CN110227531A - A kind of preparation method of molybdenum doping cobalt iron oxide nanometer sheet bifunctional electrocatalyst - Google Patents
A kind of preparation method of molybdenum doping cobalt iron oxide nanometer sheet bifunctional electrocatalyst Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 14
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 14
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 13
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 12
- QRXDDLFGCDQOTA-UHFFFAOYSA-N cobalt(2+) iron(2+) oxygen(2-) Chemical compound [O-2].[Fe+2].[Co+2].[O-2] QRXDDLFGCDQOTA-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 239000011733 molybdenum Substances 0.000 title claims abstract description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000000463 material Substances 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 17
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 claims abstract description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000004809 Teflon Substances 0.000 claims description 8
- 229920006362 Teflon® Polymers 0.000 claims description 8
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 8
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 229910001220 stainless steel Inorganic materials 0.000 claims description 8
- 239000010935 stainless steel Substances 0.000 claims description 8
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 239000006260 foam Substances 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000000137 annealing Methods 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 18
- 238000000354 decomposition reaction Methods 0.000 abstract description 6
- 238000000034 method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 229910002651 NO3 Inorganic materials 0.000 description 30
- 238000004502 linear sweep voltammetry Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 9
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 7
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 6
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 6
- 230000010287 polarization Effects 0.000 description 6
- 239000003643 water by type Substances 0.000 description 6
- 239000012378 ammonium molybdate tetrahydrate Substances 0.000 description 5
- FIXLYHHVMHXSCP-UHFFFAOYSA-H azane;dihydroxy(dioxo)molybdenum;trioxomolybdenum;tetrahydrate Chemical compound N.N.N.N.N.N.O.O.O.O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O=[Mo](=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O.O[Mo](O)(=O)=O FIXLYHHVMHXSCP-UHFFFAOYSA-H 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 229960004756 ethanol Drugs 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/61—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The present invention relates to two-dimentional elctro-catalyst technical fields, disclose a kind of preparation method of molybdenum doping cobalt iron oxide nanometer sheet bifunctional electrocatalyst；Specifically by the Co (NO of molar ratio 1:1:0.001-1:1:33)2·6H2O, Fe (NO3)2·9H2O and (NH4)6Mo7O24·4H2O and urea, NH4F is added to the water to form solution, and the solution and base material are transferred in autoclave, hydrothermal synthesis CoxFeyMozO NSs, the efficient elctro-catalyst that can be used for during electrochemical decomposition water；The ultra-thin nanostructure of the present invention has bigger serface, while also having excellent charge transport ability and a large amount of active site, CoxFeyMozO NSs has excellent OER and HER activity and long-term cyclic durability.The method of the present invention is at low cost, easy to operate, is conducive to promote and apply.
Description
Technical field
The invention belongs to two-dimentional elctro-catalyst preparation technical field, specially a kind of molybdenum doping cobalt iron oxide nanometer sheet is double
The preparation method of function elctro-catalyst.
Background technique
In recent years, due to environmental pollution and energy crisis, dependence and exploration to traditional energy (fossil fuel) are reduced
The renewable and sustainable energy of human society becomes one of most pressing challenge.Electrochemical decomposition water is as a kind of offer cleaning
With the mode of sustainable energy, including oxygen evolution reaction (OER) and evolving hydrogen reaction (HER), still, from thermodynamics and kinetics this two
From the point of view of a aspect, it is the key that improve energy conversion efficiency hardly possible that Oxygen anodic evolution reaction and cathode hydrogen evolution, which react huge overpotential,
Topic.In particular, be the bottleneck of water decomposition by the slow dynamics of the oxygen evolution reaction of four electronics oxidation reaction of multi-step, this needs
The overpotential bigger than theoretical overpotential (1.23 V).In order to accelerate reaction rate, overpotential is reduced, energy conversion effect is improved
Rate, industry have explored a large amount of analysis oxygen and liberation of hydrogen catalyst.So far, with the analysis of low overpotential and Tafel slope
VPO catalysts and liberation of hydrogen catalyst are metal oxide containing precious metals (IrO respectively2Or RuO2) and Pt based compound, but these noble metals
Scarcity and high cost limit their large-scale application.Therefore, design and develop based on the earth enrich element (such as Mn,
Fe, Co, Ni and Mo) the alternative elctro-catalyst of high efficiency, low cost be necessary for overall moisture solution.
Transition metal element doped catalyst is expected to overcome noble metal as the high cost of catalyst and lacking for scarcity
Point becomes the double-function catalyzing agent material with excellent OER and HER performance instead of noble metal.Cobalt iron oxide nanometer sheet
Catalyst is proved to be a kind of material that excellent catalytic performance is shown during electrochemical decomposition water.In addition to this, it adulterates
It is a kind of extensive use and very promising technology, thus it is possible to vary the characteristic electron of transition metal ions, to be had
The synthetic material of more preferable performance, Mo, which is doped in metal oxide or hydroxide, can significantly improve reactivity and reduce
Current potential.Therefore, it is current research emphasis that the excellent transition-metal catalyst material of noble metal can be substituted by, which developing,.
Summary of the invention
The present invention overcomes the shortcomings of the prior art, prepares molybdenum doping cobalt iron oxide nanometer with the method for hydrothermal synthesis
Piece bifunctional electrocatalyst, it is therefore an objective to improve the performance of elctro-catalyst.
The present invention is achieved through the following technical solutions.
A kind of preparation method of molybdenum doping cobalt iron oxide nanometer sheet bifunctional electrocatalyst, specifically includes the following steps:
A) by Co (NO3)2·6H2O, Fe (NO3)2·9H2O, urea, NH4F and (NH4)6Mo7O24·4H2O is added to the water, and stirs
It mixes up to being completely dissolved to form solution, wherein Co (NO3)2·6H2O, Fe (NO3)2·9H2O and (NH4)6Mo7O24·4H2O moles
Amount x/y/z ratio is 1:1:0.001~1:1:3；
B) solution and base material are transferred in autoclave, are sealed at 120-200 DEG C and heat 6-15h, natural cooling
To room temperature；
C) for several times by the product washing of step b, vacuum drying, finally heated annealing obtains product and is expressed as CoxFeyMozO NSs。
Preferably, the base material is nickel foam, carbon paper, carbon cloth, any one in titanium sheet.
Preferably, the autoclave is the stainless steel autoclave with teflon lined.
It preferably, is to wash product with ultrapure water and dehydrated alcohol in the step c.
Preferably, the heating anneal of the step c is the 1-3h that anneals at 750-850 DEG C.
Preferably, the Co (NO3)2·6H2O, Fe (NO3)2·9H2O, urea, NH4F and (NH4)6Mo7O24·4H2O
Molar ratio be 1:1:5:4:0.001-1:1:5:4:3.
The present invention is generated compared with the existing technology to be had the beneficial effect that.
The Co that the present invention synthesizesxFeyMozThe efficient elctro-catalyst that O NSs can be used for during electrochemical decomposition water.With it is existing
There is technology to compare, when the ultra-thin nanostructure of the present invention makes the sample as catalytic electrode material, not only there is big ratio table
Area, while also there is excellent charge transport ability and a large amount of active site, so that the electrode material of preparation has
Better than business RuO2With OER the and HER performance of Pt/C.CoxFeyMozO NSs has excellent OER activity and stability, meanwhile,
Show excellent HER activity and long-term cyclic durability, therefore the bifunctional electrocatalyst that can be used for during electrolysis water.This
Inventive method is at low cost, easy to operate, is conducive to further scientific research and popularization and application to bifunctional electrocatalyst.
Detailed description of the invention
Fig. 1 is the Co that embodiment 2 is prepared1Fe1Mo1.8The scanning electron microscope diagram of O NSs.
Fig. 2 is Co prepared by embodiment 21Fe1Mo1.8The transmission electron microscope figure of O NSs.
Fig. 3 is embodiment 1-3 in the present invention, the LSV of the OER of blank control example and comparative example schemes.
Fig. 4 is embodiment 1-3 in the present invention, the Tafel plots of the OER of blank control example and comparative example schemes.
Fig. 5 is embodiment 1-3 in the present invention, the LSV of the HER of blank control example and comparative example schemes.
Fig. 6 is embodiment 1-3 in the present invention, the Tafel plots of the HER of blank control example and comparative example schemes.
Fig. 7 indicates Co prepared by embodiment 21Fe1Mo1.8OER the and HER stability diagram of O NSs.
Specific embodiment
In order to which technical problems, technical solutions and advantages to be solved are more clearly understood, in conjunction with reality
Example and attached drawing are applied, the present invention will be described in further detail.It should be appreciated that specific embodiment described herein is only used to
It explains the present invention, is not intended to limit the present invention.Below with reference to the examples and drawings technical solution that the present invention will be described in detail, but
The scope of protection is not limited by this.
Embodiment 1
Co1Fe1Mo1.2The preparation of O NSs
First by 1 mmol cabaltous nitrate hexahydrate (Co (NO3)2·6H2O), 1 mmol Fe(NO3)39H2O (Fe (NO3)2·
9H2O), 5 mmol urea and 4 mmol NH4The Ammonium Molybdate Tetrahydrate ((NH of F and 1.2 mmol4)6Mo7O24·4H2O it) is added
Into 36 mL ultrapure waters, stir up to being completely dissolved, wherein Co (NO3)2·6H2O, Fe (NO3)2·9H2O and (NH4)6Mo7O24·4H2O mole x/y/z ratio is 1:1:1.2.
Then, this solution and nickel foam as base material are transferred to the stainless steel of 50 mL teflon lineds
In autoclave, it is sealed against heating 10 hours at 180 DEG C, cooled to room temperature.By product ultrapure water and dehydrated alcohol
Washing for several times, is dried in vacuo at 60 DEG C, finally anneals 2 hours at 800 DEG C.Products therefrom is expressed as Co1Fe1Mo1.2O NSs@
NF。
Embodiment 2
Co1Fe1Mo1.8The preparation of O NSs
First by 1 mmol cabaltous nitrate hexahydrate (Co (NO3)2·6H2O), 1 mmol Fe(NO3)39H2O (Fe (NO3)2·
9H2O), 5 mmol urea and 4 mmol NH4The Ammonium Molybdate Tetrahydrate ((NH of F and 1.8 mmol4)6Mo7O24·4H2O it) is added
Into 36 mL ultrapure waters, stir up to being completely dissolved, wherein Co (NO3)2·6H2O, Fe (NO3)2·9H2O and (NH4)6Mo7O24·4H2O mole x/y/z ratio is 1:1:1.8.
Then, this solution and nickel foam as base material are transferred to the stainless steel of 50 mL teflon lineds
In autoclave, it is sealed against heating 10 hours at 180 DEG C, cooled to room temperature.By product ultrapure water and dehydrated alcohol
Washing for several times, is dried in vacuo at 60 DEG C, finally anneals 2 hours at 800 DEG C.Products therefrom is expressed as Co1Fe1Mo1.8O NSs@
NF。
Embodiment 3
Co1Fe1Mo2.4The preparation of O NSs
First by 1 mmol cabaltous nitrate hexahydrate (Co (NO3)2·6H2O), 1 mmol Fe(NO3)39H2O (Fe (NO3)2·
9H2O), 5 mmol urea and 4 mmol NH4The Ammonium Molybdate Tetrahydrate ((NH of F and 2.4 mmol4)6Mo7O24·4H2O it) is added
Into 36 mL ultrapure waters, stir up to being completely dissolved, wherein Co (NO3)2·6H2O, Fe (NO3)2·9H2O and (NH4)6Mo7O24·4H2O mole x/y/z ratio is 1:1:2.4.
Then, this solution and nickel foam as base material are transferred to the stainless steel of 50 mL teflon lineds
In autoclave, it is sealed against heating 10 hours at 180 DEG C, cooled to room temperature.By product ultrapure water and dehydrated alcohol
Washing for several times, is dried in vacuo at 60 DEG C, finally anneals 2 hours at 800 DEG C.Products therefrom is expressed as Co1Fe1Mo2.4O NSs@
NF。
Embodiment 4
Co1Fe1Mo2.2The preparation of O NSs
First by 1 mmol cabaltous nitrate hexahydrate (Co (NO3)2·6H2O), 1 mmol Fe(NO3)39H2O (Fe (NO3)2·
9H2O), 5 mmol urea and 4 mmol NH4The Ammonium Molybdate Tetrahydrate ((NH of F and 2.2 mmol4)6Mo7O24·4H2O it) is added
Into 36 mL ultrapure waters, stir up to being completely dissolved, wherein Co (NO3)2·6H2O, Fe (NO3)2·9H2O and (NH4)6Mo7O24·4H2O mole x/y/z ratio is 1:1:2.2.
Then, the stainless steel for this solution and titanium sheet as base material being transferred to 50 mL teflon lineds is high
It presses in kettle, is sealed against heating 15 hours at 120 DEG C, cooled to room temperature.Product is washed with ultrapure water and dehydrated alcohol
It washs for several times, is dried in vacuo at 60 DEG C, finally annealed 1 hour at 750 DEG C.Products therefrom is expressed as Co1Fe1Mo2.2O NSs。
Embodiment 5
Co1Fe1Mo0.8The preparation of O NSs
First by 1 mmol cabaltous nitrate hexahydrate (Co (NO3)2·6H2O), 1 mmol Fe(NO3)39H2O (Fe (NO3)2·
9H2O), 5 mmol urea and 4 mmol NH4The Ammonium Molybdate Tetrahydrate ((NH of F and 0.8 mmol4)6Mo7O24·4H2O it) is added
Into 36 mL ultrapure waters, stir up to being completely dissolved, wherein Co (NO3)2·6H2O, Fe (NO3)2·9H2O and (NH4)6Mo7O24·4H2O mole x/y/z ratio is 1:1:0.8.
Then, the stainless steel for this solution and carbon cloth as base material being transferred to 50 mL teflon lineds is high
It presses in kettle, is sealed against heating 6 hours at 200 DEG C, cooled to room temperature.Product is washed with ultrapure water and dehydrated alcohol
For several times, it is dried in vacuo at 60 DEG C, finally anneals 3 hours at 850 DEG C.Products therefrom is expressed as Co1Fe1Mo0.8O NSs。
Blank control example 1
First by 1 mmol cabaltous nitrate hexahydrate (Co (NO3)2·6H2O), 1 mmol Fe(NO3)39H2O (Fe (NO3)2·
9H2O), 5 mmol urea and 4 mmol NH4F is added in 36 mL ultrapure waters, is stirred up to being completely dissolved, wherein Co
(NO3)2·6H2O, Fe (NO3)2·9H2O mole x/y ratio is 1:1.
Then, this solution and nickel foam as base material are transferred to the stainless steel of 50 mL teflon lineds
In autoclave, it is sealed against heating 10 hours at 180 DEG C, cooled to room temperature.By product ultrapure water and dehydrated alcohol
Washing for several times, is dried in vacuo at 60 DEG C, finally anneals 2 hours at 800 DEG C.Products therefrom is expressed as CoFeO NSs@NF.
Comparative example 1
Commercial catalysts RuO2Base material is modified with Pt/C, preparation work electrode is as a comparison, specific as follows:
By 8 mg RuO2Or Pt/C and 100 μ L Nafion(5%) solution is dispersed in 900 μ L ethyl alcohol, ultrasonic treatment is at least
30 minutes to form uniform ink-like solution.By about 130 μ L liquid depositions, in base material, (area is 1 × 1 cm-2) on,
Vacuum drying obtains working electrode at 60 DEG C.RuO on base material2Or the load capacity of Pt/C catalyst is about 1.0375
mg cm-2, the Choice of substrate materials nickel foam of load.
Embodiment characterization and catalytic performance test:
The performance for the material being prepared is that (material being prepared is as working electrode, saturated calomel electrode by three electrodes
As reference electrode, carbon electrode is as to electrode) come what is characterized, obtain polarization curve (LSV) and Tafel curve
(Tafel plots).The three-electrode system is initially positioned in 1 M KOH solution, in 1.05-1.9V(vs.RHE current potential)
It is scanned in range using linear sweep voltammetry, obtains polarization curve (LSV), study the OER performance of material prepared.For
The OER performance for characterizing material prepared, with business RuO2Catalytic performance be compared.
Secondly the three-electrode system is placed in 1 M KOH solution, in -0.85-0.2 V(vs.RHE potential range)
It is interior to be scanned using linear sweep voltammetry, polarization curve (LSV) is obtained, the HER performance of material prepared is studied.For characterization
The HER performance of material prepared, is compared with the catalytic performance of business Pt/C.
Attached drawing 1 is the Co being prepared1Fe1Mo1.8The scanning electron microscope diagram of O NSs.
By obtained drying sample ultrasonic disperse in ethanol solution, to carry out TEM characterization to sample.Attached drawing 2
The Co being prepared for embodiment 21Fe1Mo1.8The TEM of O NSs schemes, and the performance for the material being prepared is by three electrodes (system
Standby obtained material is as working electrode, saturated calomel electrode is as reference electrode, and carbon electrode is as to electrode) it characterizes
, obtain polarization curve (LSV) and Tafel curve (Tafel plots).The three-electrode system is initially positioned at 1 M KOH
In solution, in 1.05-1.9V(vs.RHE it is scanned in potential range) using linear sweep voltammetry, it is bent to obtain polarization
Line (LSV) studies the OER performance of material prepared.Fig. 3 indicates different materials and business RuO in the present invention2LSV figure.Fig. 4
Indicate different materials and business RuO in the present invention2Tafel plots figure.
Secondly the three-electrode system is placed in 1 M KOH solution, in -0.85-0.2 V(vs.RHE potential range)
It is interior to be scanned using linear sweep voltammetry, polarization curve (LSV) is obtained, the HER performance of material prepared is studied.Fig. 5 table
Show that the LSV of different materials and business Pt/C scheme in the present invention.Fig. 6 indicates the Tafel of different materials and business Pt/C in the present invention
Plots figure.
By the above performance test it is found that the Co synthesized in the present invention1Fe1Mo1.8O NSs can be used for electrochemical decomposition water process
In efficient elctro-catalyst.Compared with prior art, the ultra-thin nanostructure of the present invention makes the sample as catalysis electrode material
When material, not only there is big specific surface area, while also there is excellent charge transport ability and a large amount of active site, to make
The electrode material that must be prepared, which has, is better than business RuO2With OER the and HER performance of Pt/C.In 10 mA cm-2When have 210 mV
Low overpotential and 32 mV dec-1Tafel slope, be better than business RuO2Performance (310 mV@, 10 mA cm-2, 123 mV
dec-1), and have excellent stability after 24 hours.Meanwhile Co1Fe1Mo1.8O NSs also shows that excellent HER is living
Property, in 10 mA cm-2When the low overpotential with 157 mV, and after 24 hours have powerful long-term cyclic durability.
Compared with most of cobalt-based elctro-catalysts being previously reported, Co1Fe1Mo1.8O NSs catalytic activity raising be attributable to Co and Fe it
Between the regulation of strong electron interaction and Mo to surface-active number of sites amount.The method of the present invention is at low cost, easy to operate, has
Conducive to the further scientific research and popularization and application to bifunctional electrocatalyst.
The above content is combine specific preferred embodiment to the further description done of the present invention, and it cannot be said that
A specific embodiment of the invention is only limitted to this, for those of ordinary skill in the art to which the present invention belongs, is not taking off
Under the premise of from the present invention, several simple deduction or replace can also be made, all shall be regarded as belonging to the present invention by being submitted
Claims determine scope of patent protection.
Claims (6)
1. a kind of preparation method of molybdenum doping cobalt iron oxide nanometer sheet bifunctional electrocatalyst, which is characterized in that specifically include
Following steps:
A) by Co (NO3)2·6H2O, Fe (NO3)2·9H2O, urea, NH4F and (NH4)6Mo7O24·4H2O is added to the water, stirring
Until be completely dissolved to form solution, wherein Co (NO3)2·6H2O, Fe (NO3)2·9H2O and (NH4)6Mo7O24·4H2O mole
X/y/z ratio is 1:1:0.001-1:1:3；
B) solution and base material are transferred in autoclave, are sealed in heating 6-15 h, natural cooling at 120-200 DEG C
To room temperature；
C) for several times by the product washing of step b, vacuum drying, finally heated annealing obtains product and is expressed as CoxFeyMozO NSs。
2. a kind of preparation method of molybdenum doping cobalt iron oxide nanometer sheet bifunctional electrocatalyst according to claim 1,
It is characterized in that, the base material is nickel foam, carbon paper, carbon cloth, any one in titanium sheet.
3. a kind of preparation method of molybdenum doping cobalt iron oxide nanometer sheet bifunctional electrocatalyst according to claim 1,
It is characterized in that, the autoclave is the stainless steel autoclave with teflon lined.
4. a kind of preparation method of molybdenum doping cobalt iron oxide nanometer sheet bifunctional electrocatalyst according to claim 1,
It is characterized in that, being to wash product with ultrapure water and dehydrated alcohol in the step c.
5. a kind of preparation method of molybdenum doping cobalt iron oxide nanometer sheet bifunctional electrocatalyst according to claim 1,
It is characterized in that, the heating anneal of the step c is the 1-3h that anneals at 750-850 DEG C.
6. a kind of preparation method of molybdenum doping cobalt iron oxide nanometer sheet bifunctional electrocatalyst according to claim 1,
It is characterized in that, Co (the NO3)2·6H2O, Fe (NO3)2·9H2O, urea, NH4F and (NH4)6Mo7O24·4H2O's rubs
You are than being 1:1:5:4:0.001-1:1:5:4:3.
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