CN113186557A - In-situ preparation method of water electrolysis oxygen evolution catalytic electrode, electrode and application - Google Patents
In-situ preparation method of water electrolysis oxygen evolution catalytic electrode, electrode and application Download PDFInfo
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- CN113186557A CN113186557A CN202110483732.0A CN202110483732A CN113186557A CN 113186557 A CN113186557 A CN 113186557A CN 202110483732 A CN202110483732 A CN 202110483732A CN 113186557 A CN113186557 A CN 113186557A
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 45
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 239000001301 oxygen Substances 0.000 title claims abstract description 29
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 29
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 25
- 238000005868 electrolysis reaction Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910001220 stainless steel Inorganic materials 0.000 claims description 104
- 239000010935 stainless steel Substances 0.000 claims description 101
- 229910000863 Ferronickel Inorganic materials 0.000 claims description 60
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 40
- 238000005406 washing Methods 0.000 claims description 18
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 238000009210 therapy by ultrasound Methods 0.000 claims description 14
- 239000012670 alkaline solution Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 8
- 238000004321 preservation Methods 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 239000000758 substrate Substances 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 229910000510 noble metal Inorganic materials 0.000 abstract description 10
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 238000011282 treatment Methods 0.000 description 25
- 239000002585 base Substances 0.000 description 18
- 239000003513 alkali Substances 0.000 description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 9
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- 238000004769 chrono-potentiometry Methods 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- DMTIXTXDJGWVCO-UHFFFAOYSA-N iron(2+) nickel(2+) oxygen(2-) Chemical compound [O--].[O--].[Fe++].[Ni++] DMTIXTXDJGWVCO-UHFFFAOYSA-N 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011419 induction treatment Methods 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- BAVYZALUXZFZLV-UHFFFAOYSA-N mono-methylamine Natural products NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M sodium bicarbonate Substances [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910006279 γ-NiOOH 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
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23G—CLEANING OR DE-GREASING OF METALLIC MATERIAL BY CHEMICAL METHODS OTHER THAN ELECTROLYSIS
- C23G1/00—Cleaning or pickling metallic material with solutions or molten salts
- C23G1/14—Cleaning or pickling metallic material with solutions or molten salts with alkaline solutions
- C23G1/19—Iron or steel
-
- 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
-
- 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)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Inorganic Chemistry (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention discloses an in-situ preparation method of a water electrolysis oxygen evolution catalytic electrode, the electrode and application thereof. The invention has the beneficial effects that: (1) the preparation method of the catalytic electrode is simple, the requirement on preparation conditions is low, the process parameters do not need to be accurately controlled, and the number of working procedures is small; (2) has large-scale application prospect; (3) the prepared catalytic electrode has excellent performance; (4) the base material is made of a non-noble metal and can be formed into various shapes as required, and can be produced by the method of the present invention.
Description
Technical Field
The invention belongs to the field of electrochemical electrodes, and particularly relates to an in-situ preparation method of a water electrolysis oxygen evolution catalytic electrode, the electrode and application.
Background
The use of clean energy sources such as water energy, wind energy, tidal energy, solar energy, nuclear energy and the like to replace traditional stone energy sources such as coal, petroleum and the like is a demand for the development of the current society. The clean energy needs to be converted into electric energy for storage and transmission, but peak period storage and conversion are not effectively solved, and hydrogen production by water electrolysis is one of the best modes for storing and converting the electric energy. In the water electrolysis process, 4 protons need to be removed from water molecules to form O-O bonds due to anodic oxygen evolution, the kinetic process is slow, the overpotential is high, and the electric Energy loss is huge, so the method is a key for limiting the application of the water electrolysis hydrogen production technology (Energy environ.Sci.,2014,7, 3519; J.Mater.Chem.A., 2016,4, 17587; ACS Catal.,2016,6, 8069). Therefore, the development of cheap and efficient oxygen evolution catalytic electrodes is the core of solving the problem of hydrogen production by water electrolysis.
At present, the electrodes for water electrolysis oxygen evolution are mainly made of Pt and RuO2、IrO2Etc. and noble metals and oxides thereof. However, the noble metals have limited application in the water electrolysis hydrogen production industry due to the problems of high price, rarity, poor stability and tolerance and the like. In view of the above problems, researchers and industries at home and abroad are dedicated to develop non-noble metal oxygen evolution catalysts to obtain cheap water electrolysis oxygen evolution catalytic electrodes with higher activity, stability and tolerance. The first transition elements (Fe, Co, Ni, Mn, etc.) are widely regarded as the ideal non-noble metals for preparing hydrogen and oxygen evolution catalytic electrodes by water electrolysis because of large earth reserves and low price (ACS appl. Mater. Interfaces,2015,7, 21852; Energy environ. Sci.,2013,6, 579; Angew. chem., int. Ed.,2014,53, 8508). Currently, there are two main ways to prepare non-noble metal oxygen evolution catalytic electrodes. Firstly, non-noble metals or non-noble metal compoundsThe powder catalyst is adhered on the surfaces of metal, glassy carbon and the like to prepare an oxygen evolution electrode (CN 106807379A; CN107326393B), but has the problems of easy stripping of powder materials, poor stability and the like; secondly, non-noble metal is deposited on substrates such as metal and semiconductor to prepare the oxygen evolution electrode (CN 106917105B; CN 105107535A), but the problems of complex deposition system, high control precision requirement and the like exist.
In the industrial hydrogen production process by water electrolysis, stainless steel is directly used as an oxygen evolution electrode due to low price and easy availability, but the overpotential is high, and further modification is needed to reduce the application cost (ACS Energy Lett.,2018,3, 574; J.Power sources,2018,395,106). However, the current method for directly modifying the surface of stainless steel is complex, and requires the use of highly toxic substances such as chlorine (Energy environ. Sci.,2015,8, 2685; ACS Catal.,2015,5,2671), which brings great harm to the environment. Chinese patent publication No. CN110791772A discloses a method for obtaining a high-performance oxygen evolution catalyst electrode by in-situ electrochemical induction treatment of nickel-iron alloy or stainless steel, but still does not satisfy the current requirements, and the problem of the electrochemical induction method is that: (1) experimental conditions such as an electrochemical window, a scanning speed and the like need to be strictly and accurately controlled, and the requirements on preparation conditions are extremely high; (2) the large-scale in-situ production is difficult, and the diversified demands of the market on the oxygen evolution electrode can not be realized; (3) the conductivity of the treated electrode is greatly reduced.
Disclosure of Invention
In view of the above, an object of the present invention is to provide an in-situ preparation method of a catalytic electrode for water electrolysis oxygen evolution.
The technical scheme is as follows:
the in-situ preparation method of the water electrolysis oxygen evolution catalytic electrode is characterized by comprising the following steps:
step one, soaking a nickel-iron stainless steel substrate in an alkaline solution, and carrying out ultrasonic treatment;
step two, transferring the alkaline solution and the nickel-iron stainless steel base material into a heat preservation device for heat preservation, then taking out the nickel-iron stainless steel base material, and washing away residual alkaline liquor on the surface of the nickel-iron stainless steel base material by using pure water;
and step three, calcining the ferronickel stainless steel substrate treated in the step two to obtain the electrode.
Preferably, the nickel content of the nickel-iron stainless steel base material is 5-65% in parts by mass.
Preferably, the nickel-iron stainless steel substrate is in the form of a block, rod, sheet or wire.
Preferably, the alkaline solution is an inorganic alkaline solution, an organic alkaline solution or a mixed solution of an inorganic alkaline and an organic alkaline, and the mass concentration of the alkaline solution is between 5 and 50 percent.
Preferably, the inorganic base is NaOH, KOH or Na2CO3、NaHCO3Or NH3。
Preferably, the organic base is methylamine, ethylamine, ethylenediamine, diethylamine or triethylamine.
Preferably, the ultrasonic frequency of the ultrasonic treatment is 20 to 100 kHz.
Preferably, the time of the ultrasonic treatment is 0.5 to 4 hours.
Preferably, in the second step, the heat preservation temperature is between normal temperature and 100 ℃, and the heat preservation time is 2-24 h.
Preferably, in the third step, the calcination temperature is 100-500 ℃, and the calcination time is 2-5 h.
It is another object of the present invention to provide an electrode. The technical scheme is as follows:
the key point of the electrode is that the electrode is prepared by adopting the method as described in any one of the above items.
The invention also aims to provide the application of the electrode as a water electrolysis oxygen evolution catalytic electrode.
Drawings
FIG. 1 is SEM images of the surface of a nickel-iron stainless steel before (1a) and after (1 b);
FIG. 2 is a XRD pattern of a nickel-iron stainless steel before and after treatment;
FIG. 3 is an XPS spectrum of a pre-treated and post-treated nickel iron stainless steel;
FIG. 4 is O1s XPS spectra for pre-and post-treated nickel-iron stainless steels;
FIG. 5 is a Ni2p XPS spectra of pre-and post-treated nickel-iron stainless steels;
FIG. 6 is a Fe2p XPS spectra of pre-and post-treated nickel-iron stainless steels;
FIG. 7 is an LSV curve for a nickel-iron stainless steel working electrode before and after treatment;
FIG. 8 is the it curve for a pre-treated and post-treated nickel-iron stainless steel working electrode;
fig. 9 is a CP curve for a nickel-iron stainless steel working electrode before and after treatment.
Detailed Description
The present invention will be further described with reference to the following examples and the accompanying drawings.
Preparation of electrocatalytic electrode
Example 1
Taking a 8cm multiplied by 8cm ferronickel stainless steel plate as a base material, washing off surface oil stain, carefully placing the ferronickel stainless steel plate in 10% wt KOH solution, setting the frequency of an ultrasonic reactor at 20kHz, and carrying out ultrasonic treatment for 0.5 h. And transferring the alkali liquor and the ferronickel stainless steel plate into a constant-temperature water bath kettle, setting the water temperature to be 50 ℃, and preserving the heat for 12 hours. And taking out the ferronickel stainless steel plate, slightly washing off the alkali liquor on the surface, putting the ferronickel stainless steel plate into an oven to be dried for 1 hour, and putting the ferronickel stainless steel plate into a muffle furnace to be calcined for 2 hours at 300 ℃ to obtain the ferronickel stainless steel electrocatalytic electrode. The purpose of calcination treatment is to improve the connection strength between the newly generated substances on the surface layer of the nickel-iron stainless steel and the matrix and improve the stability of the nickel-iron stainless steel.
Example 2
Taking a 8cm multiplied by 2cm ferronickel stainless steel plate as a base material, washing off surface oil stain with the nickel content of 20 wt%, carefully placing the stainless steel plate in 30 wt% KOH solution, setting the frequency of an ultrasonic reactor at 60kHz, and carrying out ultrasonic treatment for 1.5 h. And transferring the alkali liquor and the ferronickel stainless steel plate into a constant-temperature water bath kettle, setting the water temperature to be 50 ℃, and preserving the heat for 12 hours. And taking out the ferronickel stainless steel plate, slightly washing off the alkali liquor on the surface, putting the ferronickel stainless steel plate into an oven to be dried for 1 hour, and putting the ferronickel stainless steel plate into a muffle furnace to be calcined for 2 hours at 500 ℃ to obtain the ferronickel stainless steel electrocatalytic electrode.
Example 3
Taking a 8cm multiplied by 8cm ferronickel stainless steel plate as a base material, washing off surface oil stain with the nickel content of 10 wt%, carefully placing the base material in 30 wt% NaOH solution, setting the frequency of an ultrasonic reactor at 30kHz, and carrying out ultrasonic treatment for 2 h. And transferring the alkali liquor and the ferronickel stainless steel plate into a constant-temperature water bath kettle, setting the water temperature to be 25 ℃, and preserving the heat for 12 hours. And taking out the ferronickel stainless steel plate, slightly washing off alkali liquor on the surface, putting the ferronickel stainless steel plate into an oven to be dried for 1 hour, and putting the ferronickel stainless steel plate into a muffle furnace to be calcined for 4 hours at 200 ℃ to obtain the ferronickel stainless steel electrocatalytic electrode.
Example 4
Taking a 5cm × 10cm ferronickel stainless steel plate as a base material, the nickel content of which is 5 wt%, washing off surface oil stain, carefully placing the stainless steel plate on 10 wt% NaCO3In the solution, the frequency of the ultrasonic reactor is set at 40kHz, and ultrasonic treatment is carried out for 2 hours. And transferring the alkali liquor and the ferronickel stainless steel plate into a constant-temperature water bath kettle, setting the water temperature to 80 ℃, and preserving the heat for 5 hours. And taking out the ferronickel stainless steel plate, slightly washing off alkali liquor on the surface, putting the ferronickel stainless steel plate into an oven to be dried for 1 hour, and putting the ferronickel stainless steel plate into a muffle furnace to be calcined for 2 hours at 400 ℃ to obtain the ferronickel stainless steel electrocatalytic electrode.
Example 5
Taking a 10cm multiplied by 10cm ferronickel stainless steel plate as a base material, washing off surface oil stain, carefully placing the base material in 50 wt% ethylenediamine solution, setting the frequency of an ultrasonic reactor at 80kHz, and carrying out ultrasonic treatment for 0.5 h. And transferring the alkali liquor and the ferronickel stainless steel plate into a constant-temperature water bath kettle, setting the water temperature to be 40 ℃, and preserving the heat for 10 hours. And taking out the ferronickel stainless steel plate, slightly washing off alkali liquor on the surface, putting the ferronickel stainless steel plate into an oven to be dried for 1 hour, and putting the ferronickel stainless steel plate into a muffle furnace to be calcined for 1 hour at 200 ℃ to obtain the ferronickel stainless steel electrocatalytic electrode.
Example 6
Taking a 5cm multiplied by 5cm ferronickel stainless steel plate as a base material, washing off surface oil stain, carefully placing the base material in 10 wt% triethylamine solution, setting the frequency of an ultrasonic reactor at 80kHz, and carrying out ultrasonic treatment for 0.5 h. And transferring the alkali liquor and the ferronickel stainless steel plate into a constant-temperature water bath kettle, setting the water temperature to be 40 ℃, and preserving the heat for 10 hours. And taking out the ferronickel stainless steel plate, slightly washing off the alkali liquor on the surface, putting the ferronickel stainless steel plate into an oven to be dried for 1 hour, and putting the ferronickel stainless steel plate into a muffle furnace to be calcined for 5 hours at 100 ℃ to obtain the ferronickel stainless steel electrocatalytic electrode.
Example 7
Taking a 5cm multiplied by 10cm ferronickel stainless steel plate as a base material, washing off surface oil stain after the nickel content is 35 wt%, carefully placing the base material in 5 wt% NaOH solution, setting the frequency of an ultrasonic reactor at 100kHz, and carrying out ultrasonic treatment for 4 h. And transferring the alkali liquor and the ferronickel stainless steel plate into a constant-temperature water bath kettle, setting the water temperature to be 100 ℃, and preserving the heat for 2 hours. And taking out the ferronickel stainless steel plate, slightly washing off the alkali liquor on the surface, putting the ferronickel stainless steel plate into an oven to be dried for 1 hour, and putting the ferronickel stainless steel plate into a muffle furnace to be calcined for 5 hours at 100 ℃ to obtain the ferronickel stainless steel electrocatalytic electrode.
Example 8
Taking a 5cm multiplied by 10cm ferronickel stainless steel plate as a base material, washing off surface oil stain after the nickel content is 35 wt%, carefully placing the base material in 5 wt% NaOH solution, setting the frequency of an ultrasonic reactor at 100kHz, and carrying out ultrasonic treatment for 4 h. And transferring the alkali liquor and the ferronickel stainless steel plate into a constant-temperature water bath kettle, setting the water temperature to be 40 ℃, and preserving the heat for 24 hours. And taking out the ferronickel stainless steel plate, slightly washing off the alkali liquor on the surface, putting the ferronickel stainless steel plate into an oven to be dried for 1 hour, and putting the ferronickel stainless steel plate into a muffle furnace to be calcined for 5 hours at 100 ℃ to obtain the ferronickel stainless steel electrocatalytic electrode.
Although examples 1-8 are all made from sheet material, one skilled in the art would envision that it would be feasible to make an electro-catalytic electrode using any other shape of the nickel iron stainless steel sheet substrate, such as rod, block, wire, or other shapes.
Characterization of the electrocatalytic electrode
Taking the nickel-iron stainless steel electrocatalytic electrode sample prepared in the embodiment 2, analyzing the surface morphology of the nickel-iron stainless steel electrocatalytic electrode sample by a Scanning Electron Microscope (SEM), analyzing the crystal structure by an X-ray diffraction analysis (XRD), and researching the surface chemical components of the nickel-iron stainless steel by an X-ray photoelectron spectroscopy (XPS). The above analysis methods were performed according to the prior art, and the analysis test procedure was performed using clean nickel-iron stainless steel plates without chemical treatment as a control.
Referring to fig. 1, it can be seen that the surface of the nickel-iron stainless steel before and after the treatment was flat, the surface of the nickel-iron stainless steel (1a) after the treatment had protrusions with various shapes, and a part of the protrusions exhibited a rough porous structure, presumably nickel-iron oxide, with a maximum dimension of about 1 μm.
As in fig. 2, the XRD pattern of the pre-treated nickel iron stainless steel sample showed four distinct NiFe alloy peaks at 43.9 °, 51 °, 74.9 ° and 75.2 °. The XRD map peak position of the ferronickel stainless steel sample after treatment has changed comparatively obviously: the peak at 43.9 ° splits into two peaks, at 43.8 ° and 43.9 °, respectively. At the same time, the peak at 51 ° is also split into two peaks, at 50.9 ° and 51.1 °, respectively. Comparing with a compound XRD spectrum database, the newly generated metal oxide peaks are confirmed, namely, the nickel-iron oxide is generated on the surface of the treated nickel-iron stainless steel sample.
XPS spectra of the ferronickel stainless steel samples before and after treatment are shown in figure 3.
As shown in FIG. 4, it can be seen from the O1s XPS spectra of the samples of the ferronickel stainless steel before and after the treatment that the surface of the ferronickel stainless steel before the treatment contains a small amount of M-OH, while the surface of the ferronickel stainless steel after the treatment contains M-OH and M-O bonds, indicating that the surface of the ferronickel stainless steel after the treatment has metal oxides and metal hydroxides.
As shown in FIG. 5, from the XPS spectra of Ni2p before and after the treatment, the surface of the nickel-iron stainless steel before the treatment contains a large amount of metallic nickel (852.8eV), and the surface of the nickel-iron stainless steel after the treatment contains more Ni2+(855.8eV and 862.0eV) and in the form of Ni (OH)2And gamma-NiOOH.
As shown in FIG. 6, it can be seen from the Fe2p XPS spectra before and after the treatment that the surface of the ferronickel stainless steel before the treatment contains a large amount of metallic iron (706.6eV), the peak of the metallic iron on the surface of the ferronickel stainless steel after the treatment disappears, and Fe2+And Fe3+The peak is more pronounced (709-711eV), indicating the presence of iron oxide or hydroxide on the surface.
With reference to SEM pictures, it is estimated that the projections having different shapes on the surface of the treated nickel-iron stainless steel are oxides or hydroxides of nickel-iron.
Electrochemical performance of (III) electrocatalytic electrode
Example 9
The nickel-iron stainless steel electro-catalytic electrode prepared in example 2 was carefully sheared to 1cm × 1cm of nickel-iron stainless steel plate as a working electrode, Pt as a counter electrode, Ag/AgCl as a reference electrode, and 1mol/L KOH as a reaction medium, and electrochemical performance of the prepared electro-catalytic electrode was tested using chenhua CHI600E electrochemical workstation, and the test items included Linear Sweep Voltammetry (LSV) analysis, current-time curve (it) analysis, and Chronopotentiometry (CP) analysis. And evaluating the performance of the in-situ prepared oxygen evolution catalytic electrode by comparing the LSV curve, the it curve and the CP curve of the nickel-iron stainless steel before and after treatment.
The control example used an untreated 1cm by 1cm nickel-iron stainless steel plate as the working electrode.
As shown in fig. 7, the treated electrocatalytic electrode had a lower overpotential and a higher current density. As shown in fig. 8, it can be seen that the it curves of the pre-treated and post-treated working electrodes have similar trends, but the current density of the post-treated working electrode is greater, and the degree of decrease of the current density after treatment is significantly lower than that before treatment, indicating that the electrode stability after treatment is higher. As can be seen in fig. 9, the treated electrode can achieve the same current at a lower voltage and the stability is significantly better than the electrode before treatment.
The test results show that the electrocatalytic electrode after in-situ treatment has obviously better performances such as activity, stability, tolerance and the like than untreated ferronickel stainless steel.
Compared with the prior art, the invention has the beneficial effects that: (1) the preparation method of the catalytic electrode is simple, the requirement on preparation conditions is low, the process parameters do not need to be accurately controlled, and the number of working procedures is small; (2) has large-scale application prospect; (3) the prepared catalytic electrode has excellent performance; (4) the base material is made of a non-noble metal and can be formed into various shapes as required, and can be produced by the method of the present invention.
Finally, it should be noted that the above-mentioned description is only a preferred embodiment of the present invention, and those skilled in the art can make various similar representations without departing from the spirit and scope of the present invention.
Claims (10)
1. An in-situ preparation method of a water electrolysis oxygen evolution catalytic electrode is characterized by comprising the following steps:
step one, soaking a nickel-iron stainless steel substrate in an alkaline solution, and carrying out ultrasonic treatment;
step two, transferring the alkaline solution and the nickel-iron stainless steel base material into a heat preservation device for heat preservation, then taking out the nickel-iron stainless steel base material, and washing away residual alkaline liquor on the surface of the nickel-iron stainless steel base material by using pure water;
and step three, calcining the ferronickel stainless steel substrate treated in the step two to obtain the electrode.
2. The in-situ preparation method of the catalytic electrode for water electrolysis oxygen evolution according to claim 1, characterized in that: the nickel content of the nickel-iron stainless steel base material is 5-65% in parts by weight.
3. The in-situ preparation method of the catalytic electrode for water electrolysis oxygen evolution according to claim 1, characterized in that: the nickel-iron stainless steel base material is in a block shape, a rod shape, a sheet shape or a thread shape.
4. The in-situ preparation method of the catalytic electrode for water electrolysis oxygen evolution according to claim 1, characterized in that: the alkaline solution is an inorganic alkaline solution, an organic alkaline solution or a mixed solution of inorganic alkaline and organic alkaline, and the mass concentration of the alkaline solution is between 5 and 50 percent.
5. The in-situ preparation method of the water electrolysis oxygen evolution catalytic electrode as claimed in any one of claims 1 to 4, wherein: the ultrasonic frequency of the ultrasonic treatment is 20-100 kHz.
6. The in-situ preparation method of the catalytic electrode for water electrolysis oxygen evolution according to claim 5, characterized in that: the ultrasonic treatment time is 0.5-4 h.
7. The in-situ preparation method of the catalytic electrode for water electrolysis oxygen evolution according to claim 5, characterized in that: in the second step, the heat preservation temperature is from normal temperature to 100 ℃, and the heat preservation time is 2-24 h.
8. The in-situ preparation method of the catalytic electrode for water electrolysis oxygen evolution according to claim 5, characterized in that: in the third step, the calcining temperature is 100-500 ℃, and the calcining time is 2-5 h.
9. An electrode produced by the method according to any one of claims 1 to 8.
10. Use of the electrode of claim 9 as a catalytic electrode for the water electrolysis of oxygen.
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| CN110791772A (en) * | 2019-12-02 | 2020-02-14 | 北京化工大学 | Method for preparing high-activity oxygen evolution electrode material through electrochemical induction |
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| US20170314142A1 (en) * | 2016-04-29 | 2017-11-02 | University Of Kansas | Microwave assisted synthesis of metal oxyhydroxides |
| CN108726581A (en) * | 2018-06-06 | 2018-11-02 | 江西理工大学 | The method for preparing iron-doped nickel oxide using Ni-Fe alloy melts |
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