CN116377482A - Bimetallic electrode material and preparation method and application thereof - Google Patents
Bimetallic electrode material and preparation method and application thereof Download PDFInfo
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- CN116377482A CN116377482A CN202310637715.7A CN202310637715A CN116377482A CN 116377482 A CN116377482 A CN 116377482A CN 202310637715 A CN202310637715 A CN 202310637715A CN 116377482 A CN116377482 A CN 116377482A
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- molybdenum
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- 239000007772 electrode material Substances 0.000 title claims abstract description 36
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 163
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 71
- 239000006260 foam Substances 0.000 claims abstract description 61
- 238000000034 method Methods 0.000 claims abstract description 43
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000004202 carbamide Substances 0.000 claims abstract description 38
- 150000004767 nitrides Chemical class 0.000 claims abstract description 28
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001301 oxygen Substances 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 54
- 239000000758 substrate Substances 0.000 claims description 49
- 238000010438 heat treatment Methods 0.000 claims description 38
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 32
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 claims description 30
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 29
- 239000000463 material Substances 0.000 claims description 28
- 238000005406 washing Methods 0.000 claims description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- 229910052750 molybdenum Inorganic materials 0.000 claims description 20
- 239000011733 molybdenum Substances 0.000 claims description 20
- 239000011259 mixed solution Substances 0.000 claims description 18
- 238000009210 therapy by ultrasound Methods 0.000 claims description 13
- 239000012298 atmosphere Substances 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 229910052573 porcelain Inorganic materials 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 238000004519 manufacturing process Methods 0.000 claims description 9
- PDKHNCYLMVRIFV-UHFFFAOYSA-H molybdenum;hexachloride Chemical group [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mo] PDKHNCYLMVRIFV-UHFFFAOYSA-H 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 5
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 3
- 239000003960 organic solvent Substances 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 9
- 238000001308 synthesis method Methods 0.000 abstract description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 238000000137 annealing Methods 0.000 description 16
- 238000010586 diagram Methods 0.000 description 12
- 238000009826 distribution Methods 0.000 description 11
- 238000003756 stirring Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 229910021642 ultra pure water Inorganic materials 0.000 description 6
- 239000012498 ultrapure water Substances 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 238000004140 cleaning Methods 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 230000003749 cleanliness Effects 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000010998 test method Methods 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000013256 coordination polymer Substances 0.000 description 2
- 229920001795 coordination polymer Polymers 0.000 description 2
- NLPVCCRZRNXTLT-UHFFFAOYSA-N dioxido(dioxo)molybdenum;nickel(2+) Chemical compound [Ni+2].[O-][Mo]([O-])(=O)=O NLPVCCRZRNXTLT-UHFFFAOYSA-N 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000005121 nitriding Methods 0.000 description 2
- 150000002905 orthoesters Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical group [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910000474 mercury oxide Inorganic materials 0.000 description 1
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- -1 transition Metal Nitrides Chemical class 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- C25B11/02—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form
- C25B11/03—Electrodes; Manufacture thereof not otherwise provided for characterised by shape or form perforated or foraminous
- C25B11/031—Porous electrodes
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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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
The invention provides a bimetal electrode material, a preparation method and application thereof. The invention adopts a one-step synthesis method to anneal Mo source, ni foam and urea at high temperature in one step, so that bimetallic nitride Ni grows on the nickel foam piece 2 Mo 3 The N nano particles realize higher oxygen evolution reaction activity and simplify the complexity of the process.
Description
Technical Field
The invention relates to the technical field of electrolytic hydrogen production, in particular to a bimetal electrode material and a preparation method and application thereof.
Background
Since hydrogen has a specific high mass specific energy density (142 MJ/kg), is a promising energy carrier, utilizes renewable energy with high efficiency, and can realize zero carbon emission, electrochemical decomposition of water is considered to be a clean and efficient hydrogen production pathway, water decomposition includes Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER), four electrons (4 OH − →2H 2 O+O 2 +4 e− ) Iridium-based and ruthenium-based materials are typical OER catalysts, which are kinetically slow with respect to the two electrons involved in HER, requiring large overpotential values, but their high cost and scarcity limit their widespread use. Therefore, development of low cost and abundant materials to replace OER electrocatalysts for large scale diffusion of water decomposition systems is currently the primary task, wherein alkaline water hydrogen production has the advantage of being unable to replace in low cost hydrogen production, but the main problem faced is excessive electrolysis energy consumption, and the adoption of high performance electrodes is an effective means for reducing energy consumption.
Materials containing transition metals, such as transition metal oxides, transition Metal Nitrides (TMNs) and transition metal oxynitrides, have higher OER activity. Wherein, various single metal TMNs including Ni (Ni 3 N，Co 4 N, hfN and Mn 3 N 2 ) Has been studied as a low cost electrocatalyst. TMN has physical hardness, chemical stability, conductivity and unique electronic structure, and has great development potential. However, these monometal TMNs still exhibit limited OER performance.
Therefore, the invention discloses a novel bimetal electrode material which is a technical problem to be solved in the prior art.
Disclosure of Invention
In view of this, the present invention aims to solve the technical problem of low activity of electrode materials.
The first aspect of the invention provides a bimetallic electrode material.
The second aspect of the invention provides a preparation method of the bimetal electrode material.
The third aspect of the invention provides an application of the bimetallic electrode material.
In a fourth aspect, the invention provides a method of electrolyzing water.
Specifically, the invention is realized by the following technical scheme:
the bimetal electrode material provided by the invention comprises a foam nickel substrate and nickel-molybdenum bimetal nitride growing on the foam nickel substrate.
Compared with a single metal catalyst, the bimetallic electrode material provided by the invention has the advantages that more active sites exist on the surface of the electrode and the electronic conductivity is enhanced through the synergistic effect between the nickel metal and the molybdenum metal, so that higher catalytic activity is realized. In addition, since the nickel-molybdenum bimetal nitride is generated on the surface of the foam nickel substrate, the Ni foam serves as a Ni source, and thus, no Ni precursor is added, and the manufacturing method is simple, economical and environment-friendly.
In the technical scheme, the nickel-molybdenum bimetallic nitride is nano-particles.
In the technical scheme, the nickel-molybdenum bimetal nitride is nano particles, for example, the particle size of the nickel-molybdenum bimetal nitride is more than or equal to 1 nanometer and less than or equal to 100 nanometers, so that the specific surface area of the nickel-molybdenum bimetal nitride can be increased, more active sites are exposed, and the catalytic activity is improved.
In the technical scheme, in the nickel-molybdenum bimetallic nitride, the molar ratio of nickel element to molybdenum element to nitrogen element is 2:3:1, namely, the atomic ratio of nickel element, molybdenum element and nitrogen element is 2:3:1, at this time, the chemical formula of the nickel-molybdenum bimetallic nitride is Ni 2 Mo 3 N。
In a second aspect, the invention provides a method for preparing a bimetallic material, comprising contacting a mixed solution comprising a molybdenum source and urea with a foamed nickel substrate, and performing a heat treatment.
The preparation method of the bimetal material provided by the invention specifically comprises the steps of contacting a mixed solution containing a molybdenum source and urea with a foam nickel substrate and performing heat treatment, so that nickel-molybdenum bimetal nitride can be grown on the foam nickel substrate. The invention adopts a one-step synthesis method to anneal Mo source, ni foam and urea at high temperature in one step, so that bimetallic nitride Ni grows on the nickel foam piece 2 Mo 3 N nanoparticles, thus compared with the prior art of synthesizing nickel molybdenum oxide first and then passing NH 3 The method of nitriding synthesis simplifies the complexity of the process, saves the cost, simultaneously only needs one-step annealing in the whole process, and does not need two or more steps of annealing process, thus greatly improving the preparation efficiency.
In the above technical scheme, the heat treatment comprises lasting for 1-10 hours at a temperature of 550-650 ℃.
In the technical scheme, the heat treatment can be carried out at a temperature of 550 ℃ or more and 650 ℃ or less for 1 hour or more and 5 hours or less, so that the smooth progress of the reaction can be ensured, and the reaction rate can be ensured. Meanwhile, the reactants can be fully reacted, and the reaction rate can be prevented from being reduced due to too long reaction time.
In the above technical scheme, the heat treatment comprises the continuous 2-5 hours at the temperature of 580-620 ℃.
In this embodiment, the heat treatment may be carried out at a temperature of 580 ℃ or higher and 620 ℃ or lower for 2 hours or more and 5 hours or less, so that the reaction efficiency can be further ensured.
In the technical scheme, after the heat treatment is continued for 1-10 hours at the temperature of 550-650 ℃, the heat treatment also comprises cooling at a rate of more than or equal to 3.0 ℃/min and less than or equal to 4.0 ℃/min.
In the technical scheme, in the annealing process, the cooling speed is more than or equal to 3.0 ℃/min and less than or equal to 4.0 ℃/min, so that the surface structure of the synthesized nickel-molybdenum nitride is uniform, and the preparation efficiency can be ensured.
In the above technical scheme, the heat treatment is performed under an inert gas atmosphere. Further, the heat treatment was performed under a nitrogen atmosphere.
In the technical scheme, the heat treatment is performed under the nitrogen atmosphere, so that nitrogen elements can be provided for the synthesized bimetal electrode material, the nickel-molybdenum bimetal nitride is synthesized, and the bimetal electrode material is synthesized by replacing toxic ammonia gas with inert nitrogen, so that the environment is protected, and the development direction of society is met.
In the technical scheme, the molar ratio of urea to molybdenum source is (1-5): 1.
in the technical scheme, the molar ratio of the urea to the molybdenum source is more than or equal to 1 and less than or equal to 5, so that the urea and the molybdenum source can be ensured to fully react, incomplete waste of materials in the reaction is avoided, and the reaction rate can be ensured. Further, the molar ratio of urea to molybdenum source is 1 or more and 2 or less.
In the above technical scheme, the molybdenum source is molybdenum chloride.
In the above technical solution, the mixed solution further includes an organic solvent.
In the above technical solution, the mixed solution further includes ethanol.
In the technical schemes, molybdenum chloride is used as a molybdenum source, and molybdenum chloride and alcohol are subjected to partial violent reaction to release most of chlorine as HCl and form corresponding metal orthoesters, and then a soluble complex and a coordination polymer are formed with urea, so that the nickel-molybdenum bimetallic nitride can be obtained.
In the above technical solution, the heat treatment is performed in an alumina porcelain boat.
In the technical scheme, the heat treatment is performed in the alumina porcelain boat, so that the heat treatment efficiency can be improved, and the temperature and the like of the heat treatment can be accurately controlled.
In the technical scheme, the preparation method further comprises the step of washing the foam nickel substrate before the mixed solution is contacted with the foam nickel substrate.
In the technical scheme, the foam nickel substrate is washed before the mixed solution is contacted with the foam nickel substrate, so that the surface of the foam nickel substrate can be cleaned, and the reaction rate is prevented from being influenced by impurities on the surface of the foam nickel substrate.
In the above technical scheme, the washing treatment includes ultrasonic treatment with at least one selected from acetone, ethanol and water.
In the technical scheme, the washing treatment comprises ultrasonic treatment by adopting at least one selected from acetone, ethanol and water, and through the ultrasonic treatment, the cleaning efficiency of the foam nickel substrate can be improved, and the preparation efficiency of the product is further improved.
In the technical scheme, the ultrasonic treatment time is 10-40 minutes.
In the technical scheme, the ultrasonic treatment time is more than or equal to 10 minutes and less than or equal to 40 minutes, so that the ultrasonic treatment time is controlled, the treatment is more thorough, and the cleanliness of the foam nickel substrate is improved.
In the technical scheme, the cleaning time of washing the foam nickel substrate by acetone is more than or equal to 5min and less than or equal to 10min; washing the foam nickel substrate by ethanol for more than or equal to 5min and less than or equal to 10min; the washing time of washing the foam nickel substrate by purified water is more than or equal to 5min and less than or equal to 10min.
In the technical scheme, the cleaning time of acetone, ethanol and water is controlled, so that the cleanliness of the foam nickel substrate can be ensured, the overlong time is avoided, and the preparation efficiency is low.
The third aspect of the invention provides an application of the bimetallic electrode material provided by the first aspect of the invention or the bimetallic electrode material prepared by the preparation method of the bimetallic electrode material provided by the second aspect of the invention in preparing hydrogen and/or oxygen by electrolyzing water.
In a fourth aspect, the present invention provides a method of electrolyzing water, comprising electrolyzing water in the presence of the bimetallic electrode material provided in the first aspect of the present invention or the bimetallic electrode material prepared by the method of preparing the bimetallic electrode material provided in the second aspect of the present invention.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are required to be used in the description of the embodiments or the related art will be briefly described below, and it will be apparent to those skilled in the art that other drawings can be obtained from these drawings without inventive effort.
FIG. 1 is a schematic flow chart of a method for preparing a bimetal material according to an embodiment of the present invention;
fig. 2 is a schematic flow chart of a preparation method of a bimetal material according to a second embodiment of the present invention;
fig. 3 is a schematic flow chart of a preparation method of a bimetal material according to a third embodiment of the present invention;
fig. 4 is a flow chart of a preparation method of a bimetal material according to a fourth embodiment of the present invention;
fig. 5 is a schematic flow chart of a preparation method of a bimetal material provided in a fifth embodiment of the present invention;
fig. 6 is a schematic flow chart of a preparation method of a bimetal material provided in a sixth embodiment of the present invention;
FIG. 7 is an SEM image of a nickel-molybdenum nitride electrode surface according to one embodiment of the present invention;
FIG. 8 is a diagram showing a distribution of nickel on the surface of a nickel-molybdenum nitride electrode according to an embodiment of the present invention;
FIG. 9 is a diagram showing a molybdenum element distribution on the surface of a nickel-molybdenum nitride electrode according to an embodiment of the present invention;
fig. 10 is a diagram showing a nitrogen element distribution on the surface of a nickel-molybdenum nitride electrode according to an embodiment of the present invention.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention, and it is apparent that the described embodiments are some embodiments of the present invention, but not all embodiments of the present invention. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The bimetal electrode material provided by the embodiment of the first aspect of the invention comprises a foam nickel substrate and nickel-molybdenum bimetal nitride growing on the foam nickel substrate.
Compared with a single metal catalyst, the bimetallic electrode material provided by the embodiment has the advantages that more active sites exist on the surface of the electrode and the electronic conductivity is enhanced through the synergistic effect between the nickel metal and the molybdenum metal, so that higher catalytic activity is realized. In addition, since the nickel molybdenum bimetal nitride of the present invention is generated on the surface of the foamed nickel substrate, the Ni foam serves as a Ni source, and thus no Ni precursor is added, and thus, the manufacturing method is simple, economical and environment-friendly.
In the above embodiments, the nickel molybdenum bimetal nitride is a nanoparticle.
In this embodiment, the nickel-molybdenum bimetal nitride is a nanoparticle, for example, the particle size of the nickel-molybdenum bimetal nitride is 1 nm or more and 100 nm or less, so that the specific surface area of the nickel-molybdenum bimetal nitride can be increased, more active sites are exposed, and the catalytic activity is improved.
In the above examples, the molar ratio of nickel element, molybdenum element and nitrogen element in the nickel molybdenum bimetal nitride is 2:3:1.
embodiments of the second aspect of the present invention provide a method for preparing a bimetal material, mainly using a one-step method to grow a bimetal nitride Ni on a foam nickel substrate 2 Mo 3 N nanoparticles. Specifically, the invention adopts a one-pot method to make Mo source, ni foam and urea under the high temperature condition and N 2 Carrying out heat treatment under inert gas atmosphere to obtain the product, wherein during annealing, inert N 2 The gas replaces the toxic ammonia gas. In addition, since the Ni foam acts as a Ni source, no Ni precursor is added. Thus, this preparation method is simple, economical and environment-friendly.
The following examples are presented to illustrate the preparation of the bimetallic material of the present invention.
Example 1
Referring to fig. 1, the embodiment provides a preparation method of a bimetal material, which includes the following steps:
s102: ultrasonic washing the foam nickel with acetone, ethanol and ultrapure water for 20 minutes;
s104: 3mmol of MoCl 5 Dissolving in 2.53mL of ethanol, adding 3mmol of urea (molar ratio of urea/Mo=1) to the solution, stirring until urea is completely dissolved, transferring the solution onto an alumina porcelain boat containing nickel foam pieces, and stirring under flowing N 2 Annealing at 600℃for 3h (cooling rate 3.3℃/min) under an atmosphere (100 sccm).
The bimetal material is tested by adopting a linear volt-ampere scanning test method, a three-electrode system is used for testing, the working electrode is the bimetal material prepared by the embodiment, the reference electrode is mercury/mercury oxide, the counter electrode is a platinum mesh electrode, the electrolyte adopts lmol/L potassium hydroxide solution, and the test conditions are as follows: the voltage interval is + -5 mV under open circuit potential, the scanning frequency is 10Hz-10000Hz, the scanning range is 0.1V-0.9V, the scanning speed is 0.005V/s, under the test environment, the oxygen evolution overpotential of the bimetallic electrode prepared by the bimetallic electrode preparation method provided by the embodiment in 1M KOH is 336 mV/50 mA cm -2 ，392mV/100 mA·cm -2 The method comprises the steps of carrying out a first treatment on the surface of the Electrochemical activity specific area of 347 mF/cm 2 。
As shown in FIG. 7, the SEM image of the bimetal material prepared in this example shows that according to FIG. 7, the microstructure of the bimetal electrode material synthesized in this example is Ni 2 Mo 3 N nano particles, and Ni 2 Mo 3 The N nano particles are uniformly dispersed on the foam nickel substrate.
The bimetallic material prepared in this example has a distribution diagram of nickel element under a microscope, a distribution diagram of molybdenum element, a distribution diagram of nitrogen element, a distribution diagram of FIG. 8, a distribution diagram of molybdenum element, a distribution diagram of nitrogen element, a distribution diagram of FIG. 10, a distribution diagram of three elements, namely Ni, as can be clearly seen from the electron microscope diagrams of FIG. 8 to FIG. 10, wherein 250 μm represents the scale bar 2 Mo 3 N particles are uniformly distributed, and the catalytic effect of the uniform particles can be greatly improved.
Example two
Referring to fig. 2, the embodiment provides a preparation method of a bimetal material, which includes the following steps:
s202: ultrasonic washing the foam nickel with acetone, ethanol and ultrapure water for 20 minutes;
s204: 3mmol of MoCl 5 Dissolving in 2.53mL of ethanol, adding 4.5mmol of urea (molar ratio urea/Mo=1.5) to the solution, stirring until the urea is completely dissolved, transferring the solution onto an alumina porcelain boat containing nickel foam flakes, and stirring under flowing N 2 Annealing at 600℃for 3h (cooling rate 3.3℃/min) under an atmosphere (100 sccm).
The same test method as in example one, the bimetallic electrode prepared in this example has an oxygen evolution overpotential of 357 mV/50 mA cm in 1M KOH -2 ，412 mV/100 mA·cm -2 The method comprises the steps of carrying out a first treatment on the surface of the Electrochemical activity specific area of 302mF/cm 2 。
Embodiment III:
referring to fig. 3, the embodiment provides a preparation method of a bimetal material, which includes the following steps:
s302: ultrasonic washing the foam nickel with acetone, ethanol and ultrapure water for 20 minutes;
s304: 3mmol of MoCl 5 Dissolving in 2.53mL of ethanol, adding 6mmol of urea (molar ratio urea/Mo=2) to the solution, stirring until urea is completely dissolved, transferring the solution onto an alumina porcelain boat containing foam nickel flakes, and stirring under flowing N 2 Annealing at 600℃for 3h (cooling rate 3.3℃/min) under an atmosphere (100 sccm).
The same test method as in example one shows that the bimetallic electrode prepared in this example has an oxygen evolution overpotential of 345 mV/50 mA cm in 1M KOH -2 ，405 mV/100 mA·cm -2 The method comprises the steps of carrying out a first treatment on the surface of the Electrochemical activity specific area of 324 mF/cm 2 。
Example IV
Referring to fig. 4, the embodiment provides a preparation method of a bimetal material, which includes the following steps:
s402: and (3) contacting the mixed solution containing the molybdenum source and urea with the foam nickel substrate for heat treatment.
The preparation method of the bimetal material provided by the invention specifically comprises the steps of contacting a mixed solution containing a molybdenum source and urea with a foam nickel substrate and performing heat treatment, so that nickel-molybdenum bimetal nitride can be grown on the foam nickel substrate. The invention adopts a one-step synthesis method to anneal Mo source, ni foam and urea at high temperature in one step, so that bimetallic nitride Ni grows on the nickel foam piece 2 Mo 3 N nanoparticles, thus compared with the prior art of synthesizing nickel molybdenum oxide first and then passing NH 3 The method of nitriding synthesis simplifies the complexity of the process, saves the cost, simultaneously only needs one-step annealing in the whole process, and does not need two or more steps of annealing process, thus greatly improving the preparation efficiency.
In the above examples, the heat treatment includes a duration of 1 to 10 hours at a temperature of 550 ℃ to 650 ℃.
In this embodiment, the heat treatment may be a continuous heat preservation at a temperature of 550 ℃ or higher and 650 ℃ or lower for 1 hour or more and 5 hours or less, so that smooth progress of the reaction and a reaction rate can be ensured. Meanwhile, the reactants can be fully reacted, and the reaction rate can be prevented from being reduced due to too long reaction time.
In the above examples, the heat treatment includes a duration of 2 to 5 hours at a temperature of 580 to 620 ℃.
In this embodiment, the heat treatment may be continuous at a temperature of 580 ℃ or higher and 620 ℃ or lower for 2 hours or higher and 5 hours or lower, so that the reaction efficiency can be further ensured.
In the above embodiment, after sustaining at a temperature of 550 ℃ to 650 ℃ for 1 to 10 hours, the heat treatment further includes cooling at a rate of 3.0 ℃/min or more and 4.0 ℃/min or less.
In the embodiment, in the annealing process, the cooling speed is more than or equal to 3.0 ℃/min and less than or equal to 4.0 ℃/min, so that the surface structure of the synthesized nickel-molybdenum nitride is uniform, and the preparation efficiency can be ensured.
In the above-described embodiment, the heat treatment is performed under an inert gas atmosphere.
In the embodiment, the heat treatment is performed under the inert gas atmosphere, so that nitrogen element can be provided for the synthesized bimetal electrode material, nickel-molybdenum bimetal nitride is synthesized, and the bimetal electrode material is synthesized by replacing toxic ammonia gas with inert nitrogen gas, so that the environment is protected, and the development direction of society is met.
In the above examples, the molar ratio of urea to molybdenum source is (1-5): 1.
in the embodiment, the molar ratio of the urea to the molybdenum source is greater than or equal to 1 and less than or equal to 5, so that the urea and the molybdenum source can be ensured to fully react, incomplete waste of materials in the reaction is avoided, and the reaction rate can be ensured. Further, the molar ratio of urea to molybdenum source is 1 or more and 2 or less.
In the above embodiment, the molybdenum source is molybdenum chloride.
In the above embodiment, the organic solvent is also included in the mixed solution.
In the above embodiment, ethanol is also included in the mixed solution.
In the technical schemes, molybdenum chloride is used as a molybdenum source, and molybdenum chloride and alcohol are subjected to partial violent reaction to release most of chlorine as HCl and form corresponding metal orthoesters, and then a soluble complex and a coordination polymer are formed with urea, so that the nickel-molybdenum bimetallic nitride can be obtained.
In the above embodiment, the heat treatment is performed in an alumina porcelain boat.
In this embodiment, the heat treatment is performed in the alumina porcelain boat, so that the efficiency of the heat treatment can be improved, while the temperature and the like of the heat treatment can be controlled more precisely.
In the above embodiment, the preparation method further comprises subjecting the foamed nickel substrate to a washing treatment before the mixed solution is contacted with the foamed nickel substrate.
In this embodiment, the foam nickel substrate is subjected to a washing treatment before the mixed solution is brought into contact with the foam nickel substrate, so that the surface of the foam nickel substrate can be cleaned, and impurities on the surface of the foam nickel substrate are prevented from affecting the reaction rate.
In the above embodiment, the washing treatment includes ultrasonic treatment with at least one selected from the group consisting of acetone, ethanol, and water.
In this embodiment, the washing treatment includes ultrasonic treatment using at least one selected from the group consisting of acetone, ethanol and water, by which the washing efficiency of the foam nickel substrate can be improved, thereby improving the production efficiency of the product.
In the above examples, the time of the ultrasonic treatment was 10 to 40 minutes.
In this embodiment, the time of the ultrasonic treatment is 10 minutes or more and 40 minutes or less, and the ultrasonic treatment time is controlled, so that the treatment is more thorough, and the cleanliness of the foam nickel substrate is improved.
In the above embodiments, the cleaning time of washing the foam nickel substrate with acetone is 5min or more and 10min or less; washing the foam nickel substrate by ethanol for more than or equal to 5min and less than or equal to 10min; the washing time of washing the foam nickel substrate by purified water is more than or equal to 5min and less than or equal to 10min.
In the embodiment, the cleaning time of the acetone, the ethanol and the water is controlled, so that the cleanliness of the foam nickel substrate can be ensured, the overlong time is avoided, and the preparation efficiency is low.
Example five
Referring to fig. 5, the embodiment provides a preparation method of a bimetal material, which includes the following steps:
s502: ultrasonic washing the foam nickel with acetone, ethanol and ultrapure water for 20 minutes;
s504: 3mmol of MoCl 5 Dissolving in 2.53mL of ethanol, adding 6mmol of urea (molar ratio urea/Mo=2) to the solution, stirring until urea is completely dissolved, transferring the solution onto an alumina porcelain boat containing nickel foam flakes, and stirring under flowing N 2 Annealing at 550℃for 3h (cooling rate 3.3℃/min) under an atmosphere (100 sccm).
Ni prepared in this example 2 Mo 3 N is compared with Ni prepared in example one 2 Mo 3 N has low crystallinity, and the oxygen evolution overpotential of the bimetallic electrode prepared in the embodiment in 1M KOH is 378 mV/50 mA cm -2 ，465 mV/100 mA·cm -2 The method comprises the steps of carrying out a first treatment on the surface of the The electrochemical activity specific area is 276 mF/cm 2 。
Example six
Referring to fig. 6, the embodiment provides a preparation method of a bimetal material, which includes the following steps:
s602: ultrasonic washing the foam nickel with acetone, ethanol and ultrapure water for 20 minutes;
s604: 3mmol of MoCl 5 Dissolving in 2.53mL of ethanol, adding 6mmol of urea (molar ratio urea/Mo=2) to the solution, stirring until urea is completely dissolved, transferring the solution onto an alumina porcelain boat containing nickel foam flakes, and stirring under flowing N 2 Annealing at 650℃for 3h (cooling rate 3.3℃/min) under an atmosphere (100 sccm).
The bimetallic material prepared in this example, except for Ni formation 2 Mo 3 In addition to N, mo is also produced 2 N, the same test method as in example one, the oxygen evolution overpotential of the bimetallic electrode prepared in this example in 1M KOH is 365 mV/50 mA cm -2 ，442 mV/100 mA·cm -2 The method comprises the steps of carrying out a first treatment on the surface of the Electrochemical activity specific area of 279 mF/cm 2 。
The key points of the preparation method of the invention include the following points:
1) The substrate of the one-step synthesis method is foam nickel, and the pretreatment modes are ultrasonic washing for 20 minutes by using acetone, ethanol and ultrapure water.
2) The reaction solution was 3mmol of MoCl 5 3 to 6mmol of urea in ethanol.
4) The heat treatment conditions are that N flows 2 Annealing at 600℃for 3h (annealing rate 3.3 ℃/min) under atmosphere (100 sccm).
5) The substrate is foam nickel, and the solution is 3mmol MoCl 5 4.5mmol of urea was dissolved in 2.53mL of ethanol,the heat treatment conditions are that N flows 2 Annealing at 600℃for 3h (annealing rate 3.3 ℃/min) under an atmosphere (100 sccm), the oxygen evolution overpotential of the electrode in 1M KOH being 357 mV/50 mA cm -2 ，412 mV/100 mA·cm -2 The method comprises the steps of carrying out a first treatment on the surface of the Electrochemical activity specific area of 302mF/cm 2 。
6) The microstructure of the electrode synthesized under the condition of 5) is Ni 2 Mo 3 N nano particles are uniformly dispersed on the foam nickel substrate.
An embodiment of a third aspect of the present invention provides an application of the bimetal electrode material provided by the embodiment of the first aspect of the present invention or the bimetal electrode material prepared by the preparation method of the bimetal electrode material provided by the embodiment of the second aspect of the present invention in preparing hydrogen and/or oxygen by water electrolysis.
An embodiment of a fourth aspect of the present invention provides a method for electrolyzing water, including electrolyzing water in the presence of the bimetal electrode material provided in the embodiment of the first aspect of the present invention or the bimetal electrode material prepared by the method for preparing the bimetal electrode material provided in the embodiment of the second aspect of the present invention.
The foregoing is merely exemplary of embodiments of the present invention to enable those skilled in the art to understand or practice the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (21)
1. A bi-metallic electrode material comprising a foamed nickel substrate and a nickel molybdenum bi-metallic nitride grown on the foamed nickel substrate.
2. The bi-metallic electrode material of claim 1, wherein the nickel molybdenum bi-metallic nitride is a nanoparticle.
3. The bimetal electrode material of claim 1, wherein the molar ratio of the nickel element, the molybdenum element and the nitrogen element in the nickel-molybdenum bimetal nitride is 2:3:1.
4. a preparation method of a bimetallic material is characterized by comprising the step of contacting a mixed solution containing a molybdenum source and urea with a foam nickel substrate and performing heat treatment.
5. The method of claim 4, wherein the heat treatment comprises a duration of 1 to 10 hours at a temperature of 550 ℃ to 650 ℃.
6. The method of claim 4, wherein the heat treatment comprises a duration of 2-5 hours at a temperature of 580-620 ℃.
7. The method according to claim 5, wherein the heat treatment further comprises cooling at a rate of 3.0 ℃/min or more and 4.0 ℃/min or less after continuing for 1 to 10 hours at a temperature of 550 ℃ to 650 ℃.
8. The method according to claim 4, wherein the heat treatment is performed under an inert gas atmosphere.
9. The method according to claim 4, wherein the heat treatment is performed under a nitrogen atmosphere.
10. The method according to claim 4, wherein the molar ratio of urea to molybdenum source in the mixed solution is (1-5): 1.
11. the method according to claim 4, wherein the molar ratio of urea to molybdenum source in the mixed solution is (1-2): 1.
12. the method of claim 4, wherein the molybdenum source is molybdenum chloride.
13. The method according to claim 4, wherein the mixed solution further comprises an organic solvent.
14. The method according to claim 4, wherein the mixed solution further comprises ethanol.
15. The method of claim 4, wherein the heat treatment is performed in an alumina porcelain boat.
16. The method of preparing according to claim 4, further comprising subjecting the foamed nickel substrate to a washing treatment before the mixed solution is contacted with the foamed nickel substrate.
17. The method according to claim 16, wherein the washing treatment comprises ultrasonic treatment with at least one selected from the group consisting of acetone, ethanol, and water.
18. The method of claim 17, wherein the time of the ultrasonic treatment is 10 to 40 minutes.
19. The method of manufacturing according to claim 16, wherein the washing treatment comprises:
washing the foam nickel substrate by acetone for more than or equal to 5min and less than or equal to 10min;
washing the foam nickel substrate by ethanol for more than or equal to 5min and less than or equal to 10min;
and washing the foam nickel substrate by purified water for more than or equal to 5min and less than or equal to 10min.
20. Use of a bimetallic electrode material according to any one of claims 1 to 3 or obtained by a method of preparation according to any one of claims 4 to 19 for the preparation of hydrogen and/or oxygen.
21. A method of electrolyzing water, characterized by comprising electrolyzing water in the presence of the bimetal electrode material of any one of claims 1 to 3 or the bimetal electrode material obtained by the production method of any one of claims 4 to 19.
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| CN114182289A (en) * | 2021-12-14 | 2022-03-15 | 黑龙江大学 | Preparation method of molybdenum-nickel-based nitride for organic electro-oxidative coupling hydrogen evolution |
| CN115161700A (en) * | 2022-08-26 | 2022-10-11 | 青岛科技大学 | In-situ preparation and application of two-dimensional graphene-like nickel-molybdenum nitride composite material |
| CN115323390A (en) * | 2022-07-30 | 2022-11-11 | 中北大学 | Foam nickel loaded nitrogen-phosphorus co-doped NiMo-based composite catalyst and preparation method and application thereof |
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| CN114182289A (en) * | 2021-12-14 | 2022-03-15 | 黑龙江大学 | Preparation method of molybdenum-nickel-based nitride for organic electro-oxidative coupling hydrogen evolution |
| CN115323390A (en) * | 2022-07-30 | 2022-11-11 | 中北大学 | Foam nickel loaded nitrogen-phosphorus co-doped NiMo-based composite catalyst and preparation method and application thereof |
| CN115161700A (en) * | 2022-08-26 | 2022-10-11 | 青岛科技大学 | In-situ preparation and application of two-dimensional graphene-like nickel-molybdenum nitride composite material |
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