CN109119649A - A kind of cobalt atom is anchored on monatomic catalyst of the cobalt on carbon nano-fiber and its preparation method and application - Google Patents
A kind of cobalt atom is anchored on monatomic catalyst of the cobalt on carbon nano-fiber and its preparation method and application Download PDFInfo
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- CN109119649A CN109119649A CN201811013094.0A CN201811013094A CN109119649A CN 109119649 A CN109119649 A CN 109119649A CN 201811013094 A CN201811013094 A CN 201811013094A CN 109119649 A CN109119649 A CN 109119649A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 64
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical group [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 60
- 239000002134 carbon nanofiber Substances 0.000 title claims abstract description 54
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 41
- 239000010941 cobalt Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 229920000642 polymer Polymers 0.000 claims abstract description 41
- 238000009987 spinning Methods 0.000 claims abstract description 34
- 239000000835 fiber Substances 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 22
- 239000008139 complexing agent Substances 0.000 claims abstract description 14
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 238000006555 catalytic reaction Methods 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 8
- -1 acyl acetone cobalt Chemical compound 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229920002285 poly(styrene-co-acrylonitrile) Polymers 0.000 claims description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 5
- 238000002604 ultrasonography Methods 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000004090 dissolution Methods 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 3
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 239000011975 tartaric acid Substances 0.000 claims description 3
- 235000002906 tartaric acid Nutrition 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000008246 gaseous mixture Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims 2
- 229920001223 polyethylene glycol Polymers 0.000 claims 2
- OSNIIMCBVLBNGS-UHFFFAOYSA-N 1-(1,3-benzodioxol-5-yl)-2-(dimethylamino)propan-1-one Chemical compound CN(C)C(C)C(=O)C1=CC=C2OCOC2=C1 OSNIIMCBVLBNGS-UHFFFAOYSA-N 0.000 claims 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- 125000005909 ethyl alcohol group Chemical group 0.000 claims 1
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims 1
- SCUZVMOVTVSBLE-UHFFFAOYSA-N prop-2-enenitrile;styrene Chemical compound C=CC#N.C=CC1=CC=CC=C1 SCUZVMOVTVSBLE-UHFFFAOYSA-N 0.000 claims 1
- 229920000638 styrene acrylonitrile Polymers 0.000 claims 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 33
- 238000000034 method Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- 239000000446 fuel Substances 0.000 abstract description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 2
- 238000001523 electrospinning Methods 0.000 abstract 1
- 239000011148 porous material Substances 0.000 abstract 1
- 229910020676 Co—N Inorganic materials 0.000 description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 13
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- 238000010041 electrostatic spinning Methods 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 10
- 210000004027 cell Anatomy 0.000 description 5
- 239000005030 aluminium foil Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 230000005611 electricity Effects 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000002041 carbon nanotube Substances 0.000 description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- SZKXDURZBIICCF-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O SZKXDURZBIICCF-UHFFFAOYSA-N 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 125000004355 nitrogen functional group Chemical group 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 210000003850 cellular structure Anatomy 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002121 nanofiber Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 230000010148 water-pollination Effects 0.000 description 1
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
- H01M4/90—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)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
本发明涉及一种钴原子锚定在碳纳米纤维上的钴单原子催化剂及其制备方法和应用。所述制备方法包括如下步骤：S1：将钴源、络合剂和含氮聚合物溶解在溶剂中得外部溶液；将可溶聚合物溶解在溶剂中得内部溶液；S2：利用同轴静电丝纺将外部溶液和内部溶液丝纺得到初纺纤维；S3：将丝纺纤维中的可溶聚合物除去后，于500~1000℃下高温煅烧2~5h即得到钴单原子催化剂。本发明利用静电丝纺技术和高温煅烧制备得到的钴单原子催化剂具有直径小、孔径小、孔隙率高、纤维均一性好等优点，且具有较好的ORR和OER催化性能，优异的甲醇耐受性和稳定性，可广泛应用于燃料电池、金属‑空气电池。本发明提供的制备方法过程简单，易于操作。
The invention relates to a cobalt single-atom catalyst in which cobalt atoms are anchored on carbon nanofibers, and a preparation method and application thereof. The preparation method includes the following steps: S1: dissolving a cobalt source, a complexing agent and a nitrogen-containing polymer in a solvent to obtain an external solution; dissolving a soluble polymer in a solvent to obtain an internal solution; S2: using a coaxial electrostatic wire Spinning the outer solution and the inner solution to obtain the as-spun fiber; S3: After removing the soluble polymer in the spinning fiber, calcined at a high temperature of 500-1000 °C for 2-5 h to obtain a cobalt single-atom catalyst. The cobalt single-atom catalyst prepared by the electrospinning technology and high-temperature calcination has the advantages of small diameter, small pore size, high porosity, good fiber uniformity, etc., and has good ORR and OER catalytic performance, excellent methanol resistance. Acceptability and stability, can be widely used in fuel cells, metal-air batteries. The preparation method provided by the invention is simple in process and easy to operate.
Description
Technical field
The invention belongs to novel energy resource material technology and electrochemical catalysis fields, and in particular to a kind of cobalt atom is anchored on carbon
Monatomic catalyst of cobalt on nanofiber and its preparation method and application.
Background technique
Oxygen reduction reaction (ORR) and oxygen are precipitated (OER) and usually carry out under the catalysis of precious metals pt, are clean energy resource production
Important reaction, such as metal-air battery and fuel cell.However, the scarcity of platinum and high cost seriously limit
Its business application.A kind of catalyst has been developed for substituting precious metals pt catalyst comprising on carbon support by
The stable transition metal ions of nitrogen functional group, including being pyrolyzed and non-pyrolytic nitrogen containing metal complex compound.For the nitrogenous gold of pyrolysis
Metal complex, they usually pass through is heat-treated transition metal salt appropriate at high temperature, prepared by nitrogen/Carbon based precursor.Insertion
M-Nx(x=2,4) are considered as active site and ORR the and OER catalytic activity for being responsible for enhancing.
But doping nitrogen-atoms carbon material may be had a huge impact, such as greatly change material surface texture,
Modulation its cellular structure, the electron transfer rate enhance its hydrophily, influence material surface pKa value, improving material, to expand
Carbon nanomaterial applications in various fields range.Although exploitation has been achieved for very for the CNFs of ORR in alkaline electrolyte
More achievements, but developing for the novel monatomic CNFs catalyst of ORR and OER is still a challenging task.
Summary of the invention
It is an object of the invention to overcome in the prior art precious metals pt catalyst it is with high costs, novel monatomic CNFs is urged
It is monatomic to provide a kind of cobalt that cobalt atom is anchored on carbon nano-fiber for the OER catalytic performance of agent bad defect and deficiency
The preparation method of catalyst.The present invention has using the monatomic catalyst of cobalt that electrostatic spinning techinque and high-temperature calcination are prepared
The advantages that diameter is small, aperture is small, porosity is high, fiber homogeneity is good, and there is preferable ORR and OER catalytic performance, it is excellent
Methanol tolerance and stability can be widely applied to fuel cell, metal-air battery.Preparation method mistake provided by the invention
Journey is simple, easily operated.
Another object of the present invention is to provide a kind of cobalt atoms to be anchored on the monatomic catalyst of the cobalt on carbon nano-fiber.
Another object of the present invention is to provide above-mentioned cobalt atoms to be anchored on the monatomic catalyst of the cobalt on carbon nano-fiber
Application in electrochemical catalysis field.
For achieving the above object, the present invention adopts the following technical scheme:
A kind of cobalt atom is anchored on the preparation method of the monatomic catalyst of the cobalt on carbon nano-fiber, includes the following steps:
S1: the dissolution of cobalt source, complexing agent and polymer with nitrogen is obtained into external solution in a solvent；Soluble polymer is dissolved in solvent
In internal solution；Cobalt source in the external solution, complexing agent, polymer with nitrogen and solvent mass ratio be 1:1 ~ 2:2 ~ 4:20
~40；The mass ratio of soluble polymer and solvent is 1:5 ~ 1:10 in internal solution；
S2: external solution and internal solution silk spinning are obtained into the first spinning fibre that outer diameter is 500 ~ 1000nm using coaxial electrostatic silk spinning
Dimension；
S3: after the soluble polymer in silk spinning fiber is removed, it is former to obtain cobalt list by 2 ~ 5h of high-temperature calcination at 500 ~ 1000 DEG C
Muonic catalysis agent.
Preparation method provided by the invention prepares carbon nano-fiber pipe using coaxial electrostatic spinning and in conjunction with high-temperature calcination.
Electrostatic silk spinning can the fine structure of Effective Regulation fiber can get the material with ultra-hydrophobicity in conjunction with the substance of low-surface-energy
Material is used for self-supporting material.The present invention has certain size as-spun fibre by what electrostatic silk spinning obtained, can regulate and control final
The aperture of carbon nanotube, porosity and fiber homogeneity in product.
In addition, the as-spun fibre is alternatively arranged as template and plays the role of evenly dispersed, while polymer support can also be played
Flexibility and ease for operation, can also using catalysis material (such as Co) and polymer micro-nanometer size surface recombination generation compared with
Strong synergistic effect improves catalysis efficiency.
In addition to this, it selects polymer with nitrogen as carbon source and nitrogen source, and controls cobalt source in external solution, complexing agent, contains
The proportion of soluble polymer and solvent in the proportion and internal solution of nitrogen polymer and solvent, it can be achieved that cobalt atom complexing
It is fixed, and effectively promote the specific surface area of the monatomic catalyst of cobalt, porosity and catalytic performance.This is because (high in heat treatment
Temperature calcining) when soluble polymer resolve into small molecule organic gas and release, formed between carbon nano-fiber pipe a large amount of
Hole increases specific surface, increases active site.It is mixed in addition, the nitrogen in polymer with nitrogen can enter carbon lattice with forming nitrogen
Miscellaneous carbon realizes that in carbon nano tube surface, nitrogen functional group stablizes cobalt ions, forms Co-N4 CNFs.As N doping can excessively be broken
The excellent structure of bad carbon itself, leads to carbon reduced performance；If doping is too low, then the complexing that cannot achieve cobalt atom is fixed.
The present invention by the monatomic catalyst of cobalt that is prepared of control optimization of each condition have diameter is small, aperture is small,
The advantages that porosity is high, fiber homogeneity is good, and there is preferable ORR and OER catalytic performance, excellent methanol tolerance and steady
It is qualitative, it can be widely applied to fuel cell, metal-air battery.Preparation method process provided by the invention is simple, is easy to grasp
Make.
Conventional cobalt source and solvent in the art are used equally in the present invention.
Preferably, the cobalt source is one of cobalt nitrate, cobalt chloride, cobalt acetate and acetylacetone cobalt or a variety of；It is described
Solvent is one of ethyl alcohol, isopropanol, N,N-dimethylformamide, deionized water, dimethyl formyl, methylene chloride or formic acid
Or it is a variety of.
The complexing agent that the present invention selects can be the complexing agent of this field routine.
In order to further increase the catalytic performance of the monatomic catalyst of cobalt, the present invention selects nitrogenous complexing agent.
Preferably, the complexing agent is citric acid, Phen, ethylenediamine tetra-acetic acid, tartaric acid, m- tetraphenylporphines
One of or it is a variety of.
The nitrogenous compound and soluble polymer of this field routine are used equally in the present invention.
In order to further increase ORR and OER catalytic performance, the present invention selects high carbonization and conversion ratio and high nitrogen-containing
The nitrogenous compound raw material of element.
Preferably, the polymer with nitrogen is polyvinylpyrrolidone, N-Methyl pyrrolidone, polyacrylonitrile, polyoxygenated
One of ethylene and styrene-acrylonitrile copolymer are a variety of.
Preferably, the soluble polymer is polyvinylpyrrolidone, N-Methyl pyrrolidone, polyacrylonitrile, polyoxy
Change one of ethylene and styrene-acrylonitrile copolymer or a variety of.
Preferably, in S1 at 50 ~ 150 DEG C, stirring 1 ~ dissolved for 24 hours.
The more uniform as-spun fibre of size in order to obtain, the present invention have carried out further the process conditions of electrostatic silk spinning
Optimization.
Preferably, in S2 the coaxial spinning head of coaxial electrostatic silk spinning internal diameter be 0.16 ~ 1.07mm, outer diameter be 0.55 ~
3.5mm。
Preferably, the feed rate of external solution is 0.4 ~ 1.5 ml/h, and the feed rate of internal solution is 0.1 ~ 1.0
ml/h。
Preferably, the distance of the needle of spinning head to collector is 10 ~ 25cm, and voltage is 5 ~ 30KV.
Means commonly used in the art can be taken to remove soluble polymer, the present invention provides two kinds of preferable removal sides herein
Formula.
Preferably, silk spinning fiber is placed in water ultrasound in S3, removes soluble polymer.
Preferably, silk spinning fiber is placed in 1 ~ 4h of standing at 200 ~ 500 DEG C in S3, removes soluble polymer.
Soluble polymer is removed by heating, a large amount of hole can be formed between carbon nano-fiber pipe, is further increased
Large ratio surface increases active site.
Preferably, the time ultrasonic in S3 is 5 ~ 60min.
Preferably, the atmosphere of S3 high temperature calcining is one in ammonia, argon gas, nitrogen, oxygen, hydrogen or argon hydrogen gaseous mixture
Kind is a variety of.
A kind of monatomic catalyst of cobalt that cobalt atom is anchored on carbon nano-fiber is also claimed in the present invention.By above-mentioned
Preparation method is prepared.
Above-mentioned cobalt atom is anchored on application of the monatomic catalyst of the cobalt on carbon nano-fiber in electrochemical catalysis field
Also within the scope of the present invention.
Preferably, application of the monatomic catalyst of the cobalt in ORR and OER reaction.
Preferably, the monatomic catalyst of the cobalt is preparing the application in fuel cell or metal-air battery.
Compared with prior art, the invention has the following beneficial effects:
The present invention has that diameter is small, aperture using the monatomic catalyst of cobalt that electrostatic spinning techinque and high-temperature calcination are prepared
Small, the advantages that porosity is high, fiber homogeneity is good, and there is preferable ORR and OER catalytic performance, excellent methanol tolerance
And stability, it can be widely applied to fuel cell, metal-air battery.Preparation method process provided by the invention is simple, is easy to
Operation.
Detailed description of the invention
Fig. 1 is the Co-N that the embodiment of the present invention 1 provides4 The SEM of CNFs catalyst schemes；
Fig. 2 is the Co-N that the embodiment of the present invention 1 provides4 The SEM of CNFs catalyst schemes；
Fig. 3 is the Co-N that the embodiment of the present invention 1 provides4 The SEM of CNFs catalyst schemes；
Fig. 4 is the Co-N that the embodiment of the present invention 1 provides4 The SEM of CNFs catalyst schemes；
Fig. 5 is the Co-N that the embodiment of the present invention 1 provides4 The SEM of CNFs catalyst schemes；
Fig. 6 is the Co-N that the embodiment of the present invention 1 provides4 The ORR polarization curve of CNFs catalyst；
Fig. 7 is the Co-N that the embodiment of the present invention 1 provides4 The OER polarization curve of CNFs catalyst；
Fig. 8 is the Co-N that the embodiment of the present invention 1 provides4 The methanol tolerance figure of CNFs catalyst.
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 cobalt atoms to be anchored on the monatomic Co-N of the cobalt on carbon nano-fiber4 CNFs catalyst passes through such as lower section
Method is prepared.
Weigh the acetylacetone cobalt of 0.1g, the m- tetraphenylporphines complexing agent of 0.2g and the dissolution of 0.4g polyacrylonitrile polymer
External solution is used in 4g n,N-Dimethylformamide solvent, while the polyethylene oxide polymer for weighing 0.5g to be dissolved in
Internal solution is used in 5g N,N-dimethylformamide solvent.
Two kinds of solution are vigorously stirred 8h to being completely dissolved at 70 DEG C, two kinds of viscous solutions are drawn onto syringe, are implemented
Coaxial electrostatic spinning technique.During electrostatic spinning, choose with spinning head internal diameter and outer diameter be respectively 0.35mm and
1.05mm adjusts coaxial spinning head, and the distance from the needle of spinning head to collector is 12 cm, and keeps the electricity of 15 kV
Pressure, while the feed rate for controlling external solution is 0.6 ml/h and the feed rate of internal solution is 0.4 ml/h, will
To as-spun fibre collect on aluminium foil.
As-spun fibre is put into ultrasound 5min in deionized water, removes the polymer in as-spun fibre, is dried after cleaning standby
With.As-spun fibre dries sample 800 DEG C of calcining 5h under argon gas in being placed on tube furnace, then grinds monatomic to get cobalt is arrived
Catalyst is named as Co-N4 CNFs。
The Co-N that embodiment 1 is provided4 CNFs catalyst characterizes its result in the following ways:
1. using Hitachi-Su8010 type scanning electron microscope (SEM) to carry out before and after sample microscopic appearance, structure etc. into
Row analysis.It can be seen that Co-N from Fig. 1 ~ 54 CNFs catalyst is hollow tubular carbon nano-fiber, and carbon nano-fiber
Diameter is 500nm.
2. using the rotating ring electrode device (RRDE 3A) and occasion China CHI750e type electrochemical operation of ALS company of Japan
It stands to Co-N4 CNFs catalyst and Pt/C catalyst carry out electrocatalysis characteristic characterization.As shown in fig. 6, using glass carbon disk as work
Make electrode, catalyst layer laid on is used as using Pt electrodes to electrode using Ag/AgCl electrode as reference electrode.Its
In, the half wave potential of Pt/C is 0.81V (vs .RHE), Co-N4 The half wave potential of CNFs is 0.78V (vs .RHE), Pt/C
The limiting current density of catalyst is about 5.8mA cm-2, Co-N4 The limiting current density of CNFs is about 5.9mA cm-2。
3. by Co-N prepared by the present invention4 Pt/C (20%) catalyst and RuO of CNFs catalyst and business2-IrO2
(20%) catalyst carries out analysis oxygen performance test.As shown in fig. 7, Co-N4 CNFs, Pt/C (20%) and and RuO2-IrO2
(20%) catalyst is in 0 .1mol L-1KOH solution in LSV, rotating disk electrode (r.d.e) revolving speed is 1600rpm, and sweep speed is
5mVs-1.As can be seen from Figure 7, Co-N provided in this embodiment4 CNFs has preferable ORR and OER catalytic performance.
Poison comparative test 4. taking and carrying out methanol tolerance with the Pt/C catalyst of business (20%Pt content), using certain
The electric current that catalyst is measured under potential range, the methanol that 4mL is added after waiting electric currents to stablize see curent change situation to measure catalysis
The methanol tolerance toxicity of agent.It is added before and after 4mL methanol, as shown in figure 8, Co-N prepared by the present invention4 CNFs catalyst curent change
Less, and Pt/C catalyst electric current drops sharply to the 20% of initial current, arrive 3000s when, electric current is just restored to initial current
50%, it is very big to illustrate that the addition of methanol influences Pt/C catalyst, further illustrates Co-N prepared by the present invention4 CNFs catalysis
There is agent ratio Pt/C catalyst better methanol tolerance to poison performance and stability.
Embodiment 2
The present embodiment provides cobalt atoms to be anchored on the monatomic Co-N of the cobalt on carbon nano-fiber4 CNFs catalyst passes through such as lower section
Method is prepared.
Weigh the cobalt nitrate of 0.1g, the agent of 0.1g EDTA complex and the dissolution of 0.2g polyvinyl pyrrolidone polymers
External solution is used in 2g isopropanol solvent, while the polyethylene oxide polymer for weighing 0.5g to be dissolved in 2.5 g isopropyls
Internal solution is used in alcohol.
Two kinds of solution are vigorously stirred 12h to being completely dissolved at 80 DEG C, two kinds of viscous solutions are drawn onto syringe, are implemented
Coaxial electrostatic spinning technique.During electrostatic spinning, choose with spinning head internal diameter and outer diameter be respectively 0.41mm and
1.25mm adjusts coaxial spinning head, and the distance from the needle of spinning head to collector is 10 cm, and keeps the electricity of 20 kV
Pressure, while the feed rate for controlling external solution is 0.5 ml/h and the feed rate of internal solution is 0.3 ml/h, will
To as-spun fibre collect on aluminium foil.
As-spun fibre is put into ultrasound 10min in deionized water, removes the polymer in as-spun fibre, is dried after cleaning standby
With.As-spun fibre dries sample 900 DEG C of calcining 4h under argon gas in being placed on tube furnace, then grinds monatomic to get cobalt is arrived
Catalyst is named as Co-N4 CNFs。
Co-N provided in this embodiment4 CNFs catalyst is similar with the performance of catalyst that embodiment 1 provides.
Embodiment 3
The present embodiment provides cobalt atoms to be anchored on the monatomic Co-N of the cobalt on carbon nano-fiber4 CNFs catalyst passes through such as lower section
Method is prepared.
The cobalt chloride of 0.1g is weighed, 0.15g Phen complexing agent and 0.3g styrene-acrylonitrile copolymer polymer are molten
Solution is used for external solution in 3g dichloromethane solvent, while the polyacrylonitrile polymer for weighing 0.5g is dissolved in 3g dichloromethane
Internal solution is used in alkane solvents.
Two kinds of solution are vigorously stirred 12h to being completely dissolved at 90 DEG C, two kinds of viscous solutions are drawn onto syringe, are implemented
Coaxial electrostatic spinning technique.During electrostatic spinning, choose with spinning head internal diameter and outer diameter be respectively 0.45mm and
1.35mm adjusts coaxial spinning head, and the distance from the needle of spinning head to collector is 15 cm, and keeps the electricity of 25 kV
Pressure, while the feed rate for controlling external solution is 0.9 ml/h and the feed rate of internal solution is 0.7 ml/h, will
To as-spun fibre collect on aluminium foil.
As-spun fibre is put into ultrasound 25min in deionized water, removes the polymer in as-spun fibre, is dried after cleaning standby
With.As-spun fibre dries sample 1000 DEG C of calcining 3h under argon gas in being placed on tube furnace, then grinds monatomic to get cobalt is arrived
Catalyst is named as Co-N4 CNFs。
Co-N provided in this embodiment4 CNFs catalyst is similar with the performance of catalyst that embodiment 1 provides.
Embodiment 4
The present embodiment provides cobalt atoms to be anchored on the monatomic Co-N of the cobalt on carbon nano-fiber4 CNFs catalyst passes through such as lower section
Method is prepared.
The cobalt acetate of 0.1g is weighed, 0.2g tartaric acid complexing agent and 0.4gN- crassitude ketone polymer are dissolved in 4g first
External solution is used in sour solvent, while the styrene-acrylonitrile copolymer polymer for weighing 0.5g to be dissolved in 4g formic acid solvent
In be used for internal solution.
Two kinds of solution are vigorously stirred 5h to being completely dissolved at 140 DEG C, two kinds of viscous solutions are drawn onto syringe, are implemented
Coaxial electrostatic spinning technique.During electrostatic spinning, choose with spinning head internal diameter and outer diameter be respectively 0.51mm and
2.11mm adjusts coaxial spinning head, and the distance from the needle of spinning head to collector is 20 cm, and keeps the electricity of 20 kV
Pressure, while the feed rate for controlling external solution is 1.0ml/h and the feed rate of internal solution is 1.0 ml/h, will obtain
As-spun fibre collect on aluminium foil.
As-spun fibre is placed at 400 DEG C after constant temperature 3h and is placed in tube furnace 700 DEG C of calcining 5h under argon gas, is then ground
Mill is named as Co-N to get the monatomic catalyst of cobalt is arrived4 CNFs。
Co-N provided in this embodiment4 CNFs catalyst is similar with the performance of catalyst that embodiment 1 provides.
Those of ordinary skill in the art will understand that embodiment here be to help reader understand it is of the invention
Principle, it should be understood that protection scope of the present invention is not limited to such specific embodiments and embodiments.This field it is common
Technical staff disclosed the technical disclosures can make the various various other tools for not departing from essence of the invention according to the present invention
Body variations and combinations, these variations and combinations are still within the scope of the present invention.
Claims (10)
1. the preparation method that a kind of cobalt atom is anchored on the monatomic catalyst of the cobalt on carbon nano-fiber, which is characterized in that including
Following steps:
S1: the dissolution of cobalt source, complexing agent and polymer with nitrogen is obtained into external solution in a solvent；Soluble polymer is dissolved in solvent
In internal solution；Cobalt source in the external solution, complexing agent, polymer with nitrogen and solvent mass ratio be 1:1 ~ 2:2 ~ 4:20
~40；The mass ratio of soluble polymer and solvent is 1:5 ~ 1:10 in internal solution；
S2: external solution and internal solution silk spinning are obtained into the first spinning fibre that outer diameter is 500 ~ 1000nm using coaxial electrostatic silk spinning
Dimension；
S3: after the soluble polymer in silk spinning fiber is removed, it is former to obtain cobalt list by 2 ~ 5h of high-temperature calcination at 500 ~ 1000 DEG C
Muonic catalysis agent.
2. preparation method according to claim 1, which is characterized in that the cobalt source is cobalt nitrate, cobalt chloride, cobalt acetate and second
One of acyl acetone cobalt is a variety of；The solvent is ethyl alcohol, isopropanol, N,N-dimethylformamide, deionized water, dimethyl
One of formyl, methylene chloride or formic acid are a variety of.
3. preparation method according to claim 1, which is characterized in that the complexing agent is citric acid, Phen, ethylenediamine
One of tetraacethyl, tartaric acid, m- tetraphenylporphines are a variety of.
4. preparation method according to claim 3, which is characterized in that the polymer with nitrogen is polyvinylpyrrolidone, N-
One of methyl pyrrolidone, polyacrylonitrile, polyethylene glycol oxide and styrene-acrylonitrile copolymer are a variety of；It is described solvable
Property polymer be that polyvinylpyrrolidone, N-Methyl pyrrolidone, polyacrylonitrile, polyethylene glycol oxide and styrene-acrylonitrile are total
One of polymers is a variety of.
5. preparation method according to claim 1, which is characterized in that in S1 at 50 ~ 150 DEG C, stirring 1 ~ carry out for 24 hours it is molten
Solution.
6. preparation method according to claim 1, which is characterized in that the internal diameter of the coaxial spinning head of coaxial electrostatic silk spinning in S2
For 0.16 ~ 1.07mm, outer diameter is 0.55 ~ 3.5mm；The feed rate of external solution be 0.4 ~ 1.5 ml/h, internal solution into
Material rate is 0.1 ~ 1.0 ml/h；The distance of the needle of spinning head to collector is 10 ~ 25cm, and voltage is 5 ~ 30KV.
7. preparation method according to claim 1, which is characterized in that silk spinning fiber is placed in water ultrasound in S3, dries, goes
Except soluble polymer；Or 1 ~ 4h is stood at 200 ~ 500 DEG C, remove soluble polymer.
8. the preparation method according to claim 1, which is characterized in that S3 high temperature calcining atmosphere be ammonia, argon gas,
One of nitrogen, oxygen, hydrogen or argon hydrogen gaseous mixture are a variety of.
9. a kind of cobalt atom is anchored on the monatomic catalyst of the cobalt on carbon nano-fiber, which is characterized in that by claim 1 ~ 8
Any preparation method is prepared.
10. cobalt atom described in claim 9 is anchored on the monatomic catalyst of the cobalt on carbon nano-fiber in electrochemical catalysis field
In application.
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