CN110227531B - Preparation method of molybdenum-doped cobalt-iron oxide nanosheet bifunctional electrocatalyst - Google Patents
Preparation method of molybdenum-doped cobalt-iron oxide nanosheet bifunctional electrocatalyst Download PDFInfo
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- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 21
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 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 11
- 239000002135 nanosheet Substances 0.000 title claims abstract description 11
- 230000001588 bifunctional effect Effects 0.000 title claims 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 31
- 238000000034 method Methods 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 11
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-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 11
- 239000000758 substrate Substances 0.000 claims abstract description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 15
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 14
- 239000012498 ultrapure water Substances 0.000 claims description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- 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
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 229910052799 carbon Inorganic materials 0.000 claims description 7
- 238000000137 annealing Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 5
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004744 fabric Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000001351 cycling effect Effects 0.000 abstract description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 14
- 229910002651 NO3 Inorganic materials 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 10
- 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
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 6
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 6
- 230000010287 polarization Effects 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
- 230000000052 comparative effect Effects 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000007772 electrode material Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000008859 change Effects 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
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- 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—
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- 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
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- 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
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- 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
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- 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
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- 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 invention relates to the technical field of two-dimensional electrocatalysts, and discloses a preparation method of a molybdenum-doped cobalt-iron oxide nanosheet dual-functional electrocatalyst; specifically, Co (NO) with the molar ratio of 1:1:0.001-1:1:33)2·6H2O，Fe(NO3)2·9H2O and (NH)4)6Mo7O24·4H2O, and urea, NH4F is added into water to form a solution, the solution and the substrate material are transferred into an autoclave, and Co is hydrothermally synthesizedxFeyMozO NSs, a high efficiency electrocatalyst useful in the electrochemical water splitting process; the ultrathin nanostructure has large specific surface area, excellent charge transmission capability and a large number of active sites, CoxFeyMozO NSs have excellent OER and HER activity and long-term cycling durability. The method has low cost and easy operation, and is beneficial to popularization and application.
Description
Technical Field
The invention belongs to the technical field of preparation of two-dimensional electrocatalysts, and particularly relates to a preparation method of a molybdenum-doped cobalt iron oxide nanosheet dual-functional electrocatalyst.
Background
In recent years, due to environmental pollution and energy crisis, the dependence on conventional energy (fossil fuel) is reduced and exploration is conductedRenewable and sustainable energy sources for human society have become one of the most pressing challenges. Electrochemical water splitting as a means of providing clean and sustainable energy sources includes Oxygen Evolution Reaction (OER) and Hydrogen Evolution Reaction (HER), but the huge overpotential of anodic and cathodic oxygen evolution reactions is a key challenge to improve energy conversion efficiency from both thermodynamic and kinetic perspectives. In particular, the slow kinetics of oxygen evolution reactions through multi-step four electron oxidation reactions is a bottleneck for water decomposition, which requires an overpotential greater than the theoretical overpotential (1.23V). In order to increase the reaction rate, lower the overpotential, and improve the energy conversion efficiency, the industry has explored a number of oxygen and hydrogen evolution catalysts. Hitherto, oxygen-evolution catalysts and hydrogen-evolution catalysts having a low overpotential and Tafel slope, respectively, were noble metal oxides (IrO)2Or RuO2) And Pt-based compounds, but the scarcity and high cost of these precious metals limits their large-scale application. Therefore, it is highly desirable to design and develop efficient, low cost alternative electrocatalysts based on earth-rich elements (e.g., Mn, Fe, Co, Ni and Mo) for bulk water splitting.
The transition metal element doped catalyst is expected to overcome the defects of high cost and scarcity of the noble metal as the catalyst, and becomes a bifunctional catalyst material which replaces the noble metal and has excellent OER and HER performances. Cobalt iron oxide nanosheet catalysts have proven to be a material that exhibits excellent catalytic performance in the electrochemical decomposition of water. In addition, doping is a widely used and promising technique, which can change the electronic characteristics of transition metal ions to obtain a synthetic material with better performance, and doping Mo into metal oxides or hydroxides can significantly improve the reactivity and reduce the overpotential. Therefore, the development of an excellent transition metal catalyst material capable of replacing noble metals is currently the focus of research.
Disclosure of Invention
The invention overcomes the defects of the prior art, and prepares the molybdenum-doped cobalt-iron oxide nanosheet bifunctional electrocatalyst by a hydrothermal synthesis method, aiming at improving the performance of the electrocatalyst.
The invention is realized by the following technical scheme.
A preparation method of a molybdenum-doped cobalt iron oxide nanosheet bifunctional electrocatalyst specifically comprises the following steps:
a) mixing Co (NO)3)2·6H2O，Fe(NO3)2·9H2O, urea, NH4F and (NH)4)6Mo7O24·4H2Adding O into water, stirring until completely dissolving to form solution, wherein Co (NO)3)2·6H2O，Fe(NO3)2·9H2O and (NH)4)6Mo7O24·4H2The molar weight x/y/z ratio of O is 1:1:0.001-1:1: 3;
b) transferring the solution and the substrate material into an autoclave, sealing and heating at the temperature of 120-200 ℃ for 6-15h, and naturally cooling to room temperature;
c) washing the product obtained in the step b for a plurality of times, drying in vacuum, and finally heating and annealing to obtain a product expressed as CoxFeyMozO NSs。
Preferably, the substrate material is any one of foamed nickel, carbon paper, carbon cloth and titanium sheet.
Preferably, the autoclave is a stainless steel autoclave with a polytetrafluoroethylene liner.
Preferably, the product is washed by ultrapure water and absolute ethyl alcohol in the step c.
Preferably, the thermal annealing of step c is annealing at 750-850 ℃ for 1-3 h.
Preferably, said Co (NO)3)2·6H2O，Fe(NO3)2·9H2O, urea, NH4F and (NH)4)6Mo7O24·4H2The molar ratio of O is 1:1:5:4:0.001-1:1:5:4: 3.
Compared with the prior art, the invention has the beneficial effects that.
Co synthesized by the inventionxFeyMozO NSs can be used forHigh-efficiency electrocatalyst in the process of electrochemically decomposing water. Compared with the prior art, the ultrathin nanostructure of the invention ensures that the sample has large specific surface area, excellent charge transmission capability and a large number of active sites when being used as a catalytic electrode material, thereby ensuring that the prepared electrode material has better performance than commercial RuO2And OER and HER performance of Pt/C. CoxFeyMozO NSs have excellent OER activity and stability, and at the same time, exhibit excellent HER activity and long-term cycle durability, and thus can be used as bifunctional electrocatalysts in the electrolysis of water. The method has low cost and easy operation, and is favorable for further scientific research, popularization and application of the bifunctional electrocatalyst.
Drawings
FIG. 1 shows Co prepared in example 21Fe1Mo1.8Scanning electron microscopy images of O NSs.
FIG. 2 shows Co prepared in example 21Fe1Mo1.8Transmission electron microscopy images of O NSs.
FIG. 3 is a LSV plot of OERs of examples 1-3, blank control examples, and comparative examples of the present invention.
FIG. 4 is a Tafel plots of OERs of examples 1-3 of the present invention, blank control and comparative example.
Figure 5 is a graph of the LSV of HER for examples 1-3, blank control, and comparative examples of the invention.
FIG. 6 is a Tafel plots of HER for examples 1-3 of the present invention, blank control and comparative example.
FIG. 7 shows Co prepared in example 21Fe1Mo1.8OER and HER stability profiles for O NSs.
Detailed Description
In order to make the technical problems, technical solutions and advantageous effects to be solved by the present invention more clearly apparent, the present invention is further described in detail with reference to the embodiments and the accompanying drawings. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. The technical solution of the present invention is described in detail below with reference to the embodiments and the drawings, but the scope of protection is not limited thereto.
Example 1
Co1Fe1Mo1.2Preparation of O NSs
First 1 mmol of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O), 1 mmol of iron nitrate nonahydrate (Fe (NO)3)2·9H2O), 5 mmol of urea and 4 mmol of NH4F, and 1.2 mmol of ammonium molybdate tetrahydrate ((NH)4)6Mo7O24·4H2O) was added to 36 mL of ultrapure water, stirred until completely dissolved, wherein Co (NO)3)2·6H2O，Fe(NO3)2·9H2O and (NH)4)6Mo7O24·4H2The molar weight of O, x/y/z, was 1:1: 1.2.
Then, this solution and foamed nickel as a base material were transferred to a 50 mL polytetrafluoroethylene-lined stainless steel autoclave, which was sealed and heated at 180 ℃ for 10 hours, and naturally cooled to room temperature. The product was washed several times with ultrapure water and absolute ethanol, vacuum dried at 60 ℃ and finally annealed at 800 ℃ for 2 hours. The product obtained is expressed as Co1Fe1Mo1.2O NSs@NF。
Example 2
Co1Fe1Mo1.8Preparation of O NSs
First 1 mmol of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O), 1 mmol of iron nitrate nonahydrate (Fe (NO)3)2·9H2O), 5 mmol of urea and 4 mmol of NH4F, and 1.8 mmol of ammonium molybdate tetrahydrate ((NH)4)6Mo7O24·4H2O) was added to 36 mL of ultrapure water, stirred until completely dissolved, wherein Co (NO)3)2·6H2O，Fe(NO3)2·9H2O and (NH)4)6Mo7O24·4H2The molar weight of O, x/y/z, was 1:1: 1.8.
Then, the solution is used as a base materialThe nickel foam was transferred to a 50 mL teflon-lined stainless steel autoclave, sealed and heated at 180 ℃ for 10 hours, and allowed to cool to room temperature. The product was washed several times with ultrapure water and absolute ethanol, vacuum dried at 60 ℃ and finally annealed at 800 ℃ for 2 hours. The product obtained is expressed as Co1Fe1Mo1.8O NSs@NF。
Example 3
Co1Fe1Mo2.4Preparation of O NSs
First 1 mmol of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O), 1 mmol of iron nitrate nonahydrate (Fe (NO)3)2·9H2O), 5 mmol of urea and 4 mmol of NH4F, and 2.4 mmol of ammonium molybdate tetrahydrate ((NH)4)6Mo7O24·4H2O) was added to 36 mL of ultrapure water, stirred until completely dissolved, wherein Co (NO)3)2·6H2O，Fe(NO3)2·9H2O and (NH)4)6Mo7O24·4H2The molar weight of O, x/y/z, was 1:1: 2.4.
Then, this solution and foamed nickel as a base material were transferred to a 50 mL polytetrafluoroethylene-lined stainless steel autoclave, which was sealed and heated at 180 ℃ for 10 hours, and naturally cooled to room temperature. The product was washed several times with ultrapure water and absolute ethanol, vacuum dried at 60 ℃ and finally annealed at 800 ℃ for 2 hours. The product obtained is expressed as Co1Fe1Mo2.4O NSs@NF。
Example 4
Co1Fe1Mo2.2Preparation of O NSs
First 1 mmol of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O), 1 mmol of iron nitrate nonahydrate (Fe (NO)3)2·9H2O), 5 mmol of urea and 4 mmol of NH4F, and 2.2 mmol of ammonium molybdate tetrahydrate ((NH)4)6Mo7O24·4H2O) was added to 36 mL of ultrapure water, stirred until completely dissolved, whereinCo(NO3)2·6H2O，Fe(NO3)2·9H2O and (NH)4)6Mo7O24·4H2The molar weight of O, x/y/z, was 1:1: 2.2.
Then, this solution and the titanium plate as a base material were transferred to a 50 mL stainless steel autoclave lined with polytetrafluoroethylene, which was sealed and heated at 120 ℃ for 15 hours, and naturally cooled to room temperature. The product was washed several times with ultrapure water and absolute ethanol, dried under vacuum at 60 ℃ and finally annealed at 750 ℃ for 1 hour. The product obtained is expressed as Co1Fe1Mo2.2O NSs。
Example 5
Co1Fe1Mo0.8Preparation of O NSs
First 1 mmol of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O), 1 mmol of iron nitrate nonahydrate (Fe (NO)3)2·9H2O), 5 mmol of urea and 4 mmol of NH4F, and 0.8 mmol of ammonium molybdate tetrahydrate ((NH)4)6Mo7O24·4H2O) was added to 36 mL of ultrapure water, stirred until completely dissolved, wherein Co (NO)3)2·6H2O，Fe(NO3)2·9H2O and (NH)4)6Mo7O24·4H2The molar weight of O, x/y/z, was 1:1: 0.8.
Then, this solution and a carbon cloth as a base material were transferred to a 50 mL stainless steel autoclave lined with polytetrafluoroethylene, which was sealed and heated at 200 ℃ for 6 hours, and naturally cooled to room temperature. The product was washed several times with ultrapure water and absolute ethanol, vacuum dried at 60 ℃ and finally annealed at 850 ℃ for 3 hours. The product obtained is expressed as Co1Fe1Mo0.8O NSs。
Blank control example 1
First 1 mmol of cobalt nitrate hexahydrate (Co (NO)3)2·6H2O), 1 mmol of iron nitrate nonahydrate (Fe (NO)3)2·9H2O), 5 mmol of urea and 4 mmol of NH4F was added to 36 mL of ultrapure water and stirred until completely dissolved, wherein Co (NO)3)2·6H2O，Fe(NO3)2·9H2The molar weight of O x/y ratio was 1:1.
Then, this solution and foamed nickel as a base material were transferred to a 50 mL polytetrafluoroethylene-lined stainless steel autoclave, which was sealed and heated at 180 ℃ for 10 hours, and naturally cooled to room temperature. The product was washed several times with ultrapure water and absolute ethanol, vacuum dried at 60 ℃ and finally annealed at 800 ℃ for 2 hours. The resulting product is expressed as CoFeO NSs @ NF.
Comparative example 1
Commercial catalyst RuO2And Pt/C modified substrate material, and preparing a working electrode for comparison, wherein the working electrode comprises the following specific components:
mixing 8 mg of RuO2Or Pt/C and 100. mu.L Nafion (5%) solution were dispersed in 900. mu.L ethanol and sonicated for at least 30 minutes to form a homogeneous ink-like solution. About 130. mu.L of the solution was deposited on a base material (area 1X 1 cm)-2) And vacuum drying at 60 deg.c to obtain the working electrode. Ruo on substrate material2Or the loading of the Pt/C catalyst is about 1.0375 mg cm-2The supported substrate material is foamed nickel.
Example characterization and catalytic performance testing:
the performance of the prepared material is characterized by three electrodes (the prepared material is used as a working electrode, a saturated calomel electrode is used as a reference electrode, and a carbon rod electrode is used as a counter electrode), and a polarization curve (LSV) and Tafel curves (Tafel plots) are obtained. The three-electrode system is first placed in a 1M KOH solution at 1.05-1.9V: (vs.RHE) is scanned within the potential range by utilizing a linear sweep voltammetry method to obtain a polarization curve (LSV), and the OER performance of the prepared material is researched. To characterize the OER Properties of the materials prepared, with commercial RuO2The catalytic performance of (c) was compared.
Secondly, the three-electrode system is put into a 1M KOH solution at-0.85-0.2V: (vs.RHE) was scanned over the potential range using linear sweep voltammetry to obtain a polarization curve (LSV)And researching the HER performance of the prepared material. To characterize the HER performance of the prepared material, the catalytic performance was compared to that of commercial Pt/C.
FIG. 1 shows the prepared Co1Fe1Mo1.8Scanning electron microscopy images of O NSs.
The resulting dried samples were ultrasonically dispersed in an absolute ethanol solution for TEM characterization of the samples. FIG. 2 shows Co prepared in example 21Fe1Mo1.8And (4) according to a TEM image of O NSs, the performance of the prepared material is characterized by three electrodes (the prepared material is used as a working electrode, a saturated calomel electrode is used as a reference electrode, and a carbon rod electrode is used as a counter electrode), and a polarization curve (LSV) and Tafel curves (Tafel plots) are obtained. The three-electrode system is first placed in a 1M KOH solution at 1.05-1.9V: (vs.RHE) is scanned within the potential range by utilizing a linear sweep voltammetry method to obtain a polarization curve (LSV), and the OER performance of the prepared material is researched. FIG. 3 shows different materials and commercial RuO of the present invention2LSV diagram of (a). FIG. 4 shows different materials and commercial RuO's in the present invention2Tafel plots of (1).
Secondly, the three-electrode system is put into a 1M KOH solution at-0.85-0.2V: (vs.RHE) was scanned within the potential range using linear sweep voltammetry to obtain the polarization curve (LSV) and study the HER properties of the prepared material. FIG. 5 shows LSV plots of various materials and commercial Pt/C in accordance with the present invention. FIG. 6 shows Tafel plots of different materials and commercial Pt/C of the present invention.
As can be seen from the above performance tests, Co synthesized in the present invention1Fe1Mo1.8The O NSs can be used as a high-efficiency electrocatalyst in the electrochemical water decomposition process. Compared with the prior art, the ultrathin nanostructure of the invention ensures that the sample has large specific surface area, excellent charge transmission capability and a large number of active sites when being used as a catalytic electrode material, thereby ensuring that the prepared electrode material has better performance than commercial RuO2And OER and HER performance of Pt/C. At 10 mA cm-2Has a low overpotential of 210 mV and a dec of 32 mV-1Tafel slant ofRate superior to commercial RuO2Performance of (310 mV @10 mA cm)-2，123 mV dec-1) And has excellent stability after 24 hours. At the same time, Co1Fe1Mo1.8O NSs also showed excellent HER activity at 10 mA cm-2Has a low overpotential of 157 mV and has a strong long-term cycling durability after 24 hours. Co compares to most previously reported cobalt-based electrocatalysts1Fe1Mo1.8The enhanced catalytic activity of O NSs can be attributed to the strong electronic interaction between Co and Fe and the regulation and control of Mo on the number of surface active sites. The method has low cost and easy operation, and is favorable for further scientific research, popularization and application of the bifunctional electrocatalyst.
The above is a further detailed description of the present invention with reference to specific preferred embodiments, which should not be considered as limiting the invention to the specific embodiments described herein, but rather as a matter of simple derivation or substitution within the scope of the invention as defined by the appended claims, it will be understood by those skilled in the art to which the invention pertains.
Claims (4)
1. A preparation method of a molybdenum-doped cobalt iron oxide nanosheet bifunctional electrocatalyst is characterized by specifically comprising the following steps of:
a) mixing Co (NO)3)2·6H2O，Fe(NO3)2·9H2O, urea, NH4F and (NH)4)6Mo7O24·4H2Adding O into water, stirring until completely dissolving to form solution, wherein Co (NO)3)2·6H2O，Fe(NO3)2·9H2O and (NH)4)6Mo7O24·4H2The molar weight of O is 1:1:0.001-1:1: 3;
b) transferring the solution and the substrate material into an autoclave, sealing and heating at the temperature of 120-;
c) washing the product obtained in the step b for several times, drying in vacuum, and finally heating and annealing to obtain a product represented as CoxFeyMozONSs;
the heating annealing in the step c is annealing at the temperature of 750-850 ℃ for 1-3 h;
the Co (NO)3)2·6H2O，Fe(NO3)2·9H2O, urea, NH4F and (NH)4)6Mo7O24·4H2The molar ratio of O is 1:1:5:4:0.001-1:1:5:4: 3.
2. The preparation method of the molybdenum-doped cobalt iron oxide nanosheet bifunctional electrocatalyst according to claim 1, wherein the base material is any one of foamed nickel, carbon paper, carbon cloth, and titanium sheet.
3. The method for preparing a bifunctional electrocatalyst with molybdenum doped with cobalt-iron oxide nanosheets, as claimed in claim 1, wherein the autoclave is a stainless steel autoclave lined with polytetrafluoroethylene.
4. The method for preparing the molybdenum-doped cobalt iron oxide nanosheet bifunctional electrocatalyst according to claim 1, wherein in step c the product is washed with ultrapure water and anhydrous ethanol.
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