disk electrode (r.d.e)；
Fig. 5 is the resulting catalyst of embodiment 5-7 and 40 wt % of Britain Jonhson-Matthey business Pt/C(Pt) catalyst
Hydrogen reduction linear scan curve in rotating disk electrode (r.d.e)；
Fig. 6 is the transmission electron microscope map of embodiment 5；
Fig. 7 is 40 wt % of the resulting catalyst of embodiment 1,7,8 and Britain Jonhson-Matthey business Pt/C(Pt) catalysis
Hydrogen reduction linear scan curve of the agent in rotating disk electrode (r.d.e)；
Fig. 8 is 40 wt % of the resulting catalyst of embodiment 1,7,8 and Britain Jonhson-Matthey business Pt/C(Pt) catalysis
Linear scan curve is precipitated in oxygen of the agent in rotating disk electrode (r.d.e).
Specific embodiment
Combined with specific embodiments below, the present invention is further illustrated.
Embodiment 1
The carbon of a kind of nitrogen, fluorine and transition metal codope graphene-structured when transition metal is cobalt, and carburizing temperature is 950 DEG C
One step carbonization manufacture method of material.
Step 1, the mixing of raw material, with melamine powder, the mass ratio of polytetrafluorethylepowder powder and metal salt cobalt acetate
Meet 1:1.5:0.002, weigh 3.0 g of 2.0 g of melamine powder and polytetrafluorethylepowder powder, is added 2 mL, 0.035 M's
The ethanol solution of cobalt acetate is mixed, is ground, and obtains uniformly mixed powder sample after mill is dry within hand-ground 1 hour；
Step 2, one step carbonization, the uniform powder sample that step 1 is obtained is put to be carbonized in a nitrogen atmosphere, with heating
Speed is 5 DEG C/min, is started to warm up from room temperature between 950 DEG C, then keeps the temperature carbonization 1 hour.
The present embodiment ORR performance is shown in Fig. 1, polarization curve 2.
Fig. 2 is the transmission electron microscope map of embodiment 1, which shows graphene-structured, illustrates a kind of nitrogen, fluorine and transition gold
In the method for belonging to the preparation of codope graphene structural carbon material one step carbonization, when nitrogen, fluorine, cobalt codope and in 950 DEG C of one step
When carbonization, the structure of available graphene.
Fig. 3 is the EDX energy spectrum diagram of embodiment 1.It may be seen that nitrogen, fluorine, cobalt have been evenly distributed in the graphene
On the material of structure.Prepared by a kind of nitrogen of the present invention, fluorine and transition metal codope graphene structural carbon material one step carbonization
Method, can be by nitrogen, fluorine and transition metal uniformly on such carbon material.
In order to prove whether the shadow containing metallic element and different metal constituent content to material hydrogen reduction catalytic performance
It rings, gives comparative example and embodiment 2 without transition metal, compare research with embodiment 1.
Comparative example:
Without metallic element, an a kind of step carbon of the carbon material of nitrogen, fluorin-doped graphene-structured when carburizing temperature is 950 DEG C
Change preparation method.
Not specified step is identical as preparation method described in embodiment 1 in specific steps, the difference is that: institute
The mass ratio for stating step 1 melamine powder, polytetrafluorethylepowder powder and metal salt meets 1:1.5:0, that is, is added without cobalt acetate
Ethanol solution.
This comparative example ORR performance is shown in Fig. 1, polarization curve 3.
Embodiment 2
When transition metal is cobalt, and carburizing temperature is 950 DEG C, the carbon of a kind of nitrogen, fluorine and transition metal codope graphene-structured
One step carbonization manufacture method of material.
Not specified step is identical as preparation method described in embodiment 1 in specific steps, the difference is that: institute
The mass ratio for stating step 1 melamine powder, polytetrafluorethylepowder powder and metal salt meets 1:1.5:0.004, and 4 mL are added
The ethanol solution of the cobalt acetate of 0.035 M.
The present embodiment ORR performance is shown in Fig. 1, polarization curve 1.
The result of the hydrogen reduction performance characterization of embodiment 1, comparative example and embodiment 2 by Fig. 1 as shown in Figure 1, obtained following
Conclusion:
1, containing transition metal element can significantly improve the hydrogen reduction catalytic performance of material；
2, different transition metal contents also can material property influence, the content that can be mixed by adjusting transition metal is come
Regulate and control the performance of catalyst.
Wherein, the hydrogen reduction catalysis half wave potential of 1 material prepared of embodiment is 0.86V, prepared catalyst performance
Most excellent (Fig. 1, polarization curve 2).This explanation, the content that we can mix by adjusting metal, to regulate and control the property of catalyst
Energy.Wherein, embodiment 1(Fig. 1, polarization curve 2) and embodiment 2(Fig. 1, polarization curve 1) ORR performance, hence it is evident that be higher than comparison
The performance of example (Fig. 1, polarization curve 3)；This conclusion shows a kind of nitrogen, fluorine and transition metal codope graphene structural carbon material
In, the ORR performance for mixing transition metal will will be significantly improved than being not incorporated into the correlated performance of transition metal.
In order to prove influence of the carburizing temperature to material hydrogen reduction catalytic performance of the present invention, give when transition metal is cobalt
When, the embodiment 3 and 4 of different carburizing temperatures.
Embodiment 3
The carbon of a kind of nitrogen, fluorine and transition metal codope graphene-structured when transition metal is cobalt, and carburizing temperature is 900 DEG C
One step carbonization manufacture method of material.
Not specified step is identical as preparation method described in embodiment 1 in specific steps, the difference is that: institute
Step 2 is stated to be warming up at 900 DEG C.
The present embodiment ORR performance is shown in Fig. 2, polarization curve 2.
Embodiment 4
A kind of nitrogen, fluorine and transition metal codope graphene-structured when transition metal is cobalt, and carburizing temperature is 1000 DEG C
One step carbonization manufacture method of carbon material.
Not specified step is identical as preparation method described in embodiment 1 in specific steps, the difference is that: institute
Step 2 is stated to be warming up at 1000 DEG C.
The present embodiment ORR performance is shown in Fig. 4, polarization curve 4.
Embodiment 1,3 and the result of 4 hydrogen reduction performance characterizations are as shown in figure 4, carburizing temperature influences significantly material property.
Wherein, the half wave potential of prepared material is 0.86 V(Fig. 4, polarization curve 3 when 1 carburizing temperature of embodiment is 950 DEG C), be
Optimal cases in 3 carburizing temperatures.
The significant technical effect of the present invention, by being compared with the prior art:
The first, with 40 wt % of Britain Jonhson-Matthey business Pt/C(Pt) catalyst half wave potential 0.825V(Fig. 4,
Polarization curve 1) it compares, it has been higher by 35 mV；
The second, with the half wave potential 0.80V phase of Fe-Mn cycle and transference catalyst disclosed in Chinese patent 201510568447.3
Than being higher by 60 mV.
In order to prove codope is single, different metal is to material hydrogen reduction catalytic performance of the present invention influence and carbon
The influence for changing temperature gives when transition metal is iron, the embodiment 5-7 of different carburizing temperatures.
Embodiment 5
The carbon of a kind of nitrogen, fluorine and transition metal codope graphene-structured when transition metal is iron, and carburizing temperature is 900 DEG C
One step carbonization manufacture method of material.
Not specified step is identical as preparation method described in embodiment 1 in specific steps, the difference is that: institute
The metal salt for stating step 1 is iron chloride；Carburizing temperature is 900 DEG C of 1 hours of heat preservation in the step 2.
The present embodiment ORR performance is shown in Fig. 5, polarization curve 2.
Fig. 6 is the transmission electron microscope map of embodiment 5, which shows ultra-thin silk ribbon shape class graphene-structured；Illustrate one kind
The method of nitrogen, fluorine and the preparation of transition metal codope graphene structural carbon material one step carbonization, when nitrogen, fluorine, iron codope exist
When 900 DEG C of one step carbonization, the structure of available class graphene.
From the graph it is known that the carbon materials of nitrogen, fluorine and transition codope can be changed by adjusting different metal in 2 and Fig. 6
The pattern of material doping carbon material, allows its structure with graphene or class graphene.
Embodiment 6
The carbon of a kind of nitrogen, fluorine and transition metal codope graphene-structured when transition metal is iron, and carburizing temperature is 800 DEG C
One step carbonization manufacture method of material.
Not specified step is identical as preparation method described in embodiment 5 in specific steps, the difference is that: institute
Step 2 is stated to be warming up at 800 DEG C.
The present embodiment ORR performance is shown in Fig. 5, polarization curve 1.
Embodiment 7
The carbon of a kind of nitrogen, fluorine and transition metal codope graphene-structured when transition metal is iron, and carburizing temperature is 950 DEG C
One step carbonization manufacture method of material.
Not specified step is identical as preparation method described in embodiment 5 in specific steps, the difference is that: institute
Step 2 is stated to be warming up at 950 DEG C.
The present embodiment ORR performance is shown in Fig. 5, polarization curve 3.
The hydrogen reduction performance characterization result of embodiment 5-7 is as shown in Figure 5.Wherein, when 5 carburizing temperature of embodiment is 900 DEG C
The half wave potential of prepared material is 0.86 V, is optimal cases in 3 carburizing temperatures.
In conjunction with Fig. 4 and Fig. 5, Fig. 2 and Fig. 6, it can be deduced that conclusion:
The first, preparation method of the present invention is applicable to a variety of transition metal elements, and when adulterating different transition metal, pattern is different
Sample；
The second, when adulterating different transition metal, the optimal carburizing temperature of catalytic performance be will be different.
When third, the different transition metal of doping, the variation of carburizing temperature has significant impact to material property.
The significant technical effect of the present invention, by being compared with the prior art:
The first, with 40 wt % of Britain Jonhson-Matthey business Pt/C(Pt) catalyst half wave potential 0.825V(Fig. 5,
Polarization curve 4) it compares, it has been higher by 35 mV；
The second, with the half wave potential 0.83V phase of Fe-Mn cycle and transference catalyst disclosed in Chinese patent 201510568447.3
Than being higher by 30 mV.
In order to prove that a variety of different transition metal codopes may be implemented in preparation method of the present invention, and due to a variety of transition gold
Synergistic effect between category, it will usually make such material that there is better hydrogen reduction catalytic performance, the present invention gives together herein
When two kinds of transition metal of codope metallic iron and metallic cobalt when embodiment 8.
Embodiment 8
Two kinds of transition metal of codope metallic iron and metallic cobalt simultaneously, a kind of nitrogen, fluorine and transition gold when carburizing temperature is 950 DEG C
Belong to a step carbonization manufacture method of the carbon material of codope graphene-structured.
Not specified step is identical as preparation method described in embodiment 7 in specific steps, the difference is that: institute
The metal salt for stating step 1 is cobalt acetate and two kinds of iron chloride, and the ratio between cobalt acetate and the amount of substance of iron chloride are 1:1, that is, is added 1
The ethanol solution of the cobalt acetate of 0.035 M of ethanol solution and 1 mL of the iron chloride of 0.035 M of mL.
The present embodiment ORR performance is shown in Fig. 7, polarization curve 4.The present embodiment OER performance is shown in Fig. 8, polarization curve 4.
Test results are shown in figure 7 by the ORR of embodiment 1,7,8, and result of study shows: catalyst prepared by embodiment 8
Performance (Fig. 7, polarization curve 4) is most excellent in four catalyst oxygen reduction catalyst, and half wave potential is 0.90 V.
The significant technical effect of the present invention, can by comparing with other doping single transition metal embodiments and the prior art
Know:
The first, compared with adulterating single metal embodiments with other in the present invention, 8 half wave potential of embodiment is that 0.90 V compares embodiment
In 1, in the material (Fig. 7, polarization curve 2) and embodiment 7 of nitrogen, fluorine and cobalt codope, the material (figure of nitrogen, fluorine and iron codope
7, polarization curve 3) high 40mV；
The second, with 40 wt % of Britain Jonhson-Matthey business Pt/C(Pt) catalyst half wave potential 0.825V(Fig. 7, pole
Change curve 1) it compares, the present invention has been higher by 75 mV；
Iron disclosed in third, patent 201810496378.3, cobalt, nitrogen co-doped catalyst half wave potential are compared for 0.81V,
The present invention improves 90 mV.
In order to prove that the present invention not only has excellent hydrogen reduction catalytic, while performance also is precipitated with outstanding oxygen；
Prove that the present invention is a kind of excellent double-function catalyzing.The present invention gives the oxygen of embodiment 1,7,8, and performance test characterization is precipitated.
Test results are shown in figure 8 for it.
It is significant that result of study shows that codope metal influences material property, wherein embodiment 8(Fig. 8, polarization curve 4)
Prepared material overpotential is minimum.Hydrogen can be calculated by Gibbs Gibbs free and react the theory of generation water instead with oxygen
Answering electromotive force is 1.229 V.
It is 10 milliamperes/centimetre that the hydrogen catalyzed electromotive force reacted when generating water with oxygen, which is in current density, in the present embodiment 82
When be 1.722 V；Its overpotential is 0.493 V.
Embodiment 1(Fig. 8, polarization curve 2) be single transition metal cobalt doped corresponding carbon material, corresponding current density
Under oxygen be precipitated electromotive force be 1.980V, overpotential 0.751V；
Embodiment 7(Fig. 8, polarization curve 3) be single transition metal Fe2O3 doping corresponding carbon material, under corresponding current density
It is 1.873V, overpotential 0.644V that electromotive force, which is precipitated, in oxygen；
40 wt % of Britain Jonhson-Matthey business Pt/C(Pt) catalyst, under corresponding current density it is hydrogen catalyzed with
Electromotive force when oxygen reaction generates water is 2.090 V, overpotential 0.861V.
The significant technical effect of the present invention, by embodiment related to the present invention and the prior art compare:
The first, the embodiment of the present invention 1,7,8 directly relatively it is found that a kind of nitrogen, fluorine and transition metal codope graphene-structured
In one step carbonization manufacture method of carbon material, when transition metal is iron and two kinds of cobalt, catalytic activity is precipitated than having served as in oxygen
It crosses high when metal is iron or cobalt single transition metal.
It the second, is 0.861V with the overpotential of 40 wt % of Britain Jonhson-Matthey business Pt/C(Pt) catalyst
(Fig. 4, polarization curve 1) is compared, and overpotential of the invention reduces 0.368 V.
This shows a kind of method of nitrogen, fluorine and the preparation of transition metal codope graphene structural carbon material one step carbonization,
When nitrogen, fluorine, iron, cobalt codope, the platinum carbon catalyst that performance is substantially better than business is precipitated in oxygen.
Claims (6)
1. the carbon material of a kind of nitrogen, fluorine and transition metal codope graphene-structured, it is characterised in that: with melamine, poly- four
Vinyl fluoride, metal salt are raw material, and after being mixed, being ground uniformly, it is total to prepare nitrogen, fluorine and transition metal using one step carbonization
Adulterate carbon material；Graphene or class graphene-structured is presented in gained carbon material；Nitrogen, fluorine and distributions of metallic elements are uniform.
2. carbon material according to claim 1, it is characterised in that: the transition metal be titanium, manganese, iron, cobalt, nickel, copper,
Zinc, zirconium, molybdenum, ruthenium element it is one or more.
3. a step carbonization manufacture method of carbon material according to claim 1, it is characterised in that the following steps are included:
Step 1, the mixing of raw material weighs melamine powder, polytetrafluorethylepowder powder and metal salt, by metal by a certain percentage
Salt is configured to certain density metal salt solution, and metal salt solution is added in melamine powder and polytetrafluorethylepowder powder and is carried out
Mixing, grinding obtain uniformly mixed powder sample after mill is dry；
Step 2, one step carbonization, by step 1 gained powder sample, under certain condition, step carbonization can be obtained nitrogen, fluorine
With the carbon material of transition metal codope.
4. step carbonization manufacture method according to claim 3, it is characterised in that: step 1 melamine powder is gathered
The mass ratio of metal meets 1:(0.25-4.0 in tetrafluoroethene powder and metal salt): (0.00001-0.2)；The side of the grinding
Method can be hand-ground or mechanical ball mill.
5. step carbonization manufacture method according to claim 3, it is characterised in that: the method that the step 1 is ground is hand
Dynamic grinding or mechanical ball mill；The time of grinding is 0.5-2.0 hours.
6. step carbonization manufacture method according to claim 3, it is characterised in that: the condition that the step 2 is carbonized be
Under inert atmosphere, with heating rate for 3-10 DEG C/min, start to warm up from room temperature between 600 DEG C -1200 DEG C, then keep the temperature carbon
Change 0.5-3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910482806.1A CN110148762B (en) | 2019-06-26 | 2019-06-26 | Carbon material with nitrogen, fluorine and transition metal co-doped graphene structure and one-step carbonization preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910482806.1A CN110148762B (en) | 2019-06-26 | 2019-06-26 | Carbon material with nitrogen, fluorine and transition metal co-doped graphene structure and one-step carbonization preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110148762A true CN110148762A (en) | 2019-08-20 |
| CN110148762B CN110148762B (en) | 2022-05-31 |
Family
ID=67590564
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910482806.1A Active CN110148762B (en) | 2019-06-26 | 2019-06-26 | Carbon material with nitrogen, fluorine and transition metal co-doped graphene structure and one-step carbonization preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110148762B (en) |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111672521A (en) * | 2020-05-14 | 2020-09-18 | 中国科学院福建物质结构研究所 | Transition metal monoatomic material and preparation method and application thereof |
| CN112158829A (en) * | 2020-09-29 | 2021-01-01 | 中国地质大学（武汉） | Graphite-like supermolecule and preparation method thereof, doped graphene and preparation method thereof |
| CN112531178A (en) * | 2020-11-23 | 2021-03-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Fuel cell cathode multi-metal doped multi-element non-metal oxygen reduction catalyst and preparation method thereof |
| CN112652779A (en) * | 2020-12-11 | 2021-04-13 | 广东邦普循环科技有限公司 | High-activity oxygen reduction catalyst and preparation method and application thereof |
| CN112652780A (en) * | 2020-12-15 | 2021-04-13 | 河南师范大学 | Fe/Fe3Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst |
| CN112952119A (en) * | 2021-01-29 | 2021-06-11 | 中国地质大学（武汉） | Transition metal doped two-dimensional carbon nanosheet and preparation method and application thereof |
| CN113299914A (en) * | 2020-02-21 | 2021-08-24 | 中国科学院宁波材料技术与工程研究所 | Fluorocarbon-containing material and preparation method and application thereof |
| CN114763260A (en) * | 2021-01-14 | 2022-07-19 | 中国科学院广州能源研究所 | High-pore-volume fluorine-doped hollow carbon sphere and preparation method and application thereof |
| CN116239162A (en) * | 2023-03-31 | 2023-06-09 | 蜂巢能源科技(无锡)有限公司 | Positive electrode material precursor and preparation method and application thereof |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974381A (en) * | 2012-11-30 | 2013-03-20 | 中国科学院长春应用化学研究所 | Fluorine and nitrogen co-doping carbon black catalyst and preparation method thereof |
| CN105742655A (en) * | 2014-12-11 | 2016-07-06 | 中国科学院大连化学物理研究所 | Graded porous carbon material for fuel cell and preparation and application of graded porous carbon material |
| CN105731437A (en) * | 2016-01-26 | 2016-07-06 | 苏州大学 | Exotic-atom-doped graphene, and preparation method and application thereof |
| CN106876728A (en) * | 2017-02-14 | 2017-06-20 | 中国科学技术大学 | Monatomic graphene-based catalyst of load of high density transition metal and preparation method thereof |
| DE102016102594A1 (en) * | 2016-02-15 | 2017-08-17 | Albert-Ludwigs-Universität Freiburg | Process for the preparation of doped graphene oxide and / or graphene |
| CN109437165A (en) * | 2018-12-25 | 2019-03-08 | 桂林电子科技大学 | A kind of fluorine, nitrogen co-doped three-dimensional grapheme material and one walk carbonization manufacture method |
-
2019
- 2019-06-26 CN CN201910482806.1A patent/CN110148762B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102974381A (en) * | 2012-11-30 | 2013-03-20 | 中国科学院长春应用化学研究所 | Fluorine and nitrogen co-doping carbon black catalyst and preparation method thereof |
| CN105742655A (en) * | 2014-12-11 | 2016-07-06 | 中国科学院大连化学物理研究所 | Graded porous carbon material for fuel cell and preparation and application of graded porous carbon material |
| CN105731437A (en) * | 2016-01-26 | 2016-07-06 | 苏州大学 | Exotic-atom-doped graphene, and preparation method and application thereof |
| DE102016102594A1 (en) * | 2016-02-15 | 2017-08-17 | Albert-Ludwigs-Universität Freiburg | Process for the preparation of doped graphene oxide and / or graphene |
| CN106876728A (en) * | 2017-02-14 | 2017-06-20 | 中国科学技术大学 | Monatomic graphene-based catalyst of load of high density transition metal and preparation method thereof |
| CN109437165A (en) * | 2018-12-25 | 2019-03-08 | 桂林电子科技大学 | A kind of fluorine, nitrogen co-doped three-dimensional grapheme material and one walk carbonization manufacture method |
Non-Patent Citations (1)
| Title |
|---|
| HONGLIANG PENG ET AL.: "Nitrogen and Fluorine co-doped carbon catalyst with high oxygen", 《ELECTROCHIMICA ACTA》 * |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113299914B (en) * | 2020-02-21 | 2022-08-19 | 中国科学院宁波材料技术与工程研究所 | Fluorocarbon-containing material and preparation method and application thereof |
| CN113299914A (en) * | 2020-02-21 | 2021-08-24 | 中国科学院宁波材料技术与工程研究所 | Fluorocarbon-containing material and preparation method and application thereof |
| CN111672521A (en) * | 2020-05-14 | 2020-09-18 | 中国科学院福建物质结构研究所 | Transition metal monoatomic material and preparation method and application thereof |
| CN112158829A (en) * | 2020-09-29 | 2021-01-01 | 中国地质大学（武汉） | Graphite-like supermolecule and preparation method thereof, doped graphene and preparation method thereof |
| CN112158829B (en) * | 2020-09-29 | 2022-02-01 | 中国地质大学（武汉） | Graphite-like supermolecule and preparation method thereof, doped graphene and preparation method thereof |
| CN112531178A (en) * | 2020-11-23 | 2021-03-19 | 上海纳米技术及应用国家工程研究中心有限公司 | Fuel cell cathode multi-metal doped multi-element non-metal oxygen reduction catalyst and preparation method thereof |
| CN112652779A (en) * | 2020-12-11 | 2021-04-13 | 广东邦普循环科技有限公司 | High-activity oxygen reduction catalyst and preparation method and application thereof |
| CN112652780A (en) * | 2020-12-15 | 2021-04-13 | 河南师范大学 | Fe/Fe3Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst |
| CN112652780B (en) * | 2020-12-15 | 2022-11-11 | 河南师范大学 | Fe/Fe 3 Preparation method of C nano-particle loaded porous nitrogen-doped carbon-based oxygen reduction catalyst |
| CN114763260A (en) * | 2021-01-14 | 2022-07-19 | 中国科学院广州能源研究所 | High-pore-volume fluorine-doped hollow carbon sphere and preparation method and application thereof |
| CN114763260B (en) * | 2021-01-14 | 2023-09-05 | 中国科学院广州能源研究所 | Fluorine-doped hollow carbon sphere with high pore volume and preparation method and application thereof |
| CN112952119A (en) * | 2021-01-29 | 2021-06-11 | 中国地质大学（武汉） | Transition metal doped two-dimensional carbon nanosheet and preparation method and application thereof |
| CN116239162A (en) * | 2023-03-31 | 2023-06-09 | 蜂巢能源科技(无锡)有限公司 | Positive electrode material precursor and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110148762B (en) | 2022-05-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110148762A (en) | The carbon material and one of a kind of nitrogen, fluorine and transition metal codope graphene-structured walk carbonization manufacture method | |
| CN104681823B (en) | A kind of nitrogen-doped graphene and Co3O4 hollow nano-sphere composites and its preparation method and application | |
| CN113270595B (en) | Nitrogen-doped carbon-supported non-noble metal nano catalyst prepared based on MOF | |
| CN109678153A (en) | The preparation method and its catalytic applications in fuel battery negative pole of a kind of N doping porous carbon | |
| CN109524678A (en) | A kind of analysis oxygen ferrocobalt-cobalt ferrite/nitrogen-doped nanometer carbon pipe composite catalyst and its preparation method and application | |
| CN107808963A (en) | A kind of hydrogen reduction/oxygen separates out bifunctional catalyst preparation method | |
| CN109652821A (en) | For the Ni-N-C catalyst of carbon dioxide electro-reduction reaction and preparation and application | |
| CN111001428B (en) | Metal-free carbon-based electrocatalyst, preparation method and application | |
| CN110993975B (en) | Nitrogen-doped porous carbon non-metal catalyst, preparation method thereof and application thereof in redox reaction | |
| CN113437314B (en) | Nitrogen-doped carbon-supported low-content ruthenium and Co 2 Three-function electrocatalyst of P nano particle and preparation method and application thereof | |
| CN110721713B (en) | Mo 2 C catalytic material and preparation method and application thereof | |
| CN108080015A (en) | The preparation of functional carbon material based on schiff bases-MOF and the application as elctro-catalyst | |
| CN108878909A (en) | A kind of three-dimensional porous composite material and preparation method and application based on biomass | |
| CN110504456B (en) | Oxygen reduction electrode based on nitrogen-oxygen doped ball/sheet porous carbon material and preparation method and application thereof | |
| CN103816894A (en) | Pt-Ru alloy nano electro-catalyst having doped graphene carrier and preparation method thereof | |
| CN108358181A (en) | Hydrogen evolution reaction electrocatalyst of phosphide, preparation method and application | |
| CN113571713A (en) | PtZn-loaded nitrogen-doped carbon catalyst, preparation method thereof and hydrogen-oxygen fuel cell | |
| Yu et al. | A multi-shelled CeO 2/Co@ N-doped hollow carbon microsphere as a trifunctional electrocatalyst for a rechargeable zinc–air battery and overall water splitting | |
| CN109860645B (en) | Preparation method and application of biogel nitrogen fixation doped porous carbon | |
| CN114628696B (en) | Preparation method of porous carbon-supported cobalt-based bifunctional oxygen catalyst | |
| CN115312790A (en) | Preparation and application of binary palladium-tin nano-alloy catalyst loaded on selenium-doped MXene | |
| CN113659153B (en) | Preparation method of oxygen reduction/oxygen precipitation reaction difunctional transition metal nitride heterojunction electrocatalyst | |
| CN113201759B (en) | Three-dimensional porous carbon supported bismuth sulfide/bismuth oxide composite catalyst and preparation method and application thereof | |
| CN114725405A (en) | Preparation and application of composite carbon nanoparticles loaded with cobalt-iron core-shell structure | |
| CN112002909B (en) | Preparation method of Zn-Cu-N-based co-doped carbon composite material |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |