CN105826574A - Nitrogen-doped graphene/ ferrocobalt hydrotalcite-like compound difunctional oxygen-reduction catalyst and preparing method and application thereof - Google Patents
Nitrogen-doped graphene/ ferrocobalt hydrotalcite-like compound difunctional oxygen-reduction catalyst and preparing method and application thereof Download PDFInfo
- Publication number
- CN105826574A CN105826574A CN201610172917.9A CN201610172917A CN105826574A CN 105826574 A CN105826574 A CN 105826574A CN 201610172917 A CN201610172917 A CN 201610172917A CN 105826574 A CN105826574 A CN 105826574A
- Authority
- CN
- China
- Prior art keywords
- ldh
- ferro
- cobalt
- nitrogen
- houghite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 47
- RIVZIMVWRDTIOQ-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co].[Co] RIVZIMVWRDTIOQ-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title abstract description 28
- 150000001875 compounds Chemical class 0.000 title abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 8
- 230000003446 memory effect Effects 0.000 claims abstract description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002135 nanosheet Substances 0.000 claims abstract description 3
- 238000002360 preparation method Methods 0.000 claims description 36
- 239000000243 solution Substances 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 17
- 229910021641 deionized water Inorganic materials 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 12
- 238000005119 centrifugation Methods 0.000 claims description 11
- 238000005406 washing Methods 0.000 claims description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 10
- 239000006185 dispersion Substances 0.000 claims description 10
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 10
- 239000012498 ultrapure water Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 239000000446 fuel Substances 0.000 claims description 8
- 238000013019 agitation Methods 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 6
- 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 6
- 238000010790 dilution Methods 0.000 claims description 6
- 239000012895 dilution Substances 0.000 claims description 6
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 6
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 6
- 238000001556 precipitation Methods 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 5
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- 239000000376 reactant Substances 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000000227 grinding Methods 0.000 claims description 3
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 24
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 239000000203 mixture Substances 0.000 abstract description 7
- 239000010970 precious metal Substances 0.000 abstract description 3
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- 239000002243 precursor Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000009467 reduction Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 21
- 238000006555 catalytic reaction Methods 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- 239000002131 composite material Substances 0.000 description 8
- 239000003792 electrolyte Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 230000027756 respiratory electron transport chain Effects 0.000 description 5
- 238000009792 diffusion process Methods 0.000 description 4
- 125000005842 heteroatom Chemical group 0.000 description 4
- 239000011229 interlayer Substances 0.000 description 4
- 239000010410 layer Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 150000001450 anions Chemical class 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000004146 energy storage Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000010408 sweeping Methods 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- 241000446313 Lamella Species 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9091—Unsupported catalytic particles; loose particulate catalytic materials, e.g. in fluidised state
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention discloses a nitrogen-doped graphene/ ferrocobalt hydrotalcite-like compound non-precious metal difunctional oxygen-reduction catalyst and a preparing method and application thereof. A bimetallic oxide is used as a precursor, the memory effect of a hydrotalcite-like compound is utilized, oxidized graphene and the ferrocobalt hydrotalcite-like compound are assembled, and then the compound is doped with carbon nitride nanosheets under the reduction condition to obtain a nitrogen-doped graphene/ ferrocobalt hydrotalcite-like compound composition. The oxygen-reduction catalyst has high catalytic activity to oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) at the same time under the alkaline condition and has high stability and excellent methyl alcohol tolerance, the cost of adopted raw materials is low, the preparing method is simple, operation is easy, and large-scale production can be achieved conveniently.
Description
Technical field:
The invention belongs to novel energy resource material technology and electrochemical catalysis field, be specifically related to nitrogen-doped graphene/difunctional VPO catalysts of ferro-cobalt houghite；Further relate to the preparation method of described catalyst and the electro-catalysis application in the reaction of electrolyzed alkaline water Oxygen anodic evolution and fuel battery negative pole oxygen reduction reaction thereof.
Background technology:
Along with cleaning and sustainable energy demand are continuously increased by the mankind, great effort has been put into the research and development aspect of energy conversion efficient, low cost and environmentally friendly and stocking system by scientists.Wherein oxygen reduction reaction (ORR) is the cathode reaction generally existed in fuel cell and metal-air battery, and oxygen evolution reaction (OER) then plays an important role in the synthesis of solar energy fuel and water-splitting energy storage system.Therefore, catalyst particularly VPO catalysts has been the Main Bottleneck of restriction new forms of energy development.In view of activity and the stability of catalyst, the catalyst for ORR reaction mainly has Pt and alloy thereof, and the catalyst being used for OER mainly has IrO2Or RuO2, but these noble metals are the most rare in nature, make current supply unit cost too high.Therefore, research and development non-precious metal catalyst becomes hot subject of concern in this field.
Houghite (writing a Chinese character in simplified form LDH) is a class two-dimensional nanometer anionic clay, and its composition formula is represented by [M1-x 2+Mx 3+(OH)2]x+(An-)x/n·mH2O, is made up of positively charged hydroxide laminate and the interlayer anion that electric charge balances each other therewith.Its preparation method is more, frequently with coprecipitation, ion exchange or calcining restoring method based on self memory effect.nullDue to adjustable chemical composition，Different electroactive metal such as Fe、Ni、Co、Mn may participate in the structure of double-metal hydroxide octahedron houghite layer，LDH material is made to present good application prospect [X.Long in energy conversion and field of storage,Z.Wang,S.Xiao,Y.AnandS.Yang.Transitionmetalbasedlayereddoublehydroxidestailoredforenergyconversionandstorage.MaterialsToday(2015),http://dx.doi.org/10.1016/j.mattod.2015.10.006].But, in actual application, LDH catalyst material there is also poorly conductive, the easily shortcoming such as gathering and poor stability.In order to overcome the disadvantage mentioned above of LDH, the materials such as some material with carbon elements such as Graphene (GR) and CNT (CNT) are generally intercalated in LDH interlayer by researcher, the electric conductivity of composite can be improved first, second stop LDH to assemble, improve its stability.GR is a kind of sp2The two-dimensional material with a carbon atom thickness of hydbridized carbon atoms composition, specific surface area (～the 2600m of tool superelevation2/ g) and excellent electric conductivity (～106S/cm), it is possible to the charge transfer being greatly improved in electrocatalytic reaction and mass-transfer efficiency.And electronegative graphene oxide (GO) and the positively charged LDH nanometer sheet other static buildup of face-to-face molecular level, the transition metal-catalyzed center of LDH and the sp of conduction can be made2Hydbridized carbon atoms is in close contact, and is greatly shortened the diffusion length [X.Long, etal.Angew.Chem.126 (2014) 7,714 7718.] of electrolyte.Although assembling LDH and GR by electrostatic attraction can solve the problems such as LDH material conductivity difference and gathering, but GR is usually present the competition with other aniones during compound, other aniones present in anion as intrinsic in LDH interlayer and system, cause GR with LDH combined efficiency the best, if single increase GR consumption, not only fail to strengthen himself competitiveness with other aniones, the GR that the most also can make surplus is coated on LDH surface, cause covering of avtive spot, thus greatly reduce its catalysis activity.Therefore, the actual combined efficiency improving composite further remains the significant challenge of exploitation efficient electric catalyst.
Graphite type carbon nitride (g-C3N4) it is commonly called as the substituted graphite of nitrogen, having the two-dimensional slice structure similar to Graphene, this lamella is formed by van der Waals interaction stacked in multi-layers, has higher nitrogen content, unique heat stability and suitable mechanical strength, the carbon the abundantest by reserves on the earth and nitrogen are elementary composition.Lyth etc. find g-C at first3N4ORR catalysis specific activity white carbon black in acid medium is high, illustrate that it has certain oxygen reducing ability, [S.M.Lyth, Y.Nabae, S.Moriya, et.al.Carbonnitrideasanonpreciouscatalystforelectrochemi caloxygenreduction.ThejournalofphysicalchemistryC (2009), http://dx.doi.doi/pdf/10.1021/jp907928j] but g-C3N4nullThe energy gap (～2.6eV) that self is bigger，The contact resistance of sheet interlayer and relatively low specific surface area make its electric conductivity excessively poor，Be equivalent to quasiconductor，Therefore strongly limit its electron transfer rate and electrochemical catalysis performance [Y.Zhao,J.WangandL.T.Qu.Graphiticcarbonnitride/graphenehybridsasnewactivematerialsforenergyconversionandstorage.Chemistryofnanomaterialsforenergy,biologyandmore(2015),http://dx.doi.org/10.1002/cnma.201500060].And Graphene is frequently utilized for the improvement of semiconducting electrical conductivity energy, and Graphene has similar 2D plane layer structure to carbonitride, usually by both combinations thus prepare nitrogen-doped graphene, nitrogen makes Graphene prepare at material as foreign atom, be catalyzed and the association area such as energy storage has possessed more novel using value.But g-C3N4It is still limited by its less specific surface area, thus is difficult to electrochemistry and the catalytic performance estimated.
In order to prepare the eelctro-catalyst with high combined efficiency, the ferro-cobalt houghite after calcining is dividedly in some parts in GO aqueous dispersions by the present invention, obtains GO/LDH under certain condition after mix homogeneously, and adulterate g-C the most under the reducing conditions3N4Nanometer sheet prepares lamellar nitrogen-doped graphene/ferro-cobalt houghite (NG/LDH) nanocatalyst.Use the method to prepare NG/LDH efficient composite catalyst and this catalyst at present to have not been reported for the research of electrolyzed alkaline water anode OER and fuel battery negative pole ORR.
What the present invention was utilized is the memory effect of LDH, its calcined product bimetallic oxide (LDO) is dividedly in some parts in the GO aqueous dispersions that anion species is single and restores, carry out N doping the most under the reducing conditions, thus it is prepared for lamellar NG/LDH catalyst, this preparation method avoids the competition of recombination process GO and other aniones, obtain the GO/LDH catalyst of high efficiency composition, the C of state will have been peeled off3N4Nanometer sheet and GO/LDH hydro-thermal under having hydrazine hydrate existence condition is combined, and avoids quasiconductor C while introducing atom N3N4A large amount of participations, obtain the NG/LDH catalyst with laminated structure, not only increase the electric conductivity of catalyst, also avoid the gathering of LDH self, and achieve the N doping of real meaning, gained VPO catalysts effectively reduces the overpotential of OER and ORR, shows that its ORR process majority 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 course of reaction.The method gained eelctro-catalyst has given full play to LDH, GR and hetero atom N synergism in terms of electro-catalysis, and exploitation novel electrochemical catalyst and energy conversion and memory device are had important theoretical and practical significance.
Summary of the invention:
Studying and the demand of application for the deficiencies in the prior art and this area, an object of the present invention is to provide a kind of nitrogen-doped graphene/difunctional VPO catalysts of ferro-cobalt houghite；I.e. LDO is for preparing precursor, first ferro-cobalt houghite high-temperature calcination is become ferro-cobalt bimetallic oxide, the memory effect utilizing houghite is recovered in the aqueous dispersions of graphene oxide, graphene oxide is assembled on ferro-cobalt houghite sheet, form graphene oxide/ferro-cobalt houghite complex, then under hydrazine hydrate existence condition, carry out the doping of azotized carbon nano sheet, form nitrogen-doped graphene/ferro-cobalt houghite flake nano composite catalyst.
The two of the purpose of the present invention are to provide the preparation method of a kind of nitrogen-doped graphene/difunctional VPO catalysts of ferro-cobalt houghite, specifically include following steps:
The preparation of (a) CoFe-LDO hybrid
Cobalt chloride hexahydrate and ferric chloride hexahydrate are dissolved in ultra-pure water by certain mol proportion, making metal ion total concentration is 0.215mol/L, stirring makes it be completely dissolved, and the most at the uniform velocity instills 1.5mol/LNaOH, until pH=8, this mixed liquor is moved in reactor, 24h are reacted, after reactant liquor centrifugation, respectively by deionized water and washing with alcohol three times in 130 DEG C, in the lower 500 DEG C of calcining 5h of air atmosphere after drying and grinding, products therefrom is CoFe-LDO hybrid；
The preparation of (b) GO/LDH complex
A certain amount of GO is scattered in ultra-pure water, ultrasonic disperse 4 hours, 5000rpm is centrifuged 10min and removes unstripped GO, making its ultimate density is 1.0～6.0mg/mL, pipette this solution of 50mL, be slowly added to 50mg under stirring condition by gained CoFe-LDO hybrid in step (a), and stir 12h at room temperature, then 3000rpm is centrifuged 10min, and gained precipitation is GO/LDH complex；
The preparation of (c) NG/LDH VPO catalysts
Weigh 0.5g graphite phase carbon nitride, be designated as C3N4, it is dissolved in 14mL concentrated sulfuric acid solution, adds the dilution of 50mL deionized water after being stirred at room temperature two hours, after ultrasonic 2h, mixed liquor is washed till neutrality, obtains 0.3～0.7mg/mLC3N4Nanometer sheet aqueous dispersions, in this solution of 80mL, gained GO/LDH complex in a certain amount of step (b) it is dividedly in some parts under ultrasound condition, add 2mL hydrazine hydrate the most under agitation, after stirring, mixed liquor is moved in reactor, 20h is reacted under the conditions of 180 DEG C, by deionized water and washing with alcohol three times after gained solid sample centrifugation, dried difunctional VPO catalysts NG/LDH.
Wherein the mol ratio of cobalt chloride hexahydrate described in step (a) and ferric chloride hexahydrate is 3:1, the VPO catalysts of gained structure in the form of sheets in step (c), and mean diameter is 125～150nm, and specific surface area is 134.09～168.63m2/g。
The three of the object of the invention are to provide a kind of nitrogen-doped graphene/ferro-cobalt houghite difunctional VPO catalysts application in electrolyzed alkaline water anode OER and fuel battery negative pole ORR.
The present invention utilizes the memory effect of LDH, uses calcining restoring method first to be assembled by GO with LDH, then through C in hydrazine hydrate3N4Doping obtained the NG/LDH catalyst with laminated structure；Not only increasing electric conductivity and the combined efficiency of catalyst, and gained VPO catalysts effectively reduces the overpotential of OER and ORR, result shows that its ORR process is mainly 4 electronic catalytic mechanism, is ideal ORR course of reaction.
Compared with prior art, the present invention has following major advantage and a beneficial effect:
1) difunctional VPO catalysts of the present invention is base metal composite, and raw materials used being prone to is bought and preparation, and aboundresources and price are relatively low, and its extensive preparation cost is low；
2) methanol tolerance that difunctional VPO catalysts of the present invention has had, adds 1mol/L methanol in 0.1mol/LKOH electrolyte, and the catalysis activity of catalyst is almost without decay；
3) difunctional VPO catalysts of the present invention is a kind of novel three-dimensional composite, has preferable OER and ORR activity, and base metal/non-metallic catalyst one-side ORR activity of more current research report has significant advantage；
4) difunctional VPO catalysts of the present invention is compared with the Pt/C catalyst of commercialization 20wt%, and stability is significantly improved, and can keep good catalysis activity in fuel cell life-time service；
5) the OER activity of difunctional VPO catalysts of the present invention, is better than the material with carbon element/non-precious metal catalyst of the Heteroatom doping of current research report；
6) difunctional VPO catalysts preparation method of the present invention is simple, it is easy to operation, it is simple to large-scale production.
Accompanying drawing illustrates:
Fig. 1 is embodiment 2 gained NG/LDH complex scanning electron microscope (SEM) photograph.
Fig. 2 is the OER linear volt-ampere curve figure that embodiment 2 gained NG/LDH complex, comparative example 1 gained LDH, comparative example 2 gained N/LDH complex and comparative example 3 gained G/LDH complex modify Nifoam electrode.
Fig. 3 is that embodiment 2 gained NG/LDH complex modifies Nifoam electrode in 15mA/cm2Under P-t curve chart.
Fig. 4 is the ORR linear volt-ampere curve figure that embodiment 2 gained NG/LDH complex, comparative example 1 gained LDH, comparative example 2 gained N/LDH complex and comparative example 3 gained G/LDH complex modify RDE.
Fig. 5 is the ORR kinetic curve that embodiment 2 gained NG/LDH complex modifies RDE.
Fig. 6 is the ORR kinetic curve that embodiment 2 gained NG/LDH complex modifies RRDE.
Fig. 7 be under 1600rpm embodiment 2 gained NG/LDH complex modify the ORR linear volt-ampere curve figure of RDE, after 5000 cyclic voltammetry scans ORR linear volt-ampere curve figure and add the ORR linear volt-ampere curve figure after methanol.
Detailed description of the invention:
For being further appreciated by the present invention, the invention will be further described with embodiment below in conjunction with the accompanying drawings, but and limits the present invention never in any form.
Embodiment 1:
The preparation of (a) CoFe-LDO hybrid
Cobalt chloride hexahydrate and ferric chloride hexahydrate are dissolved in ultra-pure water by certain mol proportion, making metal ion total concentration is 0.215mol/L, stirring makes it be completely dissolved, and the most at the uniform velocity instills 1.5mol/LNaOH, until pH=8, this mixed liquor is moved in reactor, 24h are reacted, after reactant liquor centrifugation, respectively by deionized water and washing with alcohol three times in 130 DEG C, in the lower 500 DEG C of calcining 5h of air atmosphere after drying and grinding, products therefrom is CoFe-LDO hybrid；
The preparation of (b) GO/LDH complex
A certain amount of GO is scattered in ultra-pure water, ultrasonic disperse 4 hours, 5000rpm is centrifuged 10min and removes unstripped GO, making its ultimate density is 1.0mg/mL, pipette this solution of 50mL, be slowly added to 50mg under stirring condition by gained CoFe-LDO hybrid in step (a), and stir 12h at room temperature, then 3000rpm is centrifuged 10min, and gained precipitation is GO/LDH complex；
The preparation of (c) NG/LDH VPO catalysts
Weigh the C of 0.5g3N4It is dissolved in 14mL concentrated sulfuric acid solution, adds the dilution of 50mL deionized water after being stirred at room temperature two hours, after ultrasonic 2h, mixed liquor is washed till neutrality, obtains 0.5mg/mLC3N4Nanometer sheet aqueous dispersions, in this solution of 80mL, gained GO/LDH complex in 100mg step (b) it is dividedly in some parts under ultrasound condition, add 2mL hydrazine hydrate the most under agitation, after stirring, mixed liquor is moved in reactor, 20h is reacted under the conditions of 180 DEG C, by deionized water and washing with alcohol three times after gained solid sample centrifugation, dried difunctional VPO catalysts NG/LDH, its mean diameter is 142nm, and specific surface area is 151.52m2/g。
Embodiment 2:
The preparation of (a) CoFe-LDO hybrid
Prepare according to method and the condition of step (a) in embodiment 1；
The preparation of (b) GO/LDH complex
A certain amount of GO is scattered in ultra-pure water, ultrasonic disperse 4 hours, 5000rpm is centrifuged 10min and removes unstripped GO, making its ultimate density is 3.0mg/mL, pipette this solution of 50mL, be slowly added to 50mg under stirring condition by gained CoFe-LDO hybrid in step (a), and stir 12h at room temperature, then 3000rpm is centrifuged 10min, and gained precipitation is GO/LDH complex；
The preparation of (c) NG/LDH VPO catalysts
Preparing according to method and the condition of step (c) in embodiment 1, its mean diameter is 136nm, and specific surface area is 142.38m2/g。
Embodiment 3:
The preparation of (a) CoFe-LDO hybrid
Prepare according to method and the condition of step (a) in embodiment 1；
The preparation of (b) GO/LDH complex
A certain amount of GO is scattered in ultra-pure water, ultrasonic disperse 4 hours, 5000rpm is centrifuged 10min and removes unstripped GO, making its ultimate density is 6.0mg/mL, pipette this solution of 50mL, be slowly added to 50mg under stirring condition by gained CoFe-LDO hybrid in step (a), and stir 12h at room temperature, then 3000rpm is centrifuged 10min, and gained precipitation is GO/LDH complex；
The preparation of (c) NG/LDH VPO catalysts
Preparing according to method and the condition of step (c) in embodiment 1, its mean diameter is 125nm, and specific surface area is 168.63m2/g。
Embodiment 4:
The preparation of (a) CoFe-LDO hybrid
Prepare according to method and the condition of step (a) in embodiment 1；
The preparation of (b) GO/LDH complex
Prepare according to method and the condition of step (b) in embodiment 2；
The preparation of (c) NG/LDH VPO catalysts
Weigh the C of 0.5g3N4It is dissolved in 14mL concentrated sulfuric acid solution, adds the dilution of 50mL deionized water after being stirred at room temperature two hours, after ultrasonic 2h, mixed liquor is washed till neutrality, obtains 0.5mg/mLC3N4Nanometer sheet aqueous dispersions, in this solution of 80mL, gained GO/LDH complex in 100mg step (b) it is dividedly in some parts under ultrasound condition, add 2mL hydrazine hydrate the most under agitation, after stirring, mixed liquor is moved in reactor, 20h is reacted under the conditions of 180 DEG C, by deionized water and washing with alcohol three times after gained solid sample centrifugation, dried difunctional VPO catalysts NG/LDH, its mean diameter is 150nm, and specific surface area is 134.09m2/g。
Embodiment 5:
The preparation of (a) CoFe-LDO hybrid
Prepare according to method and the condition of step (a) in embodiment 1；
The preparation of (b) GO/LDH complex
Prepare according to method and the condition of step (b) in embodiment 2；
The preparation of (c) NG/LDH VPO catalysts
Weigh the C of 0.5g3N4It is dissolved in 14mL concentrated sulfuric acid solution, adds the dilution of 50mL deionized water after being stirred at room temperature two hours, after ultrasonic 2h, mixed liquor is washed till neutrality, obtains 0.7mg/mLC3N4Nanometer sheet aqueous dispersions, in this solution of 80mL, gained GO/LDH complex in 100mg step (b) it is dividedly in some parts under ultrasound condition, add 2mL hydrazine hydrate the most under agitation, after stirring, mixed liquor is moved in reactor, 20h is reacted under the conditions of 180 DEG C, by deionized water and washing with alcohol three times after gained solid sample centrifugation, dried difunctional VPO catalysts NG/LDH, its mean diameter is 138nm, and specific surface area is 140.16m2/g。
Comparative example 1:
The preparation of (a) CoFe-LDH hybrid
Cobalt chloride hexahydrate and ferric chloride hexahydrate are dissolved in ultra-pure water by the mol ratio of 3:1, making metal ion total concentration is 0.215mol/L, stirring makes it be completely dissolved, the most at the uniform velocity instill 1.5mol/LNaOH, until pH=8, this mixed liquor is moved in reactor, 24h is reacted in 130 DEG C, after reactant liquor centrifugation, respectively by deionized water and washing with alcohol three times, it is CoFe-LDH hybrid；
Comparative example 2:
The preparation of (a) CoFe-LDO hybrid
Prepare according to method and the condition of step (a) in embodiment 1；
The preparation of the LDH complex N/LDH of (b) carbonitride doping
Weigh this C of 0.5g3N4It is dissolved in 14mL concentrated sulfuric acid solution, adds the dilution of 50mL deionized water, the most ultrasonic 2h after being stirred at room temperature two hours, then mixed liquor is washed till neutrality, obtain 0.5mg/mLC3N4Nanometer sheet aqueous dispersions, gained CoFe-LDO hybrid in 100mg embodiment 1 step (a) it is dividedly in some parts in this solution of 80mL, add 2mL hydrazine hydrate the most under agitation, after stirring, mixed liquor is moved in reactor, 20h is reacted under the conditions of 180 DEG C, by deionized water and washing with alcohol three times after gained solid sample centrifugation, dried difunctional VPO catalysts N/LDH.
Comparative example 3:
The preparation of (a) CoFe-LDO hybrid
Prepare according to method and the condition of step (a) in embodiment 1；
The preparation of (b) GO/LDH complex
Prepare according to method and the condition of step (b) in embodiment 2；
The preparation of (c) G/LDH VPO catalysts
Step (b) gained GO/LDH complex in 100mg embodiment 2 is dissolved in 80mL ultra-pure water, add 2mL hydrazine hydrate the most under agitation, after stirring, mixed liquor is moved in reactor, 20h is reacted under the conditions of 180 DEG C, by deionized water and washing with alcohol three times after gained solid sample centrifugation, dried difunctional VPO catalysts G/LDH.
Fig. 1 is the scanning electron microscope (SEM) photograph of embodiment 2 gained NG/LDH complex, hexagonal sheet pattern intrinsic for LDH as shown in the figure occurs in that irregular, this is to be probably caused by hetero atom N or special hybridization conditions, and its pattern presents composite construction, the graphene platelet of silk shape it has been mingled with between irregular nanometer sheet, this demonstrate that Graphene is combined with the effective of houghite, also make LDH original two-dimensional structure body present hierarchy by compound with graphene sheet layer simultaneously, there is three-D space structure, so the specific surface area of composite is greatly improved.
Embodiment 6:
Respectively the catalyst of 10mg embodiment 2, comparative example 1, comparative example 2 and comparative example 3 gained is scattered in 400 μ L ethanol and 20 μ L polytetrafluoroethylsolution solution, after ultrasonic mixing solution, takes 15 μ L slurry drops and be applied to 1 × 1cm2On foam nickel electrode, tabletting after it is completely dried, CHI660D electrochemical workstation measures its OER electrocatalysis characteristic, and with saturated Hg/Hg2Cl2/ KCl electrode is reference electrode, and Pt electrode is to electrode, and sweeping speed is 10mV/s, and electrolyte is N2Saturated 0.1MKOH.
Embodiment 7:
Respectively the catalyst of 10mg embodiment 2, comparative example 1, comparative example 2 and comparative example gained is scattered in 400 μ L ethanol and 15 μ LNafion solution, after ultrasonic mixing solution, takes 2 μ L slurry drops and be applied to rotating ring disk electrode (r.r.d.e) (RRDE, 0.1256cm2On), after it is completely dried, on CHI660D electrochemical workstation, measure its ORR electrocatalysis characteristic, and with saturated Hg/Hg2Cl2/ KCl electrode is reference electrode, and Pt electrode is to electrode, and sweeping speed is 10mV/s, and electrolyte is O2Saturated 0.1MKOH, test result, after Koutecky-Levich formula manipulation, can be calculated electron transfer number (n) by the K-L slope of curve (B).
J-1=Jk -1+(Bω1/2)-1
B=0.62nFC0D0 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 through following formula manipulation2O2Content:
N=4Id·(Id+Ir/N)
%H2O2=200Id/N·(Id+Ir/ N),
Wherein N=0.43.
Fig. 2 is embodiment 2 gained NG/LDH, comparative example 1 gained LDH, comparative example 2 gained N/LDH and comparative example 3 gained G/LDH complex modify the OER linear volt-ampere curve figure of Nifoam electrode.The initial overpotential of the Nifoam electrode that LDH modifies is 300mV as shown in the figure, when after LDH combined oxidation Graphene, OER initiates overpotential and is down to 240mV, then by carrying out N doping under reducing condition after, the initial overpotential of NG/LDH is down to again 225mV, and peels off state C for directly doping3N4Catalyst n/LDH, its OER to initiate overpotential be 290mV, higher than GO/LDH, this could not be improved mainly due to electric conductivity bad for LDH, causes its electro-catalysis ability poor, is embodied in the reduction of OER catalysis activity.Similarly, it is 10mA/cm when electric current density2Time, the overpotential that LDH, G/LDH, N/LDH and NG/LDH modify corresponding to RDE is respectively 410,360,290 and 270mV.Result shows the LDH hydridization by NG, significantly reduces its overpotential, this be mainly due to composite nitrogen doped graphene after LDH composite material conductive ability and electro-catalysis ability be obviously improved.
Fig. 3 is that embodiment 2 gained NG/LDH complex modifies Nifoam electrode in 15mA/cm2Under P-t curve chart.As shown in the figure, analysis oxygen process continuously through 8h, the OER current potential of NG/LDH only there occurs minor variations, this change is the lasting precipitation due to oxygen bubbles, constantly impact the NG/LDH catalyst of electrode surface, thus it be caused to cause material trace to come off, it can be seen that, NG/LDH catalyst shows good OER catalytic stability in alkaline solution, has longer service life.
The ORR linear volt-ampere curve figure that Fig. 4 is embodiment 2 gained NG/LDH complex, comparative example 1 gained LDH, comparative example 2 gained N/LDH, 3 G/LDH of comparative example must modify RDE.As it can be seen, LDH is combined after GO again through N doping, the take-off potential of ORR is just being moved to 0.80V by 0.74V, and Limited diffusion current density is also by-4.35mA/cm2Increase to-5.15mA/cm2；Compared to G/LDH, carry out merely the product N/LDH after N doping LDH, the most also preferable ORR catalytic performance is shown, thus may infer that: the existence of hetero atom N and Graphene significantly improves electronics conduction efficiency and the catalysis activity of NG/LDH complex, show as shuffling and the significant increase of electric current density in steady-state process of ORR take-off potential, it is achieved thereby that the enhancing of ORR catalytic performance.
Fig. 5 is the ORR kinetic curve that embodiment 2 gained NG/LDH complex modifies RDE.Result shows, in this ORR catalytic process, electron transfer number is about 3.8, close to without HO2 -4 electronic transfer process of product, thus illustrate that the ORR process majority that NG/LDH modified electrode is catalyzed is preferable 4 electron reaction mechanism.
Fig. 6 is the ORR kinetic curve that embodiment 2 gained NG/LDH complex modifies RRDE.Result shows, in this ORR catalytic process, electron transfer number is about 3.7, close with RDE test result, and the HO of 2 electron reaction courses2 -Product maintains less than 20% always, and further illustrating this ORR process majority is preferable 4 electron reaction mechanism, i.e. NG/LDH complex has good ORR catalysis activity.
Fig. 7 is that embodiment 2 gained NG/LDH complex modifies RDE ORR under 1600rpm linear volt-ampere curve figure.As shown in the figure, after 5000 cyclic voltammetry scans, the limiting diffusion current of this volt-ampere curve occurs in that shuffling of part, and ORR take-off potential does not almost change, this explanation is after long-time loop test, and NG/LDH still remains higher ORR catalysis activity.Similarly, after (about 50mL electrolyte instilling 1mL) after instilling 1M methanol in system, the ORR take-off potential of this volt-ampere curve occurs in that slight shuffling and increase along with the slight of half wave potential, and Limited diffusion current density does not almost change, this explanation is in the system containing methanol, ORR catalytic reaction fails to be interfered, it was demonstrated that NG/LDH catalyst has stronger methanol tolerance interference performance compared to business with noble metal decorated electrode.In sum, NG/LDH modified electrode has preferable stability under the conditions of alkalescence, and compared to noble metal electrode, it shows splendid methanol tolerance, can be as the decorative material of pluralities of fuel cell cathode.
Claims (4)
1. nitrogen-doped graphene/difunctional VPO catalysts of ferro-cobalt houghite, it is characterized in that described catalyst is first ferro-cobalt houghite high-temperature calcination to be become ferro-cobalt bimetallic oxide, the memory effect utilizing houghite is recovered in the aqueous dispersions of graphene oxide, graphene oxide is assembled on ferro-cobalt houghite sheet, form graphene oxide/ferro-cobalt houghite complex, then under hydrazine hydrate existence condition, carry out the doping of azotized carbon nano sheet, form nitrogen-doped graphene/ferro-cobalt houghite flake nano complex, described ferro-cobalt bimetallic oxide is designated as CoFe-LDO, ferro-cobalt houghite is designated as LDH, described graphene oxide is designated as GO, graphene oxide/ferro-cobalt houghite is designated as GO/LDH, nitrogen-doped graphene/ferro-cobalt houghite is designated as NG/LDH；
The preparation method of described nitrogen-doped graphene/difunctional VPO catalysts of ferro-cobalt houghite, it is characterised in that include step in detail below:
The preparation of (a) CoFe-LDO hybrid
Cobalt chloride hexahydrate and ferric chloride hexahydrate are dissolved in ultra-pure water by certain mol proportion, making metal ion total concentration is 0.215mol/L, stirring makes it be completely dissolved, and the most at the uniform velocity instills 1.5mol/LNaOH, until pH=8, this mixed liquor is moved in reactor, 24h are reacted, after reactant liquor centrifugation, respectively by deionized water and washing with alcohol three times in 130 DEG C, in the lower 500 DEG C of calcining 5h of air atmosphere after drying and grinding, products therefrom is CoFe-LDO hybrid；
The preparation of (b) GO/LDH complex
A certain amount of GO is scattered in ultra-pure water, ultrasonic disperse 4 hours, 5000rpm is centrifuged 10min and removes unstripped GO, making its ultimate density is 1.0～6.0mg/mL, pipette this solution of 50mL, be slowly added to 50mg under stirring condition by gained CoFe-LDO hybrid in step (a), and stir 12h at room temperature, then 3000rpm is centrifuged 10min, and gained precipitation is GO/LDH complex；
The preparation of (c) NG/LDH VPO catalysts
Weigh 0.5g graphite phase carbon nitride, be designated as C3N4, it is dissolved in 14mL concentrated sulfuric acid solution, adds the dilution of 50mL deionized water after being stirred at room temperature two hours, after ultrasonic 2h, mixed liquor is washed till neutrality, obtains 0.3～0.7mg/mLC3N4Nanometer sheet aqueous dispersions, in this solution of 80mL, gained GO/LDH complex in a certain amount of step (b) it is dividedly in some parts under ultrasound condition, add 2mL hydrazine hydrate the most under agitation, after stirring, mixed liquor is moved in reactor, 20h is reacted under the conditions of 180 DEG C, by deionized water and washing with alcohol three times after gained solid sample centrifugation, dried difunctional VPO catalysts NG/LDH.
A kind of nitrogen-doped graphene/difunctional VPO catalysts of ferro-cobalt houghite the most according to claim 1, it is characterised in that the mol ratio of cobalt chloride hexahydrate described in step (a) and ferric chloride hexahydrate is 3:1.
A kind of nitrogen-doped graphene/difunctional VPO catalysts of ferro-cobalt houghite the most according to claim 1 and 2, it is characterised in that this catalyst is shaggy laminated structure, and mean diameter is 125～150nm, and specific surface area is 134.09～168.63m2/g。
A kind of nitrogen-doped graphene the most according to claims 1 to 3/difunctional VPO catalysts of ferro-cobalt houghite, it is characterised in that described catalyst is for the reaction of electrolyzed alkaline water Oxygen anodic evolution and fuel battery negative pole oxygen reduction reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610172917.9A CN105826574B (en) | 2016-03-24 | 2016-03-24 | Nitrogen-doped graphene/difunctional VPO catalysts of ferro-cobalt houghite and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610172917.9A CN105826574B (en) | 2016-03-24 | 2016-03-24 | Nitrogen-doped graphene/difunctional VPO catalysts of ferro-cobalt houghite and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105826574A true CN105826574A (en) | 2016-08-03 |
| CN105826574B CN105826574B (en) | 2018-01-19 |
Family
ID=56524525
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610172917.9A Active CN105826574B (en) | 2016-03-24 | 2016-03-24 | Nitrogen-doped graphene/difunctional VPO catalysts of ferro-cobalt houghite and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105826574B (en) |
Cited By (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106532071A (en) * | 2016-12-01 | 2017-03-22 | 浙江师范大学 | Method for preparing N-doped graphene-coated ferroelectric carbide catalyst |
| CN106582772A (en) * | 2017-01-04 | 2017-04-26 | 中国科学技术大学苏州研究院 | CoFe<2>O<4>/g-C<3>N<4> magnetic nanomaterial and preparation method therefor |
| CN106898787A (en) * | 2017-03-22 | 2017-06-27 | 中国科学院理化技术研究所 | A kind of nanometer nickel-ferric spinel composite of the nitrogen co-doped carbon carrier load of cobalt and its preparation method and application |
| CN107159294A (en) * | 2017-05-18 | 2017-09-15 | 常州大学 | It is a kind of to prepare the method that carbonitride modifies cobalt-based oxygen-separating catalyst |
| CN107930631A (en) * | 2017-11-27 | 2018-04-20 | 山西大同大学 | Ferronickel oxyhydroxide adulterates the analysis oxygen catalysis material of graphene oxide |
| CN108649241A (en) * | 2018-06-01 | 2018-10-12 | 济南大学 | The fuel cell oxygen reduction catalyst and preparation method thereof of nitrogen-doped graphene load C oCx/FeCo@C |
| CN109012731A (en) * | 2018-08-17 | 2018-12-18 | 南京理工大学 | Sea urchin shape CoZnAl-LDH/RGO/g-C3N4Z-type hetero-junctions and its preparation method and application |
| CN109161923A (en) * | 2018-11-05 | 2019-01-08 | 青岛科技大学 | Carbon nanotube/ferro-cobalt acrylic/hydrotalcite-like nano piece compound preparation method and its electro-catalysis application |
| CN109399629A (en) * | 2018-12-28 | 2019-03-01 | 北京航空航天大学 | A kind of preparation method of the sol solutions containing two-dimensional nano container payload corrosion inhibiter |
| CN109518219A (en) * | 2018-12-24 | 2019-03-26 | 江苏大学 | A kind of preparation method and applications of graphene-based nickel cobalt bimetallic oxygen-separating catalyst |
| CN109659543A (en) * | 2018-12-24 | 2019-04-19 | 苏州大学 | Bimetallic oxide nano material and its preparation and application |
| CN110386597A (en) * | 2019-09-02 | 2019-10-29 | 石墨烯科技有限公司 | Large-scale production thin graphene equipment and large-scale production thin graphene method |
| CN110444772A (en) * | 2019-08-28 | 2019-11-12 | 广西师范大学 | A kind of bimetallic base Fe-Co-N-S codope C catalyst and the preparation method and application thereof |
| CN111167499A (en) * | 2020-01-21 | 2020-05-19 | 佛山科学技术学院 | NiM-LDH/g-C3N4Composite photocatalytic material and preparation method thereof |
| CN111211312A (en) * | 2020-01-21 | 2020-05-29 | 河南科技大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111446086A (en) * | 2020-03-09 | 2020-07-24 | 浙江工业大学 | Preparation method of nickel-cobalt-manganese hydroxide nanosheet/foamed nickel @ nitrogen-doped carbon electrode material |
| CN111477462A (en) * | 2020-03-09 | 2020-07-31 | 浙江工业大学 | Preparation method of nickel-cobalt-manganese hydroxide nanoneedle/nitrogen-doped carbon/foamed nickel electrode material |
| CN114792810A (en) * | 2022-04-08 | 2022-07-26 | 三峡大学 | Preparation method of Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2013132259A1 (en) * | 2012-03-09 | 2013-09-12 | Bio Nano Consulting | Graphene and graphene oxide aerogels/xerogels for co2 capture |
| US20140333264A1 (en) * | 2011-02-18 | 2014-11-13 | The Board Of Trustees Of The Leland Stanford Junior University | Battery with hybrid electrocatalysts |
| CN104588034A (en) * | 2014-12-17 | 2015-05-06 | 北京化工大学 | Graphene based supported precious metal material and preparation method thereof |
| CN105251489A (en) * | 2015-09-13 | 2016-01-20 | 中南大学 | Preparation method for iron-based non-noble metal oxygen evolution catalysts |
-
2016
- 2016-03-24 CN CN201610172917.9A patent/CN105826574B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140333264A1 (en) * | 2011-02-18 | 2014-11-13 | The Board Of Trustees Of The Leland Stanford Junior University | Battery with hybrid electrocatalysts |
| WO2013132259A1 (en) * | 2012-03-09 | 2013-09-12 | Bio Nano Consulting | Graphene and graphene oxide aerogels/xerogels for co2 capture |
| CN104588034A (en) * | 2014-12-17 | 2015-05-06 | 北京化工大学 | Graphene based supported precious metal material and preparation method thereof |
| CN105251489A (en) * | 2015-09-13 | 2016-01-20 | 中南大学 | Preparation method for iron-based non-noble metal oxygen evolution catalysts |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106532071A (en) * | 2016-12-01 | 2017-03-22 | 浙江师范大学 | Method for preparing N-doped graphene-coated ferroelectric carbide catalyst |
| CN106532071B (en) * | 2016-12-01 | 2019-05-31 | 浙江师范大学 | A method of preparing N doped graphene package cementite elctro-catalyst |
| CN106582772B (en) * | 2017-01-04 | 2019-04-16 | 中国科学技术大学苏州研究院 | A kind of CoFe2O4/g-C3N4Magnetic Nano material and preparation method thereof |
| CN106582772A (en) * | 2017-01-04 | 2017-04-26 | 中国科学技术大学苏州研究院 | CoFe<2>O<4>/g-C<3>N<4> magnetic nanomaterial and preparation method therefor |
| CN106898787A (en) * | 2017-03-22 | 2017-06-27 | 中国科学院理化技术研究所 | A kind of nanometer nickel-ferric spinel composite of the nitrogen co-doped carbon carrier load of cobalt and its preparation method and application |
| CN106898787B (en) * | 2017-03-22 | 2020-04-10 | 中国科学院理化技术研究所 | Cobalt-nitrogen co-doped carbon carrier loaded nano nickel-iron hydrotalcite composite material and preparation method and application thereof |
| CN107159294A (en) * | 2017-05-18 | 2017-09-15 | 常州大学 | It is a kind of to prepare the method that carbonitride modifies cobalt-based oxygen-separating catalyst |
| CN107930631A (en) * | 2017-11-27 | 2018-04-20 | 山西大同大学 | Ferronickel oxyhydroxide adulterates the analysis oxygen catalysis material of graphene oxide |
| CN108649241A (en) * | 2018-06-01 | 2018-10-12 | 济南大学 | The fuel cell oxygen reduction catalyst and preparation method thereof of nitrogen-doped graphene load C oCx/FeCo@C |
| CN108649241B (en) * | 2018-06-01 | 2021-03-09 | 济南大学 | Nitrogen-doped graphene-loaded CoCx/FeCo @ C fuel cell oxygen reduction catalyst and preparation method thereof |
| CN109012731A (en) * | 2018-08-17 | 2018-12-18 | 南京理工大学 | Sea urchin shape CoZnAl-LDH/RGO/g-C3N4Z-type hetero-junctions and its preparation method and application |
| CN109012731B (en) * | 2018-08-17 | 2021-04-27 | 南京理工大学 | Sea urchin-shaped CoZnAl-LDH/RGO/g-C3N4Z-type heterojunction and preparation method and application thereof |
| CN109161923A (en) * | 2018-11-05 | 2019-01-08 | 青岛科技大学 | Carbon nanotube/ferro-cobalt acrylic/hydrotalcite-like nano piece compound preparation method and its electro-catalysis application |
| CN109518219A (en) * | 2018-12-24 | 2019-03-26 | 江苏大学 | A kind of preparation method and applications of graphene-based nickel cobalt bimetallic oxygen-separating catalyst |
| CN109659543A (en) * | 2018-12-24 | 2019-04-19 | 苏州大学 | Bimetallic oxide nano material and its preparation and application |
| CN109399629A (en) * | 2018-12-28 | 2019-03-01 | 北京航空航天大学 | A kind of preparation method of the sol solutions containing two-dimensional nano container payload corrosion inhibiter |
| CN110444772A (en) * | 2019-08-28 | 2019-11-12 | 广西师范大学 | A kind of bimetallic base Fe-Co-N-S codope C catalyst and the preparation method and application thereof |
| CN110386597A (en) * | 2019-09-02 | 2019-10-29 | 石墨烯科技有限公司 | Large-scale production thin graphene equipment and large-scale production thin graphene method |
| CN111211312A (en) * | 2020-01-21 | 2020-05-29 | 河南科技大学 | Lithium-sulfur battery positive electrode material and preparation method thereof |
| CN111167499A (en) * | 2020-01-21 | 2020-05-19 | 佛山科学技术学院 | NiM-LDH/g-C3N4Composite photocatalytic material and preparation method thereof |
| CN111167499B (en) * | 2020-01-21 | 2022-11-22 | 佛山科学技术学院 | NiM-LDH/g-C 3 N 4 Composite photocatalytic material and preparation method thereof |
| CN111446086A (en) * | 2020-03-09 | 2020-07-24 | 浙江工业大学 | Preparation method of nickel-cobalt-manganese hydroxide nanosheet/foamed nickel @ nitrogen-doped carbon electrode material |
| CN111477462A (en) * | 2020-03-09 | 2020-07-31 | 浙江工业大学 | Preparation method of nickel-cobalt-manganese hydroxide nanoneedle/nitrogen-doped carbon/foamed nickel electrode material |
| CN114792810A (en) * | 2022-04-08 | 2022-07-26 | 三峡大学 | Preparation method of Fe (Ni) -NCNTs @ NiFe-LDH in-situ electrode |
| CN114792810B (en) * | 2022-04-08 | 2024-01-30 | 启东高能新能源有限公司 | Preparation method of Fe (Ni) -NCNTs@NiFe-LDH in-situ electrode |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105826574B (en) | 2018-01-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105826574B (en) | Nitrogen-doped graphene/difunctional VPO catalysts of ferro-cobalt houghite and its preparation method and application | |
| CN105514450B (en) | Nitrogen-doped graphene/difunctional VPO catalysts of ferronickel houghite and its preparation method and application | |
| Yang et al. | Advanced oxygen electrocatalysis in energy conversion and storage | |
| Wang et al. | Perovskite oxides as bifunctional oxygen electrocatalysts for oxygen evolution/reduction reactions–A mini review | |
| CN105618060B (en) | Difunctional VPO catalysts of graphene/nickel iron houghite and its preparation method and application | |
| CN109012675B (en) | Method for preparing graphene/nickel-iron hydrotalcite nanosheet bifunctional oxygen catalyst by one-step method | |
| Zhan et al. | Synthesis of mesoporous NiCo2O4 fibers and their electrocatalytic activity on direct oxidation of ethanol in alkaline media | |
| Wei et al. | Honeycombed-like nanosheet array composite NiCo2O4/rGO for efficient methanol electrooxidation and supercapacitors | |
| Li et al. | Nanoflower-branch LDHs and CoNi alloy derived from electrospun carbon nanofibers for efficient oxygen electrocatalysis in microbial fuel cells | |
| Zhang et al. | Iron triad (Fe, co, Ni) trinary phosphide nanosheet arrays as high-performance bifunctional electrodes for full water splitting in basic and neutral conditions | |
| Kakaei et al. | Fabrication of Pt–CeO2 nanoparticles supported sulfonated reduced graphene oxide as an efficient electrocatalyst for ethanol oxidation | |
| CN108543545A (en) | A kind of tri- doped carbon nanometer pipe cladded type FeNi@NCNT catalyst of Fe, Ni, N, preparation method and applications | |
| CN106025302A (en) | Single-cell-thickness nano porous cobalt oxide nanosheet array electrocatalytic material | |
| CN110142058B (en) | F127-induced three-dimensional porous FeNi-NC dual-functional electrocatalyst and preparation method thereof | |
| Yang et al. | Recent progress and prospective of nickel selenide-based electrocatalysts for water splitting | |
| CN105845951B (en) | Ionic liquid covalent modification graphene peels off difunctional VPO catalysts of houghite and its preparation method and application | |
| CN108823625B (en) | Composite metal hydroxide and preparation method and application thereof | |
| CN111206271B (en) | Preparation method, product and application of self-supporting metal doped iron nitride electrode | |
| Ye et al. | Reduced graphene oxide supporting hollow bimetallic phosphide nanoparticle hybrids for electrocatalytic oxygen evolution | |
| CN109371420A (en) | A kind of single layered porous nickel-ferric spinel base electro-catalysis analysis oxygen electrode with and its preparation method and application | |
| CN113481534A (en) | Preparation method of zirconium-doped cobalt-iron layered double hydroxide with low crystallinity and application of zirconium-doped cobalt-iron layered double hydroxide in hydrogen production by water electrolysis | |
| CN111883787B (en) | Bifunctional oxygen catalyst and preparation method thereof | |
| Sun et al. | Interfacial electronic structure and electrocatalytic performance modulation in Cu0. 81Ni0. 19 nanoflowers by heteroatom doping engineering using ionic liquid dopant | |
| CN110433810B (en) | Preparation method of copper oxide doped nickel-iron hydrotalcite nanosheet/graphene bifunctional water decomposition catalyst | |
| Du et al. | Synthesis of bifunctional NiFe layered double hydroxides (LDH)/Mo-doped g-C3N4 electrocatalyst for efficient methanol oxidation and seawater splitting |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20191122 Address after: 225500 Ho Ho Town, Jiangyan District, Jiangsu City, Taizhou Province Patentee after: Jiangsu Sanji Industry Co., Ltd. Address before: 266000 Shandong province Qingdao City, Zhengzhou Road No. 53, Qingdao University of Science & Technology Patentee before: Qingdao University of Science & Technology |
|
| TR01 | Transfer of patent right |