CN114592208B - Preparation method of nitrogen-doped graphitized modified electrode - Google Patents
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- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 207
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 100
- 229910052751 metal Inorganic materials 0.000 claims abstract description 53
- 239000002184 metal Substances 0.000 claims abstract description 53
- 238000004140 cleaning Methods 0.000 claims abstract description 45
- 239000000758 substrate Substances 0.000 claims abstract description 39
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 28
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 25
- 230000007797 corrosion Effects 0.000 claims abstract description 23
- 238000005260 corrosion Methods 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 20
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 14
- 238000005087 graphitization Methods 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 10
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 9
- 238000012986 modification Methods 0.000 claims abstract description 9
- 230000004048 modification Effects 0.000 claims abstract description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 claims abstract description 7
- 239000007787 solid Substances 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- 238000004729 solvothermal method Methods 0.000 claims abstract description 6
- 239000002344 surface layer Substances 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 3
- 239000006260 foam Substances 0.000 claims description 34
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 33
- 239000010410 layer Substances 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000012153 distilled water Substances 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 239000004519 grease Substances 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 10
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical group [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 7
- 239000011609 ammonium molybdate Substances 0.000 claims description 7
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 7
- 229940010552 ammonium molybdate Drugs 0.000 claims description 7
- 238000011049 filling Methods 0.000 claims description 7
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229920000877 Melamine resin Polymers 0.000 claims description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 239000002041 carbon nanotube Substances 0.000 claims description 5
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 235000003270 potassium fluoride Nutrition 0.000 claims description 5
- 239000011698 potassium fluoride Substances 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims description 2
- 239000002923 metal particle Substances 0.000 claims description 2
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 10
- 238000005406 washing Methods 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 8
- 238000004506 ultrasonic cleaning Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003054 catalyst 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
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 229910005809 NiMoO4 Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 241001494479 Pecora Species 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
Classifications
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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
-
- 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
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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)
- Battery Electrode And Active Subsutance (AREA)
Abstract
The application discloses a preparation method of a nitrogen-doped graphitized modified electrode, which comprises the steps of carrying out surface cleaning treatment on a metal nickel substrate to obtain a clean metal nickel substrate; subjecting the metal nickel substrate after the surface cleaning treatment to a solvothermal reaction-based corrosion treatment in a mixed solution containing molybdate and fluoride; carrying out gas-solid reaction on the metal nickel substrate subjected to corrosion treatment under the protection of inert atmosphere, and carrying out nitrogen doped graphitization modification on the substrate surface layer substance to obtain the nitrogen doped graphitization modified electrode; compared with the traditional preparation method of the nickel-based electrode, based on hydrothermal reaction, molybdenum element is introduced on the nickel substrate to form a nano rod-shaped surface structure containing bimetal, so that the specific surface area of the material is increased.
Description
Technical Field
The invention belongs to the technical field of cathode electrodes for electrolyzed water, and particularly relates to a preparation method of a nitrogen-doped graphitized modified electrode.
Background
The use of fossil fuels in large quantities causes increasingly serious environmental pollution problems and rapid exhaustion of fossil fuels, which affect people's daily lives, so the exploration and development of sustainable clean energy to replace traditional fossil energy is a great problem to be solved urgently in the leading-edge scientific research field.
Clean energy is a new energy technology capable of effectively reducing greenhouse gas emission, and is one of important methods for reducing carbon dioxide emission. The non-carbon hydrogen energy source becomes the first choice of clean energy source, and the product of hydrogen combustion is water, which is the cleanest energy source in the world. And hydrogen has the characteristic of high combustion heat value, which is 3 times of gasoline, 3.9 times of alcohol and 4.5 times of coke. The current hydrogen production by water electrolysis compatible with new energy sources (wind, light, water power and the like) is gradually developed and becomes the most green hydrogen energy acquisition way, wherein the alkaline water electrolysis is expected to become a green large-scale hydrogen production pilot sheep.
The alkaline electrolyzed water is mainly composed of two half reactions of hydrogen (Hydrogen Evolution Reaction,HER;2H2O+2e-＝H2+2OH-,E0＝-0.83 V vs SHE) and oxygen (Oxygen Evolution Reaction,OER;2OH-＝1/2O2+H2O+2e-,E0＝0.4V vs SHE) . From theoretical potential difference analysis, the theoretical reversible voltage of the total reaction of electrolyzed water (H 2O＝H2+1/2O2;E0 =1.23V vs SHE) was 1.23V. Currently, noble metal catalysts such as platinum-based materials and ruthenium dioxide are considered to be the most effective electrocatalysts for Hydrogen Evolution Reactions (HER) and Oxygen Evolution Reactions (OER). However, these noble metal catalysts are costly, poorly durable and relatively scarce and difficult to use commercially on a large scale. Accordingly, there has been a great deal of effort to find stable, efficient, low cost non-noble metal materials.
In recent years, many new efforts have been mainly directed to the development of low cost alternative catalysts, mainly NiO, ni (OH) 2、 NiMoO4、Ni2P、MnO2, etc.
Disclosure of Invention
The technical problems to be solved are as follows:
Aiming at the defects of the prior art, the application solves the technical problems that the existing noble metal catalyst has high cost, poor durability, scarcity, difficulty in large-scale commercial application and the like, and provides a preparation method of the nitrogen doped graphitized modified electrode.
The technical scheme is as follows:
In order to achieve the above purpose, the present application is realized by the following technical scheme:
the preparation method of the nitrogen-doped graphitized modified electrode comprises the following steps:
First, surface cleaning treatment: carrying out surface cleaning treatment on the metal nickel substrate to obtain a clean metal nickel substrate;
Secondly, molybdic acid root corrosion treatment: subjecting the metal nickel substrate after the surface cleaning treatment to a solvothermal reaction-based corrosion treatment in a mixed solution containing molybdate and fluoride;
Thirdly, nitrogen doped graphitization modification treatment: and carrying out gas-solid reaction on the metal nickel substrate subjected to corrosion treatment under the protection of inert atmosphere, and carrying out nitrogen doped graphitization modification on the substrate surface layer substance to obtain the nitrogen doped graphitization modified electrode.
Furthermore, the nitrogen-doped graphitized modified electrode surface layer material is a nitrogen-doped carbon nano tube and nano metal particles wrapped by the nitrogen-doped carbon nano tube, and the high-efficiency alkaline environment water electrolysis hydrogen evolution catalytic performance is shown.
Further, the metal nickel substrate is 60 mesh plain nickel screen, nickel sheet or foam nickel.
Further, the surface cleaning treatment specifically comprises the following steps: firstly, ultrasonically cleaning in an acetone solution for 10-25min, repeatedly cleaning by using ethanol to remove a metal surface grease layer, placing the metal nickel substrate after removing the metal surface grease layer in a hydrochloric acid solution with the concentration of 1-5mol/L for 5-15min, standing for 10-25min, repeatedly cleaning by using distilled water to remove a metal surface oxide layer, and drying in an oven to obtain the clean metal nickel substrate.
Further, in the second step, the molybdate is one or more of ammonium molybdate 10-30mmol/L, sodium molybdate 26mmol/L and potassium molybdate 16mmol/L, and the fluoride is potassium fluoride 24-48mmol/L and/or ammonium fluoride 24-68 mmol/L.
Further, the corrosion treatment based on solvothermal reaction in the second step comprises the following specific steps: firstly placing the metal nickel substrate subjected to surface cleaning treatment into a hydrothermal kettle containing a mixed solution of molybdate and fluoride, wherein the filling degree of the hydrothermal kettle is 40-90%, heating the hydrothermal kettle to 90-180 ℃, maintaining for 1-20h, flushing the metal nickel substrate subjected to hydrothermal reaction with distilled water, and then drying to obtain the metal nickel substrate subjected to molybdate corrosion treatment.
Further, the gas-solid reaction in the third step is to put the metal nickel substrate after corrosion treatment in the middle section of a tubular furnace under the protection of inert atmosphere, put 0.08-2.4g melamine in the middle section of the tubular furnace under the protection of inert atmosphere, heat the tubular furnace to 450-1200 ℃, keep for 0.5-12h, wash the metal nickel substrate after heat treatment in the tubular furnace with ethanol and dry in vacuum to obtain the nitrogen doped graphitization modified electrode.
The beneficial effects are that:
The application provides a preparation method of a nitrogen-doped graphitized modified electrode, which has the following beneficial effects compared with the prior art:
1. compared with the traditional preparation method of the nickel-based electrode, based on hydrothermal reaction, molybdenum element is introduced on the nickel substrate to form a nano rod-shaped surface structure containing bimetal, so that the specific surface area of the material is increased;
2. Based on gas-solid reaction, nickel and molybdenum metal nano particles wrapped by nitrogen doped carbon nano tubes are formed on the surface of the material, so that the intrinsic catalytic activity is improved;
3. the preparation process is simple, no external nickel ions are required to be introduced, the cost is low, and the method is suitable for production and popularization;
4. The invention provides a preparation method of a nitrogen-doped graphitized modified electrode. The NiMoO 4 -based electrode is prepared by a solvothermal reaction method, and then the nitrogen-doped graphitized modified electrode is prepared by a gas-solid reaction. The electrode, as a cathode for alkaline electrolyzed water, exhibits a greatly improved hydrogen evolution catalytic activity as compared with a Ni-based electrode. The alkaline hydrogen evolution reaction performance of the obtained embodiment electrode is obviously improved compared with that of a comparative embodiment electrode based on the original metal substrate, particularly, the overpotential absolute value of the electrode prepared by adopting foam nickel is only 0.198V under the current density of 10 milliamperes per square centimeter, and the overpotential absolute value is reduced by 0.130V compared with that of the electrode prepared by adopting pure foam nickel, and is reduced by 0.107V compared with that of the electrode prepared by adopting surface cleaning treatment and molybdate corrosion treatment. Meanwhile, the overpotential rise of the electrode prepared by adopting the foam nickel after the continuous oxygen evolution reaction for 20 hours is only 2 millivolts.
Drawings
Fig. 1 is a scanning electron microscope picture of a nitrogen-doped graphitized modified electrode prepared in example 4 of the present technology, wherein the left image is a scanning electron microscope picture magnified 5000 times, and the right image is a scanning electron microscope picture magnified 100000 times.
Detailed Description
The application will be further illustrated with reference to specific examples. It is to be understood that these examples are illustrative of the present application and are not intended to limit the scope of the present application. Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the teachings of the present application, and equivalent changes and modifications are also within the scope of the application as defined in the claims.
Example 1:
the preparation method of the nitrogen-doped graphitized modified electrode, which uses nickel screen as a metallic nickel substrate, comprises the following steps:
firstly, placing a 60-mesh plain nickel screen in an acetone solution for ultrasonic cleaning for 15min, and repeatedly cleaning by using ethanol to remove an oil layer on the metal surface;
Secondly, placing the nickel screen after removing the grease layer on the metal surface in hydrochloric acid solution with the concentration of 2mol/L for ultrasonic treatment for 15min, standing for 15min, repeatedly cleaning with distilled water to remove the oxide layer on the metal surface, and drying to obtain the nickel screen after surface cleaning treatment;
Thirdly, placing the nickel screen subjected to surface cleaning treatment into a hydrothermal kettle containing a mixed solution of 10mmol/L ammonium molybdate, 16mmol/L potassium molybdate and 48mmol/L potassium fluoride, wherein the filling degree of the reaction kettle is 40%, heating the hydrothermal kettle to 120 ℃, and keeping for 15 hours;
Fourthly, washing the nickel screen subjected to the hydrothermal reaction by distilled water and drying to obtain the nickel screen subjected to the molybdate corrosion treatment;
Fifth step: placing 4 square centimeters of nickel screen subjected to molybdate corrosion treatment and 0.8g of melamine in the middle section of a tubular furnace under the protection of inert atmosphere, heating the tubular furnace to 700 ℃, and keeping for 8 hours;
Sixth step: and washing the nickel screen subjected to heat treatment in a tube furnace with ethanol and vacuum drying to obtain the nitrogen-doped graphitized modified electrode.
Example 2:
The preparation method of the nitrogen-doped graphitized modified electrode, which uses foam nickel as a metallic nickel substrate, comprises the following steps:
Firstly, placing foam nickel in an acetone solution for ultrasonic cleaning for 10min, and repeatedly cleaning by using ethanol to remove a grease layer on the metal surface;
Secondly, placing the foam nickel with the oil layer on the metal surface removed in hydrochloric acid solution with the concentration of 3mol/L for ultrasonic treatment for 10min, standing for 20min, repeatedly cleaning with distilled water to remove the oxide layer on the metal surface, and drying to obtain the foam nickel with the surface cleaned;
Thirdly, placing the foam nickel after the surface cleaning treatment into a hydrothermal kettle containing a mixed solution of 20mmol/L ammonium molybdate, 26mmol/L sodium molybdate and 68mmol/L ammonium fluoride, wherein the filling degree of the reaction kettle is 80%, heating the hydrothermal kettle to 150 ℃, and keeping for 6 hours;
Fourthly, washing the foam nickel after hydrothermal reaction by distilled water and drying to obtain the foam nickel after molybdate corrosion treatment;
Fifth step: placing 4 square centimeters of foam nickel subjected to molybdate corrosion treatment in the middle section of a tubular furnace under the protection of inert atmosphere, placing 2.4g of melamine in the middle section of the tubular furnace under the protection of inert atmosphere, heating the tubular furnace to 1200 ℃, and keeping for 0.5h;
sixth step: washing the foam nickel after heat treatment by using ethanol and vacuum drying to obtain the nitrogen doped graphitization modified electrode.
Example 3
The preparation method of the nitrogen-doped graphitized modified electrode, which uses a nickel sheet as a metallic nickel substrate, comprises the following steps:
Firstly, placing a nickel sheet in an acetone solution for ultrasonic cleaning for 20min, and repeatedly cleaning by using ethanol to remove a grease layer on the metal surface;
secondly, placing the nickel sheet after removing the oil layer on the metal surface in hydrochloric acid solution with the concentration of 1mol/L for ultrasonic treatment for 20min, standing for 10min, repeatedly cleaning with distilled water to remove the oxide layer on the metal surface, and drying to obtain the nickel sheet after surface cleaning treatment;
thirdly, placing the nickel sheet subjected to surface cleaning treatment into a hydrothermal kettle containing 10mmol/L ammonium molybdate and 56mmol/L ammonium fluoride mixed solution, wherein the filling degree of the reaction kettle is 90%, heating the hydrothermal kettle to 90 ℃, and keeping for 20 hours;
fourthly, washing the nickel sheet subjected to the hydrothermal reaction by distilled water and drying to obtain a nickel sheet subjected to the molybdate corrosion treatment;
Fifth step: placing 4 square centimeters of nickel sheet subjected to molybdate corrosion treatment in the middle section of a tubular furnace under the protection of inert atmosphere, placing 0.08g of melamine in the middle section of the tubular furnace under the protection of inert atmosphere, heating the tubular furnace to 450 ℃, and keeping for 12 hours;
sixth step: and washing the nickel sheet subjected to heat treatment in a tube furnace with ethanol and vacuum drying to obtain the nitrogen-doped graphitized modified electrode.
Example 4
The preparation method of the nitrogen-doped graphitized modified electrode, which uses foam nickel as a metallic nickel substrate, comprises the following steps:
firstly, placing foam nickel in an acetone solution for ultrasonic cleaning for 25min, and repeatedly cleaning by using ethanol to remove a grease layer on the metal surface;
Secondly, placing the foam nickel with the oil layer on the metal surface removed in hydrochloric acid solution with the concentration of 5mol/L for ultrasonic treatment for 5min, standing for 25min, repeatedly cleaning with distilled water to remove the oxide layer on the metal surface, and drying to obtain the foam nickel with the surface cleaned;
the third step is to place the foam nickel after the surface cleaning treatment in a solution containing 30mmol/L ammonium molybdate, 16mmol/L potassium molybdate,
In a hydrothermal kettle of a mixed solution of 24mmol/L potassium fluoride and 24mmol/L ammonium fluoride, the filling degree of the reaction kettle is 60%, heating the hydrothermal kettle to 180 ℃, and keeping for 1h;
Fourthly, washing the foam nickel after hydrothermal reaction by distilled water and drying to obtain the foam nickel after molybdate corrosion treatment;
Fifth step: placing 4 square centimeters of foam nickel subjected to molybdate corrosion treatment in the middle section of a tubular furnace under the protection of inert atmosphere, placing 3.2g of melamine in the middle section of the tubular furnace under the protection of inert atmosphere, heating the tubular furnace to 950 ℃, and keeping for 4 hours;
sixth step: washing the foam nickel after heat treatment by using ethanol and vacuum drying to obtain the nitrogen doped graphitization modified electrode.
Comparative example 1
The comparative example directly adopts 60 mesh plain nickel screen as an electrode:
Placing a 60-mesh plain nickel screen in an acetone solution, ultrasonically cleaning for 15min, and repeatedly cleaning with ethanol to remove an oil layer on the surface of the nickel screen; s12, placing the nickel screen with the surface grease layer removed in hydrochloric acid solution with the concentration of 2mol/L for ultrasonic treatment for 15min, standing for 15min, repeatedly cleaning with distilled water to remove the oxidation layer on the metal surface, and drying to obtain the clean nickel screen.
Comparative example 2:
The comparative example directly uses foam nickel as an electrode:
placing the foam nickel in an acetone solution for ultrasonic cleaning for 25min, and repeatedly cleaning by using ethanol to remove the grease layer on the surface of the foam nickel; s12, placing the foam nickel with the surface grease layer removed in hydrochloric acid solution with the concentration of 5mol/L for ultrasonic treatment for 5min, standing for 25min, repeatedly cleaning with distilled water to remove the oxide layer on the metal surface, and drying to obtain clean foam nickel.
Comparative example 3:
the comparative example directly adopts nickel sheets as electrodes:
Placing the nickel sheet in an acetone solution, ultrasonically cleaning for 10min, and repeatedly cleaning with ethanol to remove the grease layer on the surface of the nickel sheet; s12, placing the nickel sheet with the surface grease layer removed in hydrochloric acid solution with the concentration of 1mol/L for ultrasonic treatment for 20min, standing for 10min, repeatedly cleaning with distilled water to remove the oxide layer on the metal surface, and drying to obtain the clean nickel sheet.
Comparative example 4:
the comparative example uses foamed nickel as a metallic nickel substrate, and only uses a surface cleaning treatment and a molybdate etching treatment to prepare an electrode:
firstly, placing foam nickel in an acetone solution for ultrasonic cleaning for 25min, and repeatedly cleaning by using ethanol to remove a grease layer on the metal surface;
Secondly, placing the foam nickel with the oil layer on the metal surface removed in hydrochloric acid solution with the concentration of 5mol/L for ultrasonic treatment for 5min, standing for 25min, repeatedly cleaning with distilled water to remove the oxide layer on the metal surface, and drying to obtain the foam nickel with the surface cleaned;
Thirdly, placing the foam nickel after the surface cleaning treatment into a hydrothermal kettle containing a mixed solution of 30mmol/L ammonium molybdate, 16mmol/L potassium molybdate, 24mmol/L potassium fluoride and 24mmol/L ammonium fluoride, wherein the filling degree of the reaction kettle is 60%, heating the hydrothermal kettle to 180 ℃, and keeping for 1h;
And fourthly, washing the foam nickel after the hydrothermal reaction by distilled water and drying to obtain the foam nickel after the molybdate corrosion treatment.
TABLE 1
Electrocatalyst hydrogen evolution performance analysis table of the present technical example and comparative example
While the foregoing is directed to embodiments of the present invention, other and further details of the invention may be had by the present invention, it should be understood that the foregoing description is merely illustrative of the present invention and that no limitations are intended to the scope of the invention, except insofar as modifications, equivalents, improvements or modifications are within the spirit and principles of the invention.
Claims (5)
1. A preparation method of a nitrogen-doped graphitized modified electrode is characterized by comprising the following steps of: the method comprises the following steps:
First, surface cleaning treatment: carrying out surface cleaning treatment on the metal nickel substrate to obtain a clean metal nickel substrate;
Secondly, molybdic acid root corrosion treatment: subjecting the metal nickel substrate after the surface cleaning treatment to a solvothermal reaction-based corrosion treatment in a mixed solution containing molybdate and fluoride;
thirdly, nitrogen doped graphitization modification treatment: carrying out gas-solid reaction on the metal nickel substrate subjected to corrosion treatment under the protection of inert atmosphere, and carrying out nitrogen doped graphitization modification on the substrate surface layer substance to obtain the nitrogen doped graphitization modified electrode;
The surface cleaning treatment comprises the following specific steps: firstly, ultrasonically cleaning in an acetone solution for 10-25min, repeatedly cleaning by using ethanol to remove a metal surface grease layer, ultrasonically placing a metal nickel substrate with the metal surface grease layer removed in a hydrochloric acid solution with the concentration of 1-5mol/L for 5-15min, standing for 10-25min, repeatedly cleaning by using distilled water to remove a metal surface oxide layer, and drying in an oven to obtain a clean metal nickel substrate;
The corrosion treatment based on solvothermal reaction in the second step comprises the following specific steps: firstly placing the metal nickel substrate subjected to surface cleaning treatment into a hydrothermal kettle containing a mixed solution of molybdate and fluoride, wherein the filling degree of the hydrothermal kettle is 40-90%, heating the hydrothermal kettle to 90-180 ℃, maintaining for 1-20h, flushing the metal nickel substrate subjected to hydrothermal reaction with distilled water, and then drying to obtain the metal nickel substrate subjected to molybdate corrosion treatment.
2. The method for preparing the nitrogen-doped graphitized modified electrode according to claim 1, wherein the method comprises the following steps: the nitrogen-doped graphitized modified electrode surface layer material is a nitrogen-doped carbon nano tube and nano metal particles wrapped by the nitrogen-doped carbon nano tube, and the high-efficiency alkaline environment water electrolysis hydrogen evolution catalytic performance is shown.
3. The method for preparing the nitrogen-doped graphitized modified electrode according to claim 1, wherein the method comprises the following steps: the metal nickel substrate is 60 mesh plain nickel screen, nickel sheet or foam nickel.
4. The method for preparing a nitrogen-doped graphitized modified electrode according to claim 1, wherein: in the second step, the molybdate is one or more of ammonium molybdate 10-30mmol/L, sodium molybdate 26mmol/L and potassium molybdate 16mmol/L, and the fluoride is potassium fluoride 24-48mmol/L and/or ammonium fluoride 24-68 mmol/L.
5. The method for preparing a nitrogen-doped graphitized modified electrode according to claim 1, wherein: and in the third step, the gas-solid reaction is to put the corroded metal nickel substrate in the middle section of a tubular furnace under the protection of inert atmosphere, put 0.08-2.4g melamine in the middle section of the tubular furnace under the protection of inert atmosphere, heat the tubular furnace to 450-1200 ℃, keep the temperature for 0.5-12h, rinse the metal nickel substrate after heat treatment of the tubular furnace with ethanol, and dry in vacuum to obtain the nitrogen doped graphitized modified electrode.
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| CN111013635A (en) * | 2020-01-08 | 2020-04-17 | 河北大学 | Substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material and preparation method and application thereof |
| CN111841593A (en) * | 2020-08-27 | 2020-10-30 | 中国地质大学（武汉） | Molybdenum carbide-based catalyst, preparation method and application |
| CN113249735A (en) * | 2021-04-19 | 2021-08-13 | 北京化工大学 | Preparation method of efficient molybdenum carbide hydrogen evolution catalyst |
| CN113846343A (en) * | 2021-07-17 | 2021-12-28 | 北京工业大学 | Preparation method of nickel-molybdenum carbide electrocatalyst |
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| CN111013635A (en) * | 2020-01-08 | 2020-04-17 | 河北大学 | Substrate-loaded nitrogen-doped carbon nanotube-surrounded molybdenum carbide particle composite material and preparation method and application thereof |
| CN111841593A (en) * | 2020-08-27 | 2020-10-30 | 中国地质大学（武汉） | Molybdenum carbide-based catalyst, preparation method and application |
| CN113249735A (en) * | 2021-04-19 | 2021-08-13 | 北京化工大学 | Preparation method of efficient molybdenum carbide hydrogen evolution catalyst |
| CN113846343A (en) * | 2021-07-17 | 2021-12-28 | 北京工业大学 | Preparation method of nickel-molybdenum carbide electrocatalyst |
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