CN107308977A - 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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- CN107308977A CN107308977A CN201710585199.2A CN201710585199A CN107308977A CN 107308977 A CN107308977 A CN 107308977A CN 201710585199 A CN201710585199 A CN 201710585199A CN 107308977 A CN107308977 A CN 107308977A
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- cobalt
- mercaptan
- dopamine
- nitrogen
- aeroges
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- 239000003054 catalyst Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000004966 Carbon aerogel Substances 0.000 title claims abstract description 20
- BNKWCSJBOZKTJL-UHFFFAOYSA-N [Co].[N].[S] Chemical compound [Co].[N].[S] BNKWCSJBOZKTJL-UHFFFAOYSA-N 0.000 title claims abstract description 20
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims abstract description 88
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229960003638 dopamine Drugs 0.000 claims abstract description 44
- 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 38
- 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
- 239000010941 cobalt Substances 0.000 claims abstract description 25
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 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
- 238000005119 centrifugation Methods 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
- 239000000463 material Substances 0.000 claims abstract description 6
- 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 23
- 239000000243 solution Substances 0.000 claims description 22
- 238000003756 stirring Methods 0.000 claims description 22
- 239000004964 aerogel Substances 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 17
- 229910052799 carbon Inorganic materials 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 15
- 241000894007 species Species 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000001354 calcination Methods 0.000 claims description 11
- 229910052717 sulfur Inorganic materials 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 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 class O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 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
- 238000001556 precipitation Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 239000003643 water by type Substances 0.000 claims description 7
- 238000002242 deionisation method Methods 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 5
- 239000002245 particle 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
- 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
- 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
- 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 7
- 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
- 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
- 230000008901 benefit Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003792 electrolyte 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
- 238000005516 engineering process Methods 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
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 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
- 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 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 group [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect 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
- 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
- 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 be combined 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 dopamine/mercaptan/cobalt sodium alginate aeroge of gained after freeze-drying.The catalyst is the poroid material of aeroge, and its average pore size is 2~4nm, and 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 is main with pyrroles's type and graphite mould presence.Due to the codope of cobalt, nitrogen and sulphur, the catalyst has high analysis oxygen and oxygen reduction catalytic activity simultaneously in the basic conditions, and raw materials used cost is low, preparation method is simple, it is easy to operate, and is easy to large-scale production.
Description
Technical field：
The invention belongs to novel energy resource material technology and electrochemical catalysis field, 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 technology：
As the mankind are continuously increased to 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) exists
The cathode reaction of generally existing in fuel cell and metal-air battery, oxygen evolution reaction (OER) then solar energy fuel synthesis and
Played an important role in water-splitting energy storage system.Therefore, catalyst particularly VPO catalysts have been restriction new energy dresses
The main bottleneck put.In view of the activity and stability of catalyst, mainly there are Pt and its alloy for the ORR catalyst reacted,
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 of concern 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 to be a kind of, transition metal oxide possesses following advantage, and rich reserves, price are low
It is honest and clean, easily prepared, environment-friendly etc..Because transition metals have multiple valence state such as Mn, Fe, Co, Ni, it can be formed
Oxide with various crystal structures, all has preferable electrocatalysis characteristic, but use as VPO catalysts to OER and ORR
When still suffer from electric conductivity and the defect such as bad dispersibility, smaller than surface.Electroactive kinds of transition metals is loaded into electric conductivity
The problem of can overcoming catalyst poorly conductive on excellent hetero atom (such as nitrogen or sulphur) doping carbon-based material, and can improve compound
The specific surface area and stability of catalyst, can greatly improve the OER and ORR of catalyst double-function catalyzing performance.Therefore, grind
Study 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.Compounds of many containing cobalt/cobalt oxide species and (nitrogen sulfur doping) carbon material have been developed that as the OER under alkalescence condition and
ORR bifunctional catalysts, as a result show, (nitrogen sulfur doping) carbon material can significantly improve the electrochemical catalysis performance of compound.Mesh
Before, it is cobalt oxide or cobalt sulfide to study more cobalt species, difunctional based on cobalt nanometer particle or cobalt oxide-cobalt nanometer particle
The research of VPO catalysts is considerably less.According to consulting literatures, with marine polysaccharide sodium alginate (SA) for carbon source, cobalt nitrogen sulphur codope is prepared
Carbon aerogels yet there are no report as the research of difunctional VPO catalysts.
Uniformly it is combined and the big cobalt nitrogen sulphur codope carbon of specific surface area to prepare cobalt species and nitrogen sulphur codope carbon material
Compound elctro-catalyst, after the present invention dissolves by heating SA, adds divalent cobalt and is dissolved in SA solution, fully centrifuges and removes after complexing
Remaining metal ion is removed, dopamine is added into complexing has in the SA dispersion liquids of cobalt ions, and stirring dissolves it, adds sulphur
Alcohol is sufficiently stirred for, and reaction solution is transferred in hydrothermal reaction kettle, and centrifugation obtains dopamine/mercaptan/Co-SA water-settings after hydrothermal treatment
Dopamine/mercaptan/Co-SA aeroges are freeze-dried to obtain after being cooled down in glue, refrigerator, are forged under nitrogen atmosphere in tube furnace high temperature
It is made cobalt nitrogen sulphur codope carbon aerogels (Co/NSPC) after burning, and studies that its OER and ORR in the basic conditions is difunctional to be urged
Change performance.
The present invention uses and cobalt ions is equably combined with sodium alginate, then with dopamine and mercaptan hydrothermal treatment,
Centrifugation obtains dopamine/mercaptan/Co-SA hydrogels, and dopamine/mercaptan/Co-SA aeroges of gained are through high temperature after freeze-drying
Calcining prepares Co/NSPC aeroge VPO catalysts, cobalt reactive specy and nitrogen sulphur atom can be made uniformly to be combined with carbon aerogels, this is urged
Agent effectively reduces the excessively electric of OER and ORR using carbon aerogels as matrix, therefore with good electric conductivity and specific surface area
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 courses of reaction.Elctro-catalyst obtained by this method has given full play to the carbon of cobalt reactive specy and nitrogen sulphur codope
Synergy 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.
The content of the invention：
In view of the shortcomings of the prior art and this area research and application demand, an object of the present invention is to provide one
Plant the difunctional VPO catalysts of cobalt nitrogen sulphur codope carbon aerogels；I.e. using marine polysaccharide sodium alginate as carbon source, under hydrothermal conditions,
First divalent cobalt, dopamine and mercaptan and sodium alginate are fully combined, dopamine/mercaptan/Co-SA hydrogels, refrigerator is prepared
Dopamine/mercaptan/Co-SA aeroges are freeze-dried to obtain after middle cooling, are made under nitrogen atmosphere in after the calcining of tube furnace high temperature
The difunctional VPO catalysts of cobalt nitrogen sulphur codope carbon aerogels are obtained, the sodium alginate is designated as SA, cobalt nitrogen sulphur codope carbon aerogels
It is designated 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 following steps：
(a) preparation of dopamine/mercaptan/Co-SA aeroges
A certain amount of SA is scattered in 200mL deionized waters, 80 DEG C of heating stirring 8h are completely dissolved it, and compound concentration is
40~70mg/mL SA solution；2.5g cobalt chloride hexahydrates are configured to the aqueous solution that concentration is 0.02mol/L, whipping process
In be slowly dropped in SA solution, continue stir 4h after 4000rpm centrifuge 10min, collect precipitation is scattered in 200mL again
In ionized water, stirring and dissolving after 0.6g dopamines and 40mL mercaptan is added, is transferred in hydrothermal reaction kettle, 100 DEG C of hydro-thermal reaction 2h,
Reaction solution, which centrifuges to stand after washing, obtains dopamine/mercaptan/Co-SA hydrogels, puts it into the subzero 20 DEG C of freezings of refrigerator
It is freeze-dried 36h again afterwards, obtains dopamine/mercaptan/Co-SA aeroges.
(b) preparation of the difunctional VPO catalysts of Co/NSPC aeroges
Dopamine/mercaptan/Co-SA aeroges of gained in step (a) are placed in porcelain boat, under nitrogen atmosphere with 5 DEG C/
Min speed is heated 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, is obtained
The described difunctional VPO catalysts of Co/NSPC column aeroges.
Carbon source wherein described in step (b) in the difunctional VPO catalysts of Co/NSPC columns aeroge contains in nature
The abundant marine polysaccharide SA of amount, nitrogen source derives from mercaptan in dopamine, sulphur, and cobalt reactive specy is with Co simple substance, CoO and Co3O4's
Form is present, and the particle diameter of cobalt reactive specy is 30~130nm, and the nitrogen-atoms being entrained in poroid carbon material is main with pyrroles's type nitrogen
Exist with graphitization nitrogen；The sulphur of doping is main to be existed 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 divalent cobalt ion, dopamine and mercaptan and SA are answered
Heshui prepares Co/NSPC composite aerogels after being heat-treated through being freeze-dried to obtain Co/NSPC aeroges, then through high-temperature calcination；No
The electric conductivity and specific surface area of catalyst are improve only, its catalytic site is added, and the oxygen gel catalyst is effective
OER and ORR overpotential are reduced, its ORR process is almost preferable 4 electronic catalytic mechanism.
Compared with prior art, the present invention has following major advantage and beneficial effect：
1) the difunctional VPO catalysts of aeroge of the present invention are base metal composite, raw materials used to be easy to purchase
And preparation, aboundresources and price is relatively low, it is low that it prepares cost on a large scale；
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 does not almost decay；
3) the difunctional VPO catalysts of aeroge of the present invention are compound for a kind of new cobalt nitrogen sulphur codope carbon aerogels
Material, with preferable OER and ORR catalytic activity, 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, it is easy to operate, and is easy to large-scale production.
Brief description of the drawings：
Fig. 1 is the XRD spectra of the gained Co/NSPC catalyst of embodiment 2.
Fig. 2 is the transmission electron microscope picture (left side) and high-resolution-ration transmission electric-lens figure of the gained Co/NSPC aerogel catalysts of embodiment 2
(right side)
Fig. 3 schemes for the full spectrograms of XPS (a), (b) N 1s spectrograms and the S2p of the gained Co/NSPC aerogel catalysts of embodiment 2.
Fig. 4 is the gained Co/NSPC aeroges of embodiment 2, the gained Co/NPC of comparative example 1, the gained Co/SPC of comparative example 2 catalysis
Agent and the OER polarization curves of Ni foams.
Fig. 5 be the gained Co/NSPC aeroges of embodiment 2, the gained Co/NPC of comparative example 1, the gained Co/SPC of comparative example 2 and
The ORR polarization curves (a) of Pt/C catalyst；K-L obtained by the gained Co/NSPC aerogel catalysts of embodiment 2 modification RDE is bent
Line chart (b).
Fig. 6 is the ORR polarization curves (a) and electronics turn that the gained Co/NSPC aerogel catalysts of embodiment 2 modify RRDE
Move number, HO2 -Containing spirogram.
Embodiment：
To further understand the present invention, the invention will be further described with reference to the accompanying drawings and examples, but not with
Any mode limits the present invention.
Embodiment 1：
(a) preparation of dopamine/mercaptan/Co-SA aeroges
A certain amount of SA is scattered in 200mL deionized waters, 80 DEG C of heating stirring 8h are completely dissolved it, and compound concentration is
40mg/mL SA solution；2.5g cobalt chloride hexahydrates are configured in the aqueous solution that concentration is 0.02mol/L, whipping process to delay
Slowly it is added drop-wise in SA solution, continues to stir 4h after 4000rpm centrifugation 10min, collect precipitation and is scattered in 200mL deionizations again
In water, stirring and dissolving after 0.6g dopamines and 40mL mercaptan is added, is transferred in hydrothermal reaction kettle, 100 DEG C of hydro-thermal reaction 2h, reacted
Liquid, which centrifuges to stand after washing, obtains dopamine/mercaptan/Co-SA hydrogels, puts it into after the subzero 20 DEG C of freezings of refrigerator again
36h is freeze-dried, dopamine/mercaptan/Co-SA aeroges are obtained.
(b) preparation of the difunctional VPO catalysts of Co/NSPC aeroges
Dopamine/mercaptan/Co-SA aeroges of gained in step (a) are placed in porcelain boat, under nitrogen atmosphere with 5 DEG C/
Min speed is heated in tube furnace, is first increased to 200 DEG C of heating 1h, is heated to 800 DEG C of calcining 3h, is obtained described Co/
The difunctional VPO catalysts of NSPC column aeroges, its average pore size is 2~3nm, and specific surface area is in 126.8m2/g。
Embodiment 2：
(a) preparation of dopamine/mercaptan/Co-SA aeroges
A certain amount of SA is scattered in 200mL deionized waters, 80 DEG C of heating stirring 8h are completely dissolved it, and compound concentration is
50mg/mL SA solution；2.5g cobalt chloride hexahydrates are configured in the aqueous solution that concentration is 0.02mol/L, whipping process to delay
Slowly it is added drop-wise in SA solution, continues to stir 4h after 4000rpm centrifugation 10min, collect precipitation and is scattered in 200mL deionizations again
In water, stirring and dissolving after 0.6g dopamines and 40mL mercaptan is added, is transferred in hydrothermal reaction kettle, 100 DEG C of hydro-thermal reaction 2h, reacted
Liquid, which centrifuges to stand after washing, obtains dopamine/mercaptan/Co-SA hydrogels, puts it into after the subzero 20 DEG C of freezings of refrigerator again
36h is freeze-dried, dopamine/mercaptan/Co-SA aeroges are obtained.
(b) preparation of the difunctional VPO catalysts of Co/NSPC aeroges
Prepared according to the method and condition of step (b) in embodiment 1.
The average pore size of the difunctional VPO catalysts of gained Co/NSPC column aeroges is 2.0~4.0nm, and specific surface area exists
130.0m2/g。
Embodiment 3：
(a) preparation of dopamine/mercaptan/Co-SA aeroges
A certain amount of SA is scattered in 200mL deionized waters, 80 DEG C of heating stirring 8h are completely dissolved it, and compound concentration is
60mg/mL SA solution；2.5g cobalt chloride hexahydrates are configured in the aqueous solution that concentration is 0.02mol/L, whipping process to delay
Slowly it is added drop-wise in SA solution, continues to stir 4h after 4000rpm centrifugation 10min, collect precipitation and is scattered in 200mL deionizations again
In water, stirring and dissolving after 0.6g dopamines and 40mL mercaptan is added, is transferred in hydrothermal reaction kettle, 100 DEG C of hydro-thermal reaction 2h, reacted
Liquid, which centrifuges to stand after washing, obtains dopamine/mercaptan/Co-SA hydrogels, puts it into after the subzero 20 DEG C of freezings of refrigerator again
36h is freeze-dried, dopamine/mercaptan/Co-SA aeroges are obtained.
(b) preparation of the difunctional VPO catalysts of Co/NSPC aeroges
Prepared according to the method and condition of step (b) in embodiment 1.
The average pore size of the difunctional VPO catalysts of gained Co/NSPC column aeroges is 2.5~3.5nm, and specific surface area exists
133.6m2/g。
Embodiment 4：
(a) preparation of dopamine/mercaptan/Co-SA aeroges
Prepared according to the method and condition of step (a) in embodiment 2.
(b) preparation of the difunctional VPO catalysts of Co/NSPC aeroges
Dopamine/mercaptan/Co-SA aeroges of gained in step (a) are placed in porcelain boat, under nitrogen atmosphere with 5 DEG C/
Min speed is heated in tube furnace, is first increased to 200 DEG C of heating 1h, is heated to 700 DEG C of calcining 3h, is obtained described Co/
The difunctional VPO catalysts of NSPC column aeroges, its average pore size is 2~3nm, and specific surface area is in 134.2m2/g。
Embodiment 5：
(a) preparation of dopamine/mercaptan/Co-SA aeroges
Prepared according to the method and condition of step (a) in embodiment 2.
(b) preparation of the difunctional VPO catalysts of Co/NSPC aeroges
Dopamine/mercaptan/Co-SA aeroges of gained in step (a) are placed in porcelain boat, under nitrogen atmosphere with 5 DEG C/
Min speed is heated in tube furnace, is first increased to 200 DEG C of heating 1h, is heated to 900 DEG C of calcining 3h, is obtained described Co/
The difunctional VPO catalysts of NSPC column aeroges, its average pore size is 2~3nm, and specific surface area is in 138.3m2/g。
Comparative example 1：
(a) preparation of dopamine/Co-SA aeroges
A certain amount of SA is scattered in 200mL deionized waters, 80 DEG C of heating stirring 8h are completely dissolved it, and compound concentration is
50mg/mL SA solution；2.5g cobalt chloride hexahydrates are configured in the aqueous solution that concentration is 0.02mol/L, whipping process to delay
Slowly it is added drop-wise in SA solution, continues to stir 4h after 4000rpm centrifugation 10min, collect precipitation and is scattered in 200mL deionizations again
In water, stirring and dissolving after 0.6g dopamines is added, is transferred in hydrothermal reaction kettle, 100 DEG C of hydro-thermal reaction 2h, reaction solution is centrifuged
Stood after washing and obtain dopamine/Co-SA hydrogels, be freeze-dried 36h again after putting it into the subzero 20 DEG C of freezings of refrigerator, much
Bar amine/Co-SA aeroges.
(b) preparation of the difunctional VPO catalysts of Co/NPC aeroges
Dopamine/Co-SA aeroges of gained in step (a) are placed in porcelain boat, under nitrogen atmosphere with 5 DEG C/min's
Speed is heated in tube furnace, is first increased to 200 DEG C of heating 1h, is heated to 800 DEG C of calcining 3h, is obtained described Co/NPC gas
The difunctional VPO catalysts of gel.
Comparative example 2：
(a) preparation of mercaptan/Co-SA aeroges
A certain amount of SA is scattered in 200mL deionized waters, 80 DEG C of heating stirring 8h are completely dissolved it, and compound concentration is
50mg/mL SA solution；2.5g cobalt chloride hexahydrates are configured in the aqueous solution that concentration is 0.02mol/L, whipping process to delay
Slowly it is added drop-wise in SA solution, continues to stir 4h after 4000rpm centrifugation 10min, collect precipitation and is scattered in 200mL deionizations 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 is centrifuged and washed
After washing stand obtain mercaptan/Co-SA hydrogels, put it into refrigerator it is subzero 20 DEG C freezing after be freeze-dried 36h again, obtain mercaptan/
Co-SA aeroges.
(b) preparation of the difunctional VPO catalysts of Co/SPC aeroges
Mercaptan/Co-SA aeroges of gained in step (a) are placed in porcelain boat, under nitrogen atmosphere with 5 DEG C/min speed
Rate is heated in tube furnace, is first increased to 200 DEG C of heating 1h, is heated to 800 DEG C of calcining 3h, is obtained described Co/SPC columns
The difunctional VPO catalysts of aeroge.
Fig. 1 is the XRD spectra of the gained Co/NSPC aerogel catalysts of embodiment 2.It can be seen that having at 27.8 °
002 peak of obvious 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 CoO feature diffraction at 60.4 ° and 73.9 °
Peak.It these results suggest that after calcining, cobalt ions has been oxidized to oxide phase, while under simple substance carbon existence condition, part
The oxide of cobalt is reduced for simple substance cobalt.As a result show to generate Co/NSPC catalyst.
Fig. 2 is the transmission electron microscope picture (left side) and high-resolution-ration transmission electric-lens figure of the gained Co/NSPC aerogel catalysts of embodiment 2
(right side).As can be seen that Co/NSPC aerogel catalysts are rendered as cavernous structure from left figure, cobalt reactive specy with it is unformed
Carbon plate is combined with each other, and 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 its average grain diameter is about in 30~130nm, with unformed carbon plate
It is combined together.
Fig. 3 schemes for the full spectrograms of XPS (a), (b) N 1s spectrograms and the S2p of the gained Co/NSPC aerogel catalysts of embodiment 2.
Figure a shows there is obvious 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 is cobalt reactive specy and nitrogen sulfur doping carbon material, wherein Cl derives from CoCl2Raw material.Divide in N 1s spectrograms
Not oxidized form N, graphite mould N, pyrroles's type N and pyridine type N are occurred in that 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：
The catalyst of 10mg embodiments 2, comparative example 1 and the gained of comparative example 2 is scattered in 400 μ L ethanol and 20 μ L respectively
In polytetrafluoroethylsolution solution, ultrasound is mixed after solution, takes 15 μ L slurry drops to be applied to 1 × 1cm2On foam nickel electrode, treat that its is complete
Tabletting determines its OER electrocatalysis characteristic on CHI660D electrochemical workstations after drying；Similarly, respectively by 10mg embodiments
2nd, the catalyst of comparative example 1 and the gained of comparative example 2 is scattered in 400 μ L ethanol and 15 μ L Nafion solutions, and ultrasound mixes molten
After liquid, 1 μ L slurry drops are 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 determined on chem workstation.
Above-mentioned electrocatalysis characteristic test is using saturation Ag/AgCl electrodes as reference electrode, and Pt electrodes are that sweeping speed is to electrode
10mV/s, electrolyte need to carry out N for electrolyte before 0.1M KOH, OER catalytic performance tests2Saturated process, ORR catalytic performances are surveyed
Need to carry out O before examination2Saturated process.RDE test results are after Koutecky-Levich formula manipulation, by the K-L slopes 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 results 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 the gained Co/NSPC aeroges of embodiment 2, the gained Co/NPC of comparative example 1, the gained Co/SPC of comparative example 2 catalysis
Agent and the OER polarization curves of Ni foams.The take-off potential of display doping N or S Co/NPC and Co/SPC catalyst in figure
Respectively 1.52 and 1.55V, they are much larger than the super beginning current potential (1.58V) of Ni foam electrodes, but when N and S doping simultaneously
Co/NSPC aerogel catalysts its overvoltages is 1.47V, and its value is minimum in four kinds of catalyst, illustrates N, S and cobalt spike
The codope of class has facilitation well to OER performances.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 spike
The Co/NSPC aerogel catalysts of the codope of class show 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 the gained Co/NSPC aeroges of embodiment 2, the gained Co/NPC of comparative example 1, the gained Co/SPC of comparative example 2 and
The ORR polarization curves of Pt/C catalyst.As illustrated, the take-off potential of Co/NSPC aeroges and Co/NPC catalyst is basic
It is identical, about 0.85V, just in Co/SPC and Pt/C take-off potential (essentially identical, about 0.83V).From 0.4V when pole
Limit from the point of view of dissufion current, the limiting diffusion current of Co/NSPC aeroges 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 only N or sulfur doping Co/NPC and Co/SPC catalyst
Electric current (is respectively -4.92 and -4.13mA/cm2).Result above shows, 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, the conduction of catalyst is significantly improved by synergy
Current density in property and electronics conduction efficiency, significant increase steady-state process, it is achieved thereby that the enhancing of ORR catalytic performances.
K-L curve maps obtained by the gained Co/NSPC aerogel catalysts of Fig. 5 b embodiments 2 modification RDE.It can be seen that with
The increase of rotating speed, limiting diffusion current is also in increase, and the ORR for trying to achieve Co/NSPC aerogel catalysts by K-L curve maps is catalyzed
Process electro transfer number is about 3.8, close to without HO2 -4 electronic transfer process of product, so as to illustrate that Co/NSPC aeroges are urged
The ORR processes of agent modified electrode catalysis are 4 ideal electron reaction mechanism.
Fig. 6 is that the gained Co/NSPC aerogel catalysts of embodiment 2 modify the dynamics that the ORR research institutes of RRDE progress obtain
Parameter.As a result show, electro transfer number is about 3.7 in the ORR catalytic process, basically identical with RDE test results, and 2
The HO of electron reaction course2 -Product maintains less than 5% always, and it is 4 ideal electronics to further illustrate the ORR processes
Reaction mechanism, Co/NSPC aerogel catalysts have good ORR catalytic activity.
Claims (3)
1. the difunctional VPO catalysts of a kind 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, is first fully combined divalent cobalt, dopamine and mercaptan and sodium alginate, prepares
Dopamine/mercaptan/cobalt-sodium alginate gas is freeze-dried to obtain after being cooled down in dopamine/mercaptan/cobalt-Sodium Alginate Hydrogel Films, refrigerator
Gel, then 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 designated 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
Suddenly：
(a) preparation of dopamine/mercaptan/Co-SA aeroges
A certain amount of SA is scattered in 200mL deionized waters, 80 DEG C of heating stirring 8h are completely dissolved it, compound concentration be 40~
70mg/mL SA solution；2.5g cobalt chloride hexahydrates are configured in the aqueous solution that concentration is 0.02mol/L, whipping process to delay
Slowly it is added drop-wise in SA solution, continues to stir 4h after 4000rpm centrifugation 10min, collect precipitation and is scattered in 200mL deionizations again
In water, stirring and dissolving after 0.6g dopamines and 40mL mercaptan is added, is transferred in hydrothermal reaction kettle, 100 DEG C of hydro-thermal reaction 2h, reacted
Liquid, which centrifuges to stand after washing, obtains dopamine/mercaptan/Co-SA hydrogels, puts it into after the subzero 20 DEG C of freezings of refrigerator again
36h is freeze-dried, dopamine/mercaptan/Co-SA aeroges are obtained；
(b) preparation of the difunctional VPO catalysts of Co/NSPC aeroges
Dopamine/mercaptan/Co-SA aeroges of gained in step (a) are placed in porcelain boat, under nitrogen atmosphere with 5 DEG C/min
Speed 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 aeroges.
2. the difunctional VPO catalysts of a kind of cobalt nitrogen sulphur codope carbon aerogels according to claim 1, it is characterised in that should
Carbon source in catalyst is in the marine polysaccharide SA of nature rich content, and nitrogen source is in dopamine, and sulphur derives from mercaptan, and cobalt is lived
Property species is with Co simple substance, CoO and Co3O4Form exist, the particle diameter of cobalt reactive specy is 30~130nm, is entrained in poroid carbon materials
Nitrogen-atoms in material is main with pyrroles's type nitrogen and the presence of graphitization nitrogen；The sulphur of doping is main to be existed in the form of thiophenic sulfur；The post
The average pore size of shape porous aerogel catalyst is 2~4nm, and specific surface area is in 126.8~138.3m2/g。
3. a kind of difunctional VPO catalysts of cobalt nitrogen sulphur codope carbon aerogels according to claim 1 or 2, it is characterised in that
The catalyst is used for the reaction of electrolyzed alkaline water Oxygen anodic evolution and fuel battery negative pole oxygen reduction reaction.
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