CN110354884A - A kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC and its preparation method and application - Google Patents
A kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC and its preparation method and application Download PDFInfo
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- CN110354884A CN110354884A CN201910567331.6A CN201910567331A CN110354884A CN 110354884 A CN110354884 A CN 110354884A CN 201910567331 A CN201910567331 A CN 201910567331A CN 110354884 A CN110354884 A CN 110354884A
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- 239000000463 material Substances 0.000 title claims abstract description 56
- 229910003321 CoFe Inorganic materials 0.000 title claims abstract description 50
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 46
- 239000001257 hydrogen Substances 0.000 title claims abstract description 42
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 42
- 239000001301 oxygen Substances 0.000 title claims abstract description 34
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 34
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 230000009467 reduction Effects 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000843 powder Substances 0.000 claims abstract description 41
- 239000003054 catalyst Substances 0.000 claims abstract description 38
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 15
- 239000010941 cobalt Substances 0.000 claims abstract description 15
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 14
- 238000005554 pickling Methods 0.000 claims abstract description 12
- 229910052742 iron Inorganic materials 0.000 claims abstract description 9
- 239000003446 ligand Substances 0.000 claims abstract description 9
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000002270 dispersing agent Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 6
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 33
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 20
- 238000010792 warming Methods 0.000 claims description 13
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 11
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 11
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 11
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- 150000002460 imidazoles Chemical class 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 4
- XLSZMDLNRCVEIJ-UHFFFAOYSA-N methylimidazole Natural products CC1=CNC=N1 XLSZMDLNRCVEIJ-UHFFFAOYSA-N 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- YZEUHQHUFTYLPH-UHFFFAOYSA-N 2-nitroimidazole Chemical compound [O-][N+](=O)C1=NC=CN1 YZEUHQHUFTYLPH-UHFFFAOYSA-N 0.000 claims description 2
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 238000005660 chlorination reaction Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 229910021393 carbon nanotube Inorganic materials 0.000 description 10
- 239000002041 carbon nanotube Substances 0.000 description 10
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 10
- 230000001588 bifunctional effect Effects 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000001291 vacuum drying Methods 0.000 description 9
- 238000005406 washing Methods 0.000 description 9
- 230000015572 biosynthetic process Effects 0.000 description 7
- 229910020676 Co—N Inorganic materials 0.000 description 6
- 239000002585 base Substances 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910052723 transition metal Inorganic materials 0.000 description 4
- 150000003624 transition metals Chemical class 0.000 description 4
- 239000012445 acidic reagent Substances 0.000 description 3
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 150000008614 2-methylimidazoles Chemical class 0.000 description 2
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009466 transformation Effects 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000000779 depleting effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000008246 gaseous mixture Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007603 infrared drying Methods 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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
Abstract
The present invention relates to a kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC and its preparation method and application.The preparation method includes the following steps: S1: cobalt source, source of iron, nitrogenous MOF ligand material, dispersing agent and solvent mixed, stirred, is washed, is centrifuged, it is dry, and obtain precursor powder；S2: precursor powder is calcined at hydrogen-argon-mixed atmosphere, 600~800 DEG C, obtains powder；S3: by powder pickling, it is drying to obtain the difunctional oxygen precipitation-hydrogen reduction catalysis material [email protected] method provided by the invention has process flow simple, it is low in cost, the features such as safety and environmental protection, under alkaline condition, electrocatalysis characteristic of the catalysis material being prepared in terms of ORR is substantially close with the Pt catalyst of business, its stability is even better than Pt, and also has good catalytic performance in terms of OER, is suitable for a variety of new energy air cell catalyst systems such as zinc-air battery.
Description
Technical field
The present invention relates to new energy air cell catalyst technical field, in particular to a kind of difunctional oxygen precipitation-oxygen is also
Former catalysis material CoFe@NC and its preparation method and application.
Background technique
As the problem of environmental pollution got worse for rapidly depleting and its causing of non-renewable fossil energy promotes
People explore and study new green energy resource and its transformation system.And the storage of the energy and transformation technology become the focus of people,
Such as metal-air battery, fuel cell etc..These new energy batteries often all can using noble metal catalyst such as commercialization Pt,
IrO2, the features such as but its expensive price, scarcity of resources limits development speed.Individual base metal can only often be catalyzed list
One reaction, does not have while being catalyzed the ability of different reactions, and such as Co@NC, function admirable is precipitated in oxygen, but hydrogen reduction performance has
Wait improve.Therefore, probing into a kind of high-performance, low price, environmental-friendly difunctional non-precious metal catalyst becomes particularly significant.
Transition metal is introduced in the carbon material of exotic atom doping and is often used as bifunctional catalyst, because exotic atom is mixed
Its porosity of miscellaneous carbon material is high, and large specific surface area, mass transfer rate is fast, exposes more active site, effectively improves activity
The dispersibility of substance, to improve catalytic activity.The introducing of transition metal such as Fe can be further since electronics acts synergistically
Optimizing surface structure.The mutual synergistic effect in Fe-N, Co-N double activated site, has achieved the effect that double-function catalyzing.But it is existing
OER the and ORR catalytic performance of bifunctional catalyst still have a certain distance compared with noble metal catalyst, catalytic performance is still
It is to be improved.
Therefore, developing a kind of bifunctional catalyst with good catalytic has important research significance and using valence
Value.
Summary of the invention
It is an object of the invention to the defect for overcoming the catalytic performance of existing bifunctional catalyst bad and deficiencies, provide one
The preparation method of the difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC of kind.The present invention is forerunner with MOF, in high temperature, hydrogen argon
Under conditions of gaseous mixture, surface forms carbon nanotube, and carbon skeleton still keeps the octahedral structure of presoma, there is more micropore
It is formed, which increase the specific surface areas of bifunctional catalyst CoFe@NC, mass transfer rate are accelerated, to improve catalyst
Electrocatalysis characteristic；In addition, the introducing of Co, the Co-N active site of formation is conducive to OER；And the introducing of Fe, due to coelectron
Effect, its surface texture can be advanced optimized, and Fe ratio Co is easier the features such as adsorbing OH-, OOH-, O ﹒, can be effective
Promote ORR, achieve the effect that double-function catalyzing.Preparation method process flow provided by the invention is simple, low in cost, peace
Loopful is protected；The difunctional oxygen precipitation being prepared-hydrogen reduction catalysis material CoFe@NC under alkaline condition, in terms of ORR
Electrocatalysis characteristic is substantially close with the Pt catalyst of business, and stability is even better than Pt, and also has well in terms of OER
Catalytic performance, be suitable for a variety of new energy air cell catalyst systems such as zinc-air battery.
Another object of the present invention is to provide a kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC.
Another object of the present invention is to provide above-mentioned difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC to prepare
Application in new energy air cell catalyst system.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of preparation method of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC, includes the following steps:
S1: cobalt source, source of iron, nitrogenous MOF ligand material, dispersing agent and solvent are mixed, and are stirred, and are washed, and are centrifuged, dry,
Obtain precursor powder；The molar ratio of ferro element is 4~19:1 in cobalt element and source of iron in the cobalt source；Cobalt element and ferro element
The molar ratio of integral molar quantity and nitrogenous MOF ligand material is 1~1.11:8；
S2: by precursor powder in hydrogen-argon-mixed atmosphere, 280~350 DEG C are warming up to, calcines 2~3h, then be warming up to
It 600~800 DEG C, calcines, it is cooling, obtain black powder；
S3: by powder pickling, it is drying to obtain the difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC.
Bifunctional catalyst is prepared as presoma using MOF in the present invention, under conditions of high temperature, hydrogen-argon-mixed,
Surface forms carbon nanotube, and carbon skeleton still keeps the octahedral structure of presoma, there is more mesoporous formation.Which increase double
The specific surface area of function catalyst CoFe@NC, accelerates mass transfer rate, to improve the electrocatalysis characteristic of catalyst.
In addition, further increasing its catalytic performance by the introducing of transition metal.The introducing of Co, the Co-N active sites of formation
Point is conducive to OER；And the introducing of Fe can advanced optimize its surface texture due to the effect of coelectron, and Fe ratio Co is more
It is easy absorption OH-、OOH-, O ﹒ the features such as, ORR can have been effectively promoted, achieved the effect that double-function catalyzing.
The features such as preparation method provided by the invention has process flow simple, low in cost, safety and environmental protection, in alkaline item
Under part, electrocatalysis characteristic of the catalysis material being prepared in terms of ORR is substantially close with the Pt catalyst of business, stablizes
Property be even better than Pt, and also there is good catalytic performance in terms of OER, be suitable for a variety of new energy air such as zinc-air battery
Cell catalyst system.
Cobalt source, source of iron, nitrogenous MOF ligand material, dispersing agent and the solvent of this field routine are used equally in the present invention.
Preferably, cobalt source described in S1 is one or more of cobalt nitrate, cobaltous sulfate or cobalt chloride.
Preferably, source of iron described in S1 is one or more of ferric nitrate, iron chloride, ferric sulfate or ferric acetyl acetonade.
Preferably, nitrogenous MOF ligand material described in S1 be one of methylimidazole, imidazoles or 2- nitroimidazole or
It is several.
It is further preferable that nitrogenous MOF ligand material described in S1 is methylimidazole.
Preferably, dispersing agent described in S1 is polyvinylpyrrolidone.
Preferably, solvent described in S1 is one or more of methanol or water.
Preferably, the molar ratio of ferro element is 9:1 in cobalt element and source of iron in the cobalt source.
Preferably, the volume fraction of hydrogen-argon-mixed middle hydrogen described in S2 is 5~10%.
Preferably, the time of calcining described in S2 is 2~3h.
Preferably, the temperature of calcining described in S2 is 700 DEG C, time 3h.
Preferably, in S3 pickling process are as follows: powder is soaked in acid reagent.
Acid out can remove some nonactive and unstable reunion Co particles formed in carbonisation.
It is further preferable that the acid reagent is one or more of hydrochloric acid, sulfuric acid, nitric acid.
It is further preferable that it is 0.1~1mol/L that the acid reagent, which is concentration,.
It is further preferable that the time impregnated is 6~12h.
A kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC, is prepared by above-mentioned preparation method.
Preferably, the difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC is octahedral structure.
Above-mentioned difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC is preparing new energy air cell catalyst system
In application it is also within the scope of the present invention.
Preferably, the new energy air cell is zinc-air battery.
Compared with prior art, the invention has the following beneficial effects:
(1) bifunctional catalyst is prepared as presoma using MOF in the present invention, in high temperature, hydrogen-argon-mixed condition
Under, surface forms carbon nanotube, and carbon skeleton still keeps the octahedral structure of presoma, has more micropore to be formed.This increases
The specific surface area of bifunctional catalyst CoFe@NC, accelerates mass transfer rate, to improve the electrocatalysis characteristic of catalyst.
(2) its catalytic performance is further increased by the introducing of transition metal.The introducing of Co, the Co-N active site of formation
Be conducive to OER；And the introducing of Fe can advanced optimize its surface texture due to the effect of coelectron, and Fe ratio Co more holds
Easily absorption OH-、OOH-, O ﹒ the features such as, ORR can have been effectively promoted, achieved the effect that double-function catalyzing.
(3) the features such as preparation method provided by the invention has process flow simple, low in cost, safety and environmental protection, in alkali
Property under the conditions of, electrocatalysis characteristic in terms of ORR is substantially close with the Pt catalyst of business, and stability is even better than
Pt, and also there is good catalytic performance in terms of OER, it is suitable for a variety of new energy air cell catalyst such as zinc-air battery
System.
Detailed description of the invention
Fig. 1 is the SEM figure of each presoma made from embodiment 1；
Fig. 2 is the SEM figure of catalysis material made from embodiment 1；
Fig. 3 schemes for the SEM of catalysis material obtained in embodiment 2；
Fig. 4 obtains SEM figure for catalysis material obtained in embodiment 3；
Fig. 5 schemes for the SEM of catalysis material obtained in comparative example 1；
Fig. 6 schemes for the SEM of catalyst material obtained in comparative example 2；
It is bent that Fig. 7 is embodiment 1, the ORR of catalysis material obtained by embodiment 2, embodiment 3, Pt, comparative example 1 polarizes
Line；
Fig. 8 is embodiment 1, embodiment 2, embodiment 3, IrO2, catalysis material obtained by comparative example 1 OER polarization
Curve.
Fig. 9 is the ORR polarization curve of catalysis material obtained by embodiment 2 and comparative example 2；
Figure 10 is the ORR polarization curve of catalysis material obtained by embodiment 2 and comparative example 2.
Specific embodiment
Below with reference to embodiment, the present invention is further explained.These embodiments are merely to illustrate the present invention rather than limitation
The scope of the present invention.Test method without specific conditions in lower example embodiment usually according to this field normal condition or is pressed
The condition suggested according to manufacturer；Used raw material, reagent etc., unless otherwise specified, being can be from the business such as conventional market
The raw materials and reagents that approach obtains.The variation for any unsubstantiality that those skilled in the art is done on the basis of the present invention
And replacement belongs to scope of the present invention.
Embodiment 1
The present embodiment provides a series of difunctional oxygen precipitations-hydrogen reduction catalysis material CoFe@NC, are prepared via a method which
It obtains.
(1) by 1.210g cobalt chloride, 0.228g ferric nitrate, 80mL methanol, 0.5g polyvinylpyrrolidone, 3.7g 2- first
The mixing of base imidazoles, stirring at normal temperature for 24 hours, three times with ethanol washing, are centrifuged 5min, 60 DEG C of vacuum drying obtain under the revolving speed of 8000rpm
To purple powder 1 (molar ratio of ferro-cobalt is 9:1)；
By 1.1276g cobalt chloride, 0.2798g ferric nitrate, 80mL methanol, 0.5g polyvinylpyrrolidone, 3.7g 2- methyl
Imidazoles mixing, stirring at normal temperature for 24 hours, three times with ethanol washing, are centrifuged 5min, 60 DEG C of vacuum drying obtain under the revolving speed of 8000rpm
Purple powder 3 (molar ratio of ferro-cobalt is 8.5:1.5)；
By 1.2767g cobalt chloride, 0.0933g ferric nitrate, 80mL methanol, 0.5g polyvinylpyrrolidone, 3.7g 2- methyl
Imidazoles mixing, stirring at normal temperature for 24 hours, three times with ethanol washing, are centrifuged 5min, 60 DEG C of vacuum drying obtain under the revolving speed of 8000rpm
Purple powder 4 (molar ratio of ferro-cobalt is 9.5:0.5)；
(2) each group purple powder (i.e. presoma) is respectively placed in hydrogen-argon-mixed (hydrogen volume score is 5~10%)
In, 280 DEG C then are warming up to 5 DEG C/min, 2h is calcined, then be warming up to 600 DEG C with the rate of 2 DEG C/min, calcines 3h, finally certainly
It is so cooling, obtain black powder；
(3) powder in (2) is placed in the hydrochloric acid solution of 1mol/L and impregnates 6h to carry out pickling, 60 DEG C are dried in vacuo,
Difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC is obtained, CoFe@NC-600 DEG C is denoted as.
Embodiment 2
The present embodiment provides a kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC, are prepared via a method which
It arrives.
(1) by 1.210g cobalt chloride, 0.228g ferric nitrate, 80mL methanol, 0.5g polyvinylpyrrolidone, 3.7g 2- first
The mixing of base imidazoles, stirring at normal temperature for 24 hours, three times with ethanol washing, are centrifuged 5min, 60 DEG C of vacuum drying obtain under the revolving speed of 8000rpm
To purple powder；
(2) presoma is placed in hydrogen-argon-mixed (hydrogen volume score is 5~10%), then with 5 DEG C/min heating
To 280 DEG C, 2h is calcined, then be warming up to 700 DEG C with the rate of 2 DEG C/min, calcine 3h, last natural cooling obtains black powder；
(3) powder in (2) is placed in the hydrochloric acid solution of 1mol/L and impregnates 6h to carry out pickling, 60 DEG C are dried in vacuo,
Difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC is obtained, CoFe@NC-700 DEG C is denoted as.
Embodiment 3
The present embodiment provides a kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC, are prepared via a method which
It arrives.
(1) by 1.210g cobalt chloride, 0.228g ferric nitrate, 80mL methanol, 0.5g polyvinylpyrrolidone, 3.7g 2- first
The mixing of base imidazoles, stirring at normal temperature for 24 hours, three times with ethanol washing, are centrifuged 5min, 60 DEG C of vacuum drying obtain under the revolving speed of 8000rpm
To purple powder；
(2) presoma is placed in hydrogen-argon-mixed (hydrogen volume score is 5~10%), then with 5 DEG C/min heating
To 280 DEG C, 2h is calcined, then be warming up to 800 DEG C with the rate of 2 DEG C/min, calcine 3h, last natural cooling obtains black powder；
(3) powder in (2) is placed in the hydrochloric acid solution of 1mol/L and impregnates 6h to carry out pickling, 60 DEG C are dried in vacuo,
Difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC is obtained, CoFe@NC-800 DEG C is denoted as.
Embodiment 4
The present embodiment provides a kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC, are prepared via a method which
It arrives.
(1) by 1.210g cobalt chloride, 0.228g ferric nitrate, 80mL methanol, 0.5g polyvinylpyrrolidone, 3.4g 2- first
The mixing of base imidazoles, stirring at normal temperature for 24 hours, three times with ethanol washing, are centrifuged 5min, 60 DEG C of vacuum drying obtain under the revolving speed of 8000rpm
To purple powder；
(2) presoma is placed in hydrogen-argon-mixed (hydrogen volume score is 5~10%), then with 5 DEG C/min heating
To 300 DEG C, 3h is calcined, then be warming up to 700 DEG C with the rate of 2 DEG C/min, calcine 3h, last natural cooling obtains black powder；
(3) powder in (2) is placed in the hydrochloric acid solution of 1mol/L and impregnates 6h to carry out pickling, 60 DEG C are dried in vacuo,
Obtain difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC.
Embodiment 5
The present embodiment provides a kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC, are prepared via a method which
It arrives.
(1) by 1.210g cobalt chloride, 0.228g ferric nitrate, 80mL methanol, 0.5g polyvinylpyrrolidone, 4.0g 2- first
The mixing of base imidazoles, stirring at normal temperature for 24 hours, three times with ethanol washing, are centrifuged 5min, 60 DEG C of vacuum drying obtain under the revolving speed of 8000rpm
To purple powder；
(2) presoma is placed in hydrogen-argon-mixed (hydrogen volume score is 5~10%), then with 5 DEG C/min heating
To 350 DEG C, 2h is calcined, then be warming up to 700 DEG C with the rate of 2 DEG C/min, calcine 3h, last natural cooling obtains black powder；
(3) powder in (2) is placed in the hydrochloric acid solution of 1mol/L and impregnates 6h to carry out pickling, 60 DEG C are dried in vacuo,
Obtain difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC.
Comparative example 1
This comparative example provides a kind of catalysis material Co@NC, is prepared via a method which to obtain.
(1) by 1.344g cobalt chloride, 80mL methanol, 0.5g polyvinylpyrrolidone, the mixing of 3.7g 2-methylimidazole, often
Temperature stirring for 24 hours, three times with ethanol washing, is centrifuged 5min, 60 DEG C of vacuum drying obtain purple powder under the revolving speed of 8000rpm；
(2) presoma is placed in hydrogen-argon-mixed (hydrogen volume score is 5~10%), then with 5 DEG C/min heating
To 280 DEG C, 2h is calcined, then be warming up to 700 DEG C with the rate of 2 DEG C/min, calcine 3h, last natural cooling obtains black powder；
(3) powder in (2) is placed in the hydrochloric acid solution of 1mol/L and impregnates 6h to carry out pickling, 60 DEG C are dried in vacuo,
Catalysis material Co@NC is obtained, Co@NC-700 DEG C is denoted as.
Comparative example 2
The present embodiment provides a kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC, are prepared via a method which
It arrives.
(1) by 1.210g cobalt chloride, 0.228g ferric nitrate, 80mL methanol, 0.5g polyvinylpyrrolidone, 3.7g 2- first
The mixing of base imidazoles, stirring at normal temperature for 24 hours, three times with ethanol washing, are centrifuged 5min, 60 DEG C of vacuum drying obtain under the revolving speed of 8000rpm
To purple powder；
(2) presoma is placed in argon gas, is then warming up to 280 DEG C with 5 DEG C/min, calcine 2h, then with the speed of 2 DEG C/min
Rate is warming up to 700 DEG C, calcines 3h, last natural cooling, obtain black powder；
(3) powder in (2) is placed in the hydrochloric acid solution of 1mol/L and impregnates 6h to carry out pickling, 60 DEG C are dried in vacuo,
Difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC is obtained, CoFe-700 DEG C (Ar) is denoted as.
The performance of the catalysis material of each embodiment and comparative example preparation is tested.
(1) pattern test
It is the SEM figure of purple powder obtained in step (1) in embodiment 1, from figure it is found that under three ratios such as Fig. 1
Presoma pattern is octahedral structure, compared with ratio is 8.5:1.5, the even particle size of 9.5:0.5 when ratio is 9:1.
Follow-up test is carried out with the CoFe@NC-600 DEG C that purple powder 1 in embodiment 1 obtains.
It is embodiment 1 (Fig. 2), embodiment 2 (Fig. 3), embodiment 3 (Fig. 4) and comparative example 1 (Fig. 5), comparison such as Fig. 2~6
The SEM figure for the catalysis material that example 2 (Fig. 6) provides, from figure it is found that Fig. 2, that is, CoFe@NC-600 DEG C (being obtained by purple powder 1),
Particle size is about 600nm or so, and surface has a small amount of carbon nanotube (mark in such as figure), it may be possible to which temperature is too low to be led
Presoma is caused not to be completely reduced.Fig. 2 is CoFe@NC-700 DEG C, and pattern is octahedral structure, rough surface, and is had
A large amount of carbon nanotube.Fig. 3 is CoFe@NC-800 DEG C, and pattern slightly collapses for CoFe@NC-700 DEG C, and table
The high-visible bigger more holes in face improve mass transfer rate although increasing specific surface area, are the reduction of its active sites
Point reduces catalytic performance such as Fe-N and Co-N active site.Fig. 4, that is, Co@NC-700 DEG C, can clearly find out particle size
Small, shape of octahedron is collapsed, this is also a reason of its performance not as good as CoFe@NC-700 DEG C.It is found that 600~800
Calcining at DEG C can form carbon nanotube on octahedra surface, wherein it is most with the carbon nanotube that 700 DEG C of calcinings obtain, for most
Good calcination temperature.
Fig. 6, that is, CoFe-700 DEG C (Ar), it can clearly find out that its surface does not have carbon nanotube appearance, illustrates the atmosphere of hydrogen
It is with the formation for helping carbon nanotube, and significantly improves catalytic performance.
(2) electro-chemical test
Electro-chemical test is carried out using three-electrode system.It is platinized platinum to electrode, reference electrode is saturation mercuric oxide electrode, work
The glass-carbon electrode for being coated with catalyst as electrode, wherein catalyst be embodiment 1, embodiment 2, embodiment 3, precious metals pt, it is expensive
Metal IrO2, comparative example 1, catalyst obtained by comparative example 2.When testing ORR, electrolyte is 0.1mol/L KOH aqueous solution.
When testing OER, electrolyte is 1mol/L KOH solution.Catalyst film preparation step is as follows on electrode: 5mg catalyst being taken to add
700uL isopropanol, 250uL deionized water and 50uL Nafion solution, ultrasonic disperse 30min take 10uL with the liquid-transfering gun of 10uL
It on finely dispersed hanging drop to bright and clean glass-carbon electrode, can be tested after infra-red drying, electric performance test result such as Fig. 7
With shown in Figure 10.
The catalyst of Examples 1 to 3 preparation is very close to Pt onset potential (1.234V), carrying current
(5.19236mA.cm-2) and half wave potential (1.056V).Wherein, the best CoFe@NC-700 of performance, onset potential are
1.166V, half wave potential 1.05V, carrying current 4.9921mAcm-2.Co@NC-700, either originates in comparative example 1
Potential (1.089V), half wave potential (1.03V) and carrying current (4.76994mAcm-2) all much not as good as CoFe NC-700,
It is 10mAcm in current density-2When, CoFe@NC-700 potential is 1.786V, although its performance ratio IrO2 (1.706V) still has
There are many a certain distance, but compared with the Co@NC-700 (1.848V) in comparative example 1, OER performance boost.This shows
Fe doping improves the catalytic activity of ORR and OER；Its onset potential (0.996V) of CoFe@NC-700 (Ar) in comparative example 2, half
Wave current potential (0.857V) and carrying current (2.67771mAcm-2) current density be 10mAcm-2When potential be
1.823V shows its catalytic performance much not as good as CoFe NC-700, this shows H2Presence facilitate promoted ORR and OER urge
Change activity.
It is obtained by comparative example, compared with no catalyst (comparative example 1) for introducing Fe, double function made from Examples 1 to 3
Energy catalyst has good double-function catalyzing activity, and surface forms carbon nanotube, and carbon skeleton still keeps the eight of presoma
Face body structure has more mesoporous formation, and which increase the specific surface areas of bifunctional catalyst CoFe@NC, accelerates mass transfer speed
Rate, to improve the electrocatalysis characteristic of catalyst.The Co-N active site of the introducing of another aspect Co, formation is conducive to OER；
The introducing of Fe can advanced optimize its surface texture due to the effect of coelectron, and Fe ratio Co is easier to adsorb OH-、
OOH-, O ﹒ the features such as, ORR can have been effectively promoted, achieved the effect that double-function catalyzing.In addition, compared with comparative example 2,
Surface carbon nano tube structure abundant increases specific surface area, increases active site, promotes the promotion of its catalytic performance.
Above-described specific embodiment has carried out further the purpose of the present invention, technical scheme and beneficial effects
It is described in detail, it should be understood that being not intended to limit the present invention the foregoing is merely a specific embodiment of the invention
Protection scope, all within the spirits and principles of the present invention, any modification, equivalent substitution, improvement and etc. done should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC preparation method, which is characterized in that including walking as follows
It is rapid:
S1: cobalt source, source of iron, nitrogenous MOF ligand material, dispersing agent and solvent are mixed, and are stirred, and are washed, and are centrifuged, dry, before obtaining
Drive body powder；In the cobalt source in cobalt element and source of iron ferro element 4~19:1 of molar ratio；The total moles of cobalt element and ferro element
Amount and the molar ratio of nitrogenous MOF ligand material are 1~1.11:8；
S2: by precursor powder in hydrogen-argon-mixed atmosphere, being warming up to 280~350 DEG C, calcine 2~3h, then it is warming up to 600~
It 800 DEG C, calcines, it is cooling, obtain black powder；
S3: by powder pickling, it is drying to obtain the difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC.
2. preparation method according to claim 1, which is characterized in that cobalt source described in S1 is cobalt nitrate, cobaltous sulfate or chlorination
One or more of cobalt；Source of iron described in S1 is one of ferric nitrate, iron chloride, ferric sulfate or ferric acetyl acetonade or several
Kind；Nitrogenous MOF ligand material described in S1 is one or more of methylimidazole, imidazoles or 2- nitroimidazole.
3. preparation method according to claim 1, which is characterized in that dispersing agent described in S1 is polyvinylpyrrolidone；S1
Described in solvent be one or more of methanol or water.
4. preparation method according to claim 1, which is characterized in that the volume fraction of hydrogen-argon-mixed middle hydrogen described in S2 is
5~10%.
5. preparation method according to claim 1, which is characterized in that the time of calcining described in S2 is 2~3h.
6. preparation method according to claim 1, which is characterized in that the time of calcining described in S2 is 600 DEG C~800 DEG C, when
Between be 3h.
7. preparation method according to claim 1, which is characterized in that the process of pickling in S3 are as follows: powder is soaked in sour examination
In agent.
8. a kind of difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC, which is characterized in that any by claim 1~7
The preparation method is prepared.
9. difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC according to claim 8, which is characterized in that double function
Energy oxygen precipitation-hydrogen reduction catalysis material CoFe@NC is octahedral structure.
10. any difunctional oxygen precipitation-hydrogen reduction catalysis material CoFe@NC of claim 8~9 is preparing new energy air
Application in cell catalyst system.
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