CN107308977B - Difunctional VPO catalysts of cobalt nitrogen sulphur codope carbon aerogels and its preparation method and application - Google Patents
Difunctional VPO catalysts of cobalt nitrogen sulphur codope carbon aerogels and its preparation method and application Download PDFInfo
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- CN107308977B CN107308977B CN201710585199.2A CN201710585199A CN107308977B CN 107308977 B CN107308977 B CN 107308977B CN 201710585199 A CN201710585199 A CN 201710585199A CN 107308977 B CN107308977 B CN 107308977B
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- mercaptan
- dopamine
- aeroge
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- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 238000002360 preparation method Methods 0.000 title claims abstract description 34
- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 19
- BNKWCSJBOZKTJL-UHFFFAOYSA-N [Co].[N].[S] Chemical compound [Co].[N].[S] BNKWCSJBOZKTJL-UHFFFAOYSA-N 0.000 title claims abstract description 18
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 100
- 229960003638 dopamine Drugs 0.000 claims abstract description 50
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229940005550 sodium alginate Drugs 0.000 claims abstract description 40
- 239000000661 sodium alginate Substances 0.000 claims abstract description 40
- 235000010413 sodium alginate Nutrition 0.000 claims abstract description 36
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims abstract description 33
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 26
- 239000010941 cobalt Substances 0.000 claims abstract description 26
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000000017 hydrogel Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 9
- 239000000126 substance Substances 0.000 claims abstract description 8
- 239000005864 Sulphur Substances 0.000 claims abstract description 7
- 239000011148 porous material Substances 0.000 claims abstract description 7
- 150000003233 pyrroles Chemical class 0.000 claims abstract description 7
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 claims abstract description 5
- 125000004433 nitrogen atom Chemical group N* 0.000 claims abstract description 5
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 3
- IYPQZXRHDNGZEB-UHFFFAOYSA-N cobalt sodium Chemical compound [Na].[Co] IYPQZXRHDNGZEB-UHFFFAOYSA-N 0.000 claims abstract 4
- 238000000034 method Methods 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 21
- 239000004964 aerogel Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 229910052799 carbon Inorganic materials 0.000 claims description 14
- 241000894007 species Species 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- 230000001965 increasing effect Effects 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 claims description 7
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000007710 freezing Methods 0.000 claims description 7
- 230000008014 freezing Effects 0.000 claims description 7
- 229910052573 porcelain Inorganic materials 0.000 claims description 7
- 230000001376 precipitating effect Effects 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 238000002242 deionisation method Methods 0.000 claims description 6
- 230000003111 delayed effect Effects 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 5
- 229920001282 polysaccharide Polymers 0.000 claims description 5
- 239000005017 polysaccharide Substances 0.000 claims description 5
- 239000011593 sulfur Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 3
- 239000000499 gel Substances 0.000 claims description 3
- -1 polysaccharide Sodium alginate Chemical class 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 2
- 150000004676 glycans Chemical class 0.000 claims description 2
- 238000005087 graphitization Methods 0.000 claims description 2
- 238000006902 nitrogenation reaction Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 5
- 229910002804 graphite Inorganic materials 0.000 abstract description 5
- 239000010439 graphite Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 5
- 238000005119 centrifugation Methods 0.000 abstract description 3
- 238000010335 hydrothermal treatment Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000004108 freeze drying Methods 0.000 abstract description 2
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 14
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 238000011160 research Methods 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000010287 polarization Effects 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000010953 base metal Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 239000003863 metallic catalyst Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- HOYKPPXKLRXDBR-UHFFFAOYSA-N [O].[Co].[Co] Chemical compound [O].[Co].[Co] HOYKPPXKLRXDBR-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001722 carbon compounds Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- INPLXZPZQSLHBR-UHFFFAOYSA-N cobalt(2+);sulfide Chemical compound [S-2].[Co+2] INPLXZPZQSLHBR-UHFFFAOYSA-N 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- ZZVUWRFHKOJYTH-UHFFFAOYSA-N diphenhydramine Chemical compound C=1C=CC=CC=1C(OCCN(C)C)C1=CC=CC=C1 ZZVUWRFHKOJYTH-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction 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
-
- B01J35/23—
-
- 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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- 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
-
- 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
- H01M4/9075—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
Abstract
Difunctional VPO catalysts of a kind of cobalt nitrogen sulphur codope carbon aerogels and its preparation method and application.The present invention first makes cobalt ions equably in conjunction with sodium alginate, again with dopamine and mercaptan hydrothermal treatment, centrifugation obtains dopamine/mercaptan/cobalt-Sodium Alginate Hydrogel Films, and cobalt nitrogen sulphur codope carbon aerogels VPO catalysts are made through high-temperature calcination in resulting dopamine/mercaptan/cobalt-sodium alginate aeroge after freeze-drying.The catalyst be the poroid material of aeroge, average pore size be 2~4nm, specific surface area is in 126.8~138.3m2/g；Wherein cobalt is with Co simple substance, CoO and Co3O4Form exist；The nitrogen-atoms being entrained in poroid carbon material mainly exists with pyrroles's type and graphite mould.Due to the codope of cobalt, nitrogen and sulphur, the catalyst has high analysis oxygen and oxygen reduction catalytic activity simultaneously under alkaline condition, and it is raw materials used it is at low cost, preparation method is simple, easily operated, convenient for large-scale production.
Description
Technical field:
The invention belongs to novel energy resource material technology and electrochemical catalysis fields, and in particular to cobalt nitrogen sulphur codope carbon airsetting
The difunctional VPO catalysts of glue；Further relate to the preparation method of the catalyst and its in the reaction of electrolyzed alkaline water Oxygen anodic evolution and fuel
Electro-catalysis application in cell cathode oxygen reduction reaction.
Background technique:
As the mankind are continuously increased cleaning and sustainable energy demand, great effort has been put into height by scientists
In terms of the research and development of effect, low cost and environmentally friendly energy conversion and stocking system.Wherein oxygen reduction reaction (ORR) In
Generally existing cathode reaction in fuel cell and metal-air battery, oxygen evolution reaction (OER) then solar energy fuel synthesis and
It plays an important role in water-splitting energy storage system.Therefore, catalyst especially VPO catalysts have been to restrict new energy dress
The main bottleneck set.In view of the activity and stability of catalyst, the catalyst for ORR reaction mainly has Pt and its alloy,
And the catalyst for being used for OER mainly has IrO2Or RuO2, but these noble metals are very rare in nature, make current power supply
Apparatus cost is too high.Therefore, research and development non-precious metal catalyst becomes hot subject concerned by people in the field.
Transition metal oxide represents a major class material, including single metal oxides and poly-metal deoxide.Make
The material of noble metal catalyst can be substituted for one kind, transition metal oxide has following advantage, and rich reserves, price are low
It is honest and clean, easily prepared, environmental-friendly etc..Since transition metals such as Mn, Fe, Co, Ni etc. have multiple valence state, can be formed
Oxide with various crystal structures all has preferable electrocatalysis characteristic to OER and ORR, but uses as VPO catalysts
When there are still electric conductivity and bad dispersibility, specific surface is small the defects of.Electroactive kinds of transition metals is loaded into electric conductivity
Catalyst poorly conductive can be overcome the problems, such as on excellent hetero atom (such as nitrogen or sulphur) doping carbon-based material and is improved compound
The specific surface area and stability of catalyst can greatly improve the double-function catalyzing performance of the OER and ORR of catalyst.Therefore, it grinds
Studying carefully the compound containing kinds of transition metals and nitrogen sulfur doping carbon material has important meaning to exploitation bi-functional oxygen electrode catalyst
Justice.Many containing the compounds of cobalt/cobalt oxide type and (nitrogen sulfur doping) carbon material have been developed as OER under alkaline condition and
ORR bifunctional catalyst, the results showed that, (nitrogen sulfur doping) carbon material can significantly improve the electrochemical catalysis performance of compound.Mesh
Before, study more cobalt type be cobalt oxide or cobalt sulfide, it is difunctional based on cobalt nanometer particle or cobalt oxide-cobalt nanometer particle
The research of VPO catalysts is considerably less.Cobalt nitrogen sulphur codope is prepared with marine polysaccharide sodium alginate (SA) for carbon source according to consulting literatures
Carbon aerogels yet there are no report as the research of difunctional VPO catalysts.
In order to prepare cobalt type and nitrogen sulphur codope carbon material uniformly compound and large specific surface area cobalt nitrogen sulphur codope carbon
Compound elctro-catalyst after the present invention dissolves by heating SA, is added divalent cobalt and is dissolved in SA solution, is sufficiently centrifuged and removes after complexing
Remaining metal ion is removed, dopamine, which is added to complexing, to be had in the SA dispersion liquid of cobalt ions, is stirred to dissolve, is added sulphur
Alcohol is sufficiently stirred, and reaction solution is transferred in hydrothermal reaction kettle, and centrifugation obtains dopamine/mercaptan/Co-SA water-setting after hydrothermal treatment
Glue is freeze-dried to obtain dopamine/mercaptan/Co-SA aeroge after cooling in refrigerator, forges under nitrogen atmosphere in tube furnace high temperature
Cobalt nitrogen sulphur codope carbon aerogels (Co/NSPC) are made after burning, and study that its OER and ORR under alkaline condition is difunctional to be urged
Change performance.
The present invention uses and makes cobalt ions equably in conjunction with sodium alginate, then with dopamine and mercaptan hydrothermal treatment,
Centrifugation obtains dopamine/mercaptan/Co-SA hydrogel, and resulting dopamine/mercaptan/Co-SA aeroge is through high temperature after freeze-drying
Calcining preparation Co/NSPC aeroge VPO catalysts, can make cobalt reactive specy and nitrogen sulphur atom uniformly compound with carbon aerogels, this is urged
Agent has good electric conductivity and specific surface area using carbon aerogels as matrix, effectively reduces the excessively electric of OER and ORR
Position shows that its ORR process is 4 electronic catalytic mechanism by rotating disk electrode (r.d.e) (RDE) and rotating ring disk electrode (r.r.d.e) (RRDE), is
Ideal ORR reaction process.Elctro-catalyst obtained by this method has given full play to the carbon of cobalt reactive specy and nitrogen sulphur codope
Synergistic effect of the aeroge in terms of electro-catalysis has weight to exploitation novel electrochemical catalyst and energy conversion and memory device
The theoretical and practical significance wanted.
Summary of the invention:
In view of the deficiencies of the prior art and the demand of this field research and application, an object of the present invention are to provide one
The kind difunctional VPO catalysts of cobalt nitrogen sulphur codope carbon aerogels；I.e. using marine polysaccharide sodium alginate as carbon source, under hydrothermal conditions,
It is first that divalent cobalt, dopamine and mercaptan and sodium alginate is sufficiently compound, prepare dopamine/mercaptan/Co-SA hydrogel, refrigerator
It is freeze-dried to obtain dopamine/mercaptan/Co-SA aeroge after middle cooling, is made after the calcining of tube furnace high temperature under nitrogen atmosphere
The difunctional VPO catalysts of cobalt nitrogen sulphur codope carbon aerogels are obtained, the sodium alginate is denoted as SA, cobalt nitrogen sulphur codope carbon aerogels
It is denoted as Co/NSPC；
The second object of the present invention is to provide a kind of preparation side of the difunctional VPO catalysts of cobalt nitrogen sulphur codope carbon aerogels
Method, specifically includes the following steps:
(a) dopamine/mercaptan/Co-SA aeroge preparation
It disperses a certain amount of SA in 200mL deionized water, 80 DEG C of heating stirring 8h make it completely dissolved, and compound concentration is
The SA solution of 40~70mg/mL；2.5g cobalt chloride hexahydrate is configured to the aqueous solution that concentration is 0.02mol/L, whipping process
In be slowly dropped in SA solution, continue stir 4h after in 4000rpm be centrifuged 10min, collect precipitating is scattered in 200mL again
In ionized water, stirring and dissolving after 0.6g dopamine and 40mL mercaptan is added, is transferred in hydrothermal reaction kettle, 100 DEG C of hydro-thermal reaction 2h,
It is stood after reaction solution centrifuge separation washing and obtains dopamine/mercaptan/Co-SA hydrogel, put it into the subzero 20 DEG C of freezings of refrigerator
It is freeze-dried 36h again afterwards, obtains dopamine/mercaptan/Co-SA aeroge.
(b) preparation of the difunctional VPO catalysts of Co/NSPC aeroge
Dopamine/mercaptan/Co-SA aeroge obtained in step (a) is placed in porcelain boat, under nitrogen atmosphere with 5 DEG C/
The rate of min heats in tube furnace, is first increased to 200 DEG C of heating 1h, is heated to 700~900 DEG C of 2~6h of calcining, obtains
The difunctional VPO catalysts of Co/NSPC column aeroge.
Wherein the carbon source in the difunctional VPO catalysts of the aeroge of Co/NSPC column described in step (b) contains in nature
Marine polysaccharide SA abundant is measured, nitrogen source derives from mercaptan in dopamine, sulphur, and cobalt reactive specy is with Co simple substance, CoO and Co3O4's
Form exists, and the partial size of cobalt reactive specy is 30~130nm, is entrained in the nitrogen-atoms in poroid carbon material mainly with pyrroles's type nitrogen
Exist with graphitization nitrogen；The sulphur of doping mainly exists in the form of thiophenic sulfur；This is averaged for column-shaped porous aerogel catalyst
Aperture is 2~4nm, and specific surface area is in 126.8~138.3m2/g。
The three of the object of the invention are to provide a kind of difunctional VPO catalysts of cobalt nitrogen sulphur codope carbon aerogels in alkaline electrolysis
Application in water anode OER and fuel battery negative pole ORR.
The present invention use using sodium alginate as template, the present invention first answers divalent cobalt ion, dopamine and mercaptan and SA
It is freeze-dried to obtain Co/NSPC aeroge after Heshui heat treatment, then prepares Co/NSPC composite aerogel through high-temperature calcination；No
The electric conductivity and specific surface area for improving only catalyst increase its catalytic site, and the oxygen gel catalyst is effective
The overpotential of OER and ORR are reduced, ORR process is almost ideal 4 electronic catalytic mechanism.
Compared with prior art, the present invention have following major advantage and the utility model has the advantages that
1) the difunctional VPO catalysts of aeroge of the present invention are base metal composite material, raw materials used to be easy to buy
And preparation, resourceful and price is lower, and large scale preparation is at low cost；
2) methanol tolerance that difunctional VPO catalysts of the present invention have had, in 0.1mol/L KOH electrolyte
1mol/L methanol is added, the catalytic activity of catalyst is almost without decaying；
3) the difunctional VPO catalysts of aeroge of the present invention are that a kind of novel cobalt nitrogen sulphur codope carbon aerogels are compound
Material has preferable OER and ORR catalytic activity, and base metal/non-metallic catalyst compared with current research report is one-side
OER and ORR activity has significant advantage；
4) difunctional VPO catalysts of the present invention OER activity, hence it is evident that be better than at present research report base metal/
Non-metallic catalyst, and activity is better than commercialization IrO2Catalytic activity；
5) difunctional VPO catalysts preparation method of the present invention is simple, easily operated, convenient for large-scale production.
Detailed description of the invention:
Fig. 1 is the XRD spectra of 2 gained Co/NSPC catalyst of embodiment.
Fig. 2 is the transmission electron microscope picture (left side) and high-resolution-ration transmission electric-lens figure of 2 gained Co/NSPC aerogel catalyst of embodiment
(right side)
Fig. 3 is the full spectrogram of XPS (a), (b) N 1s spectrogram and the S2p figure of 2 gained Co/NSPC aerogel catalyst of embodiment.
Fig. 4 is 2 gained Co/NSPC aeroge of embodiment, 1 gained Co/NPC of comparative example, 2 gained Co/SPC of comparative example catalysis
The OER polarization curve of agent and Ni foam.
Fig. 5 be 2 gained Co/NSPC aeroge of embodiment, 1 gained Co/NPC of comparative example, 2 gained Co/SPC of comparative example and
The ORR polarization curve (a) of Pt/C catalyst；It is bent that 2 gained Co/NSPC aerogel catalyst of embodiment modifies the resulting K-L of RDE
Line chart (b).
Fig. 6 is that 2 gained Co/NSPC aerogel catalyst of embodiment modifies the ORR polarization curve (a) of RRDE and electronics turns
Move number, HO2 -Containing spirogram.
Specific embodiment:
To further understand the present invention, present invention will be further explained below with reference to the attached drawings and examples, but not with
Any mode limits the present invention.
Embodiment 1:
(a) dopamine/mercaptan/Co-SA aeroge preparation
It disperses a certain amount of SA in 200mL deionized water, 80 DEG C of heating stirring 8h make it completely dissolved, and compound concentration is
The SA solution of 40mg/mL；2.5g cobalt chloride hexahydrate is configured to the aqueous solution that concentration is 0.02mol/L, is delayed in whipping process
Slowly be added drop-wise in SA solution, continue stir 4h after in 4000rpm be centrifuged 10min, collect precipitating is scattered in 200mL deionization again
In water, stirring and dissolving after 0.6g dopamine and 40mL mercaptan is added, is transferred in hydrothermal reaction kettle, 100 DEG C of hydro-thermal reaction 2h, reacts
It is stood after liquid centrifuge separation washing and obtains dopamine/mercaptan/Co-SA hydrogel, put it into after the subzero 20 DEG C of freezings of refrigerator again
It is freeze-dried 36h, obtains dopamine/mercaptan/Co-SA aeroge.
(b) preparation of the difunctional VPO catalysts of Co/NSPC aeroge
Dopamine/mercaptan/Co-SA aeroge obtained in step (a) is placed in porcelain boat, under nitrogen atmosphere with 5 DEG C/
The rate of min heats in tube furnace, is first increased to 200 DEG C of heating 1h, is heated to 800 DEG C of calcining 3h, obtains the Co/
The difunctional VPO catalysts of NSPC column aeroge, average pore size be 2~3nm, specific surface area is in 126.8m2/g。
Embodiment 2:
(a) dopamine/mercaptan/Co-SA aeroge preparation
It disperses a certain amount of SA in 200mL deionized water, 80 DEG C of heating stirring 8h make it completely dissolved, and compound concentration is
The SA solution of 50mg/mL；2.5g cobalt chloride hexahydrate is configured to the aqueous solution that concentration is 0.02mol/L, is delayed in whipping process
Slowly be added drop-wise in SA solution, continue stir 4h after in 4000rpm be centrifuged 10min, collect precipitating is scattered in 200mL deionization again
In water, stirring and dissolving after 0.6g dopamine and 40mL mercaptan is added, is transferred in hydrothermal reaction kettle, 100 DEG C of hydro-thermal reaction 2h, reacts
It is stood after liquid centrifuge separation washing and obtains dopamine/mercaptan/Co-SA hydrogel, put it into after the subzero 20 DEG C of freezings of refrigerator again
It is freeze-dried 36h, obtains dopamine/mercaptan/Co-SA aeroge.
(b) preparation of the difunctional VPO catalysts of Co/NSPC aeroge
According to the method and condition preparation of step (b) in embodiment 1.
The average pore size of the difunctional VPO catalysts of gained Co/NSPC column aeroge is 2.0~4.0nm, and specific surface area exists
130.0m2/g。
Embodiment 3:
(a) dopamine/mercaptan/Co-SA aeroge preparation
It disperses a certain amount of SA in 200mL deionized water, 80 DEG C of heating stirring 8h make it completely dissolved, and compound concentration is
The SA solution of 60mg/mL；2.5g cobalt chloride hexahydrate is configured to the aqueous solution that concentration is 0.02mol/L, is delayed in whipping process
Slowly be added drop-wise in SA solution, continue stir 4h after in 4000rpm be centrifuged 10min, collect precipitating is scattered in 200mL deionization again
In water, stirring and dissolving after 0.6g dopamine and 40mL mercaptan is added, is transferred in hydrothermal reaction kettle, 100 DEG C of hydro-thermal reaction 2h, reacts
It is stood after liquid centrifuge separation washing and obtains dopamine/mercaptan/Co-SA hydrogel, put it into after the subzero 20 DEG C of freezings of refrigerator again
It is freeze-dried 36h, obtains dopamine/mercaptan/Co-SA aeroge.
(b) preparation of the difunctional VPO catalysts of Co/NSPC aeroge
According to the method and condition preparation of step (b) in embodiment 1.
The average pore size of the difunctional VPO catalysts of gained Co/NSPC column aeroge is 2.5~3.5nm, and specific surface area exists
133.6m2/g。
Embodiment 4:
(a) dopamine/mercaptan/Co-SA aeroge preparation
According to the method and condition preparation of step (a) in embodiment 2.
(b) preparation of the difunctional VPO catalysts of Co/NSPC aeroge
Dopamine/mercaptan/Co-SA aeroge obtained in step (a) is placed in porcelain boat, under nitrogen atmosphere with 5 DEG C/
The rate of min heats in tube furnace, is first increased to 200 DEG C of heating 1h, is heated to 700 DEG C of calcining 3h, obtains the Co/
The difunctional VPO catalysts of NSPC column aeroge, average pore size be 2~3nm, specific surface area is in 134.2m2/g。
Embodiment 5:
(a) dopamine/mercaptan/Co-SA aeroge preparation
According to the method and condition preparation of step (a) in embodiment 2.
(b) preparation of the difunctional VPO catalysts of Co/NSPC aeroge
Dopamine/mercaptan/Co-SA aeroge obtained in step (a) is placed in porcelain boat, under nitrogen atmosphere with 5 DEG C/
The rate of min heats in tube furnace, is first increased to 200 DEG C of heating 1h, is heated to 900 DEG C of calcining 3h, obtains the Co/
The difunctional VPO catalysts of NSPC column aeroge, average pore size be 2~3nm, specific surface area is in 138.3m2/g。
Comparative example 1:
(a) dopamine/Co-SA aeroge preparation
It disperses a certain amount of SA in 200mL deionized water, 80 DEG C of heating stirring 8h make it completely dissolved, and compound concentration is
The SA solution of 50mg/mL；2.5g cobalt chloride hexahydrate is configured to the aqueous solution that concentration is 0.02mol/L, is delayed in whipping process
Slowly be added drop-wise in SA solution, continue stir 4h after in 4000rpm be centrifuged 10min, collect precipitating is scattered in 200mL deionization again
In water, stirring and dissolving after 0.6g dopamine is added, is transferred in hydrothermal reaction kettle, 100 DEG C of hydro-thermal reaction 2h, reaction solution centrifuge separation
It is stood after washing and obtains dopamine/Co-SA hydrogel, be freeze-dried 36h again after putting it into the subzero 20 DEG C of freezings of refrigerator, much
Bar amine/Co-SA aeroge.
(b) preparation of the difunctional VPO catalysts of Co/NPC aeroge
Dopamine obtained in step (a)/Co-SA aeroge is placed in porcelain boat, under nitrogen atmosphere with 5 DEG C/min's
Rate heats in tube furnace, is first increased to 200 DEG C of heating 1h, is heated to 800 DEG C of calcining 3h, obtains the Co/NPC gas
The difunctional VPO catalysts of gel.
Comparative example 2:
(a) mercaptan/Co-SA aeroge preparation
It disperses a certain amount of SA in 200mL deionized water, 80 DEG C of heating stirring 8h make it completely dissolved, and compound concentration is
The SA solution of 50mg/mL；2.5g cobalt chloride hexahydrate is configured to the aqueous solution that concentration is 0.02mol/L, is delayed in whipping process
Slowly be added drop-wise in SA solution, continue stir 4h after in 4000rpm be centrifuged 10min, collect precipitating is scattered in 200mL deionization again
In water, stirring and dissolving after 40mL mercaptan is added, is transferred in hydrothermal reaction kettle, 100 DEG C of hydro-thermal reaction 2h, reaction solution centrifuge separation is washed
After washing stand obtain mercaptan/Co-SA hydrogel, put it into refrigerator it is subzero 20 DEG C freezing after be freeze-dried 36h again, obtain mercaptan/
Co-SA aeroge.
(b) preparation of the difunctional VPO catalysts of Co/SPC aeroge
Mercaptan obtained in step (a)/Co-SA aeroge is placed in porcelain boat, under nitrogen atmosphere with the speed of 5 DEG C/min
Rate heats in tube furnace, is first increased to 200 DEG C of heating 1h, is heated to 800 DEG C of calcining 3h, obtains the Co/SPC column
The difunctional VPO catalysts of aeroge.
Fig. 1 is the XRD spectra of 2 gained Co/NSPC aerogel catalyst of embodiment.It can be seen from the figure that having at 27.8 °
002 peak of apparent agraphitic carbon, it was demonstrated that SA and dopamine have been carbonized after calcining.There is the spy of Co simple substance at 43.0 ° and 50.9 °
Levy diffraction maximum；There is Co at 56.6 °, 61.9 ° and 64.1 °3O4Characteristic diffraction peak；There is the feature diffraction of CoO at 60.4 ° and 73.9 °
Peak.These results suggest that cobalt ions has been oxidized to oxide phase, while under simple substance carbon existence condition, part after calcining
The oxide of cobalt is reduced for simple substance cobalt.The result shows that generating Co/NSPC catalyst.
Fig. 2 is the transmission electron microscope picture (left side) and high-resolution-ration transmission electric-lens figure of 2 gained Co/NSPC aerogel catalyst of embodiment
(right side).As can be seen that Co/NSPC aerogel catalyst is rendered as cavernous structure from left figure, cobalt reactive specy with it is unformed
Carbon plate is combined with each other, they are rendered as graininess, is equably coated with by unformed carbon plate.Electricity is transmitted from the high-resolution on the right
Mirror figure can be seen that cobalt reactive specy particle and be dispersed on carbon plate, and average grain diameter is about in 30~130nm, with unformed carbon plate
It is combined together.
Fig. 3 is the full spectrogram of XPS (a), (b) N 1s spectrogram and the S2p figure of 2 gained Co/NSPC aerogel catalyst of embodiment.
Figure a shows there is apparent S, Cl, C, N, O and Co at 164.0,200.0,284.8,400.7,532.8 and 782.7eV respectively
Spectral peak, it was demonstrated that there are cobalt reactive specy and nitrogen sulfur doping carbon material, wherein Cl derives from CoCl2Raw material.Divide in N 1s spectrogram
Do not occur oxidized form N, graphite mould N, pyrroles's type N and pyridine type N at 402.1,400.9,400.0 and 398.3eV, wherein with
Based on graphite mould N and pyrroles's type N, this is conducive to OER the and ORR catalytic activity of catalyst.
Embodiment 6:
400 μ L ethyl alcohol and 20 μ L are dispersed by 10mg embodiment 2, comparative example 1 and the resulting catalyst of comparative example 2 respectively
In polytetrafluoroethylsolution solution, after ultrasound mixes solution, 15 μ L slurry drops is taken to be applied to 1 × 1cm2On foam nickel electrode, completely to it
Tabletting measures its OER electrocatalysis characteristic on CHI660D electrochemical workstation after drying；Similarly, respectively by 10mg embodiment
2, comparative example 1 and the resulting catalyst of comparative example 2 are scattered in 400 μ L ethyl alcohol and 15 μ L Nafion solutions, and ultrasound mixes molten
After liquid, 1 μ L slurry drops is taken to be applied to rotating ring disk electrode (r.r.d.e) (RRDE, 0.1256cm2) on, in CHI660D electricity after it is completely dried
Its ORR electrocatalysis characteristic is measured on chem workstation.
Above-mentioned electrocatalysis characteristic test is to be saturated Ag/AgCl electrode as reference electrode, and Pt electrode is to electrode, and sweeping speed is
10mV/s, electrolyte are 0.1M KOH, and electrolyte need to carry out N before OER catalytic performance test2Saturated process, ORR catalytic performance are surveyed
It needs to carry out O before examination2Saturated process.RDE test result is after Koutecky-Levich formula manipulation, by the K-L slope of curve
(B) electron transfer number (n) can be calculated.
J-1=Jk -1+(Bω1/2)-1
B=0.62n F C0D0 2/3v1/6
Wherein F=96485C/mol, C0=1.2 × 10-3Mol/L, D0=1.9 × 10-5cm2/ s, v=0.01cm2/s。
RRDE test result can obtain electron transfer number (n) and H by following formula manipulation2O2Content:
N=4Id·(Id+Ir/N)
HO- 2%=200Id/N·(Id+Ir/ N),
Wherein N=0.43.
Fig. 4 is 2 gained Co/NSPC aeroge of embodiment, 1 gained Co/NPC of comparative example, 2 gained Co/SPC of comparative example catalysis
The OER polarization curve of agent and Ni foam.The take-off potential of the Co/NPC and Co/SPC catalyst of N or S is only adulterated in display in figure
Respectively 1.52 and 1.55V, they are much larger than the super beginning current potential (1.58V) of Ni foam electrode, but adulterated simultaneously as N and S
Its overvoltage of Co/NSPC aerogel catalyst be 1.47V, value be it is the smallest in four kinds of catalyst, illustrate N, S and cobalt reactive species
The codope of class has facilitation well to OER performance.Equally, when current density is 20mA/cm2When, Co/NSPC, Co/
The current potential of NPC, Co/SPCPC and Ni catalyst pair is respectively 1.50,1.59,1.65 and 1.75V.Apparent N, S and cobalt reactive species
The Co/NSPC aerogel catalyst of the codope of class shows optimal starting overpotential.This be primarily due to graphite mould and
Pyrroles's type nitrogen-atoms, thiophenic sulfur and different cobalt reactive specy (including CoO, Co3O4With Co simple substance) presence be greatly facilitated
The electro catalytic activity of catalyst significantly reduces its OER overpotential.
Fig. 5 a be 2 gained Co/NSPC aeroge of embodiment, 1 gained Co/NPC of comparative example, 2 gained Co/SPC of comparative example and
The ORR polarization curve of Pt/C catalyst.As shown, the take-off potential of Co/NSPC aeroge and Co/NPC catalyst is basic
It is identical, about 0.85V, just in the take-off potential of Co/SPC and Pt/C (essentially identical, about 0.83V).Pole when from 0.4V
From the point of view of limiting dissufion current, the limiting diffusion current of Co/NSPC aeroge is -5.64mA/cm2, even greater than business 20%Pt/C
Catalyst (- 5.40mA/cm2), it is far longer than the corresponding limit diffusion of Co/NPC and Co/SPC catalyst of only N or sulfur doping
Electric current (respectively -4.92 and -4.13mA/cm2).The above result shows that the Co/NSPC of the codope of N, S and cobalt reactive specy
The ORR activity of aerogel catalyst is optimal.It may infer that: graphite mould and pyrroles's type nitrogen-atoms in catalyst, thiophenic sulfur and not
With cobalt reactive specy (including CoO, Co3O4With Co simple substance) codope, by synergistic effect significantly improve the conduction of catalyst
Property and electronics conduction efficiency, the current density in significant increase steady-state process, to realize the enhancing of ORR catalytic performance.
2 gained Co/NSPC aerogel catalyst of Fig. 5 b embodiment modifies the resulting K-L curve graph of RDE.It can be seen from the figure that with
The increase of revolving speed, limiting diffusion current are also increasing, and are catalyzed by the ORR that K-L curve graph acquires Co/NSPC aerogel catalyst
Process electronics transfer number is about 3.8, close to no HO2 -4 electronic transfer process of product, to illustrate that Co/NSPC aeroge is urged
The ORR process of agent modified electrode catalysis is 4 ideal electron reaction mechanism.
Fig. 6 is the resulting dynamics of ORR research that 2 gained Co/NSPC aerogel catalyst of embodiment modifies that RRDE is carried out
Parameter.The results show that electronics transfer number is about 3.7 in the ORR catalytic process, it is almost the same with RDE test result, and 2
The HO of electron reaction course2 -Product maintains always 5% hereinafter, further illustrating the ORR process is 4 ideal electronics
Reaction mechanism, Co/NSPC aerogel catalyst have good ORR catalytic activity.
Claims (2)
1. a kind of difunctional VPO catalysts of cobalt nitrogen sulphur codope carbon aerogels, it is characterised in that the catalyst is with marine polysaccharide
Sodium alginate is carbon source, under hydrothermal conditions, first that divalent cobalt, dopamine and mercaptan and sodium alginate is sufficiently compound, preparation
Dopamine/mercaptan/cobalt-Sodium Alginate Hydrogel Films is freeze-dried to obtain dopamine/mercaptan/cobalt-sodium alginate gas after cooling in refrigerator
Then gel will obtain the difunctional VPO catalysts of cobalt nitrogen sulphur codope carbon aerogels, the sodium alginate note after its high-temperature calcination
For SA, cobalt nitrogen sulphur codope carbon aerogels are denoted as Co/NSPC；
The preparation method of the difunctional VPO catalysts of the cobalt nitrogen sulphur codope carbon aerogels, it is characterised in that including walking in detail below
It is rapid:
(a) dopamine/mercaptan/Co-SA aeroge preparation
Disperse a certain amount of SA in 200mL deionized water, 80 DEG C of heating stirring 8h make it completely dissolved, compound concentration be 40~
The SA solution of 70mg/mL；2.5g cobalt chloride hexahydrate is configured to the aqueous solution that concentration is 0.02mol/L, is delayed in whipping process
Slowly be added drop-wise in SA solution, continue stir 4h after in 4000rpm be centrifuged 10min, collect precipitating is scattered in 200mL deionization again
In water, stirring and dissolving after 0.6g dopamine and 40mL mercaptan is added, is transferred in hydrothermal reaction kettle, 100 DEG C of hydro-thermal reaction 2h, reacts
It is stood after liquid centrifuge separation washing and obtains dopamine/mercaptan/Co-SA hydrogel, put it into after the subzero 20 DEG C of freezings of refrigerator again
It is freeze-dried 36h, obtains dopamine/mercaptan/Co-SA aeroge；
(b) preparation of the difunctional VPO catalysts of Co/NSPC aeroge
Dopamine/mercaptan/Co-SA aeroge obtained in step (a) is placed in porcelain boat, under nitrogen atmosphere with 5 DEG C/min
Rate heated in tube furnace, be first increased to 200 DEG C of heating 1h, be heated to 700~900 DEG C of 2~6h of calcining, obtain described
The difunctional VPO catalysts of Co/NSPC column aeroge；
In the marine polysaccharide SA of nature rich content, nitrogen source derives from carbon source in the catalyst in dopamine, sulphur
Mercaptan, cobalt reactive specy is with Co simple substance, CoO and Co3O4Form exist, the partial size of cobalt reactive specy is 30~130nm, doping
Nitrogen-atoms in poroid carbon material mainly exists with pyrroles's type nitrogen and graphitization nitrogen；The sulphur of doping is mainly in the form of thiophenic sulfur
In the presence of；The average pore size of the column-shaped porous aerogel catalyst is 2~4nm, and specific surface area is in 126.8~138.3m2/g。
2. a kind of difunctional VPO catalysts of cobalt nitrogen sulphur codope carbon aerogels according to claim 1, it is characterised in that institute
Catalyst is stated for the reaction of electrolyzed alkaline water Oxygen anodic evolution and fuel battery negative pole oxygen reduction reaction.
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