CN116288455A - Preparation method of foam nickel-based electrolytic water oxygen evolution catalyst - Google Patents
Preparation method of foam nickel-based electrolytic water oxygen evolution catalyst Download PDFInfo
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- CN116288455A CN116288455A CN202310171447.4A CN202310171447A CN116288455A CN 116288455 A CN116288455 A CN 116288455A CN 202310171447 A CN202310171447 A CN 202310171447A CN 116288455 A CN116288455 A CN 116288455A
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- foam nickel
- water
- nickel
- foam
- oxygen evolution
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 219
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 108
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 97
- 239000006260 foam Substances 0.000 title claims abstract description 91
- 239000003054 catalyst Substances 0.000 title claims abstract description 43
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000001301 oxygen Substances 0.000 title claims abstract description 32
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 25
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 62
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 31
- 229910052786 argon Inorganic materials 0.000 claims description 31
- 239000000243 solution Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 10
- 230000004048 modification Effects 0.000 claims description 10
- 238000012986 modification Methods 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 9
- 238000001354 calcination Methods 0.000 claims description 8
- 150000003839 salts Chemical class 0.000 claims description 8
- 150000002505 iron Chemical class 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 6
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 5
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 claims 1
- 238000009832 plasma treatment Methods 0.000 abstract description 20
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- 230000000694 effects Effects 0.000 abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001257 hydrogen Substances 0.000 abstract description 9
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 9
- 230000008859 change Effects 0.000 abstract description 6
- 238000005868 electrolysis reaction Methods 0.000 abstract description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002699 waste material Substances 0.000 abstract description 5
- 239000010411 electrocatalyst Substances 0.000 abstract description 4
- 239000007788 liquid Substances 0.000 abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000002904 solvent Substances 0.000 abstract description 3
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 abstract description 2
- 239000010453 quartz Substances 0.000 description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 14
- 238000003860 storage Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- 229910052802 copper Inorganic materials 0.000 description 5
- 239000010949 copper Substances 0.000 description 5
- 230000008878 coupling Effects 0.000 description 5
- 238000010168 coupling process Methods 0.000 description 5
- 238000005859 coupling reaction Methods 0.000 description 5
- 230000001939 inductive effect Effects 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 239000012159 carrier gas Substances 0.000 description 4
- 230000001276 controlling effect Effects 0.000 description 4
- 238000011056 performance test Methods 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 239000008213 purified water Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000011144 upstream manufacturing Methods 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 229910002555 FeNi Inorganic materials 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000004070 electrodeposition Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910015189 FeOx Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000001976 improved effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical compound [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 238000007557 optical granulometry Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000008093 supporting effect Effects 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
- C25B11/02—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
- 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
- C25B11/055—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
- 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)
- Catalysts (AREA)
Abstract
The invention provides a preparation method of a foam nickel-based electrolytic water oxygen evolution catalyst, belonging to the technical field of hydrogen production by water electrolysis. The invention provides a preparation method of a foam nickel-based electrolytic water oxygen evolution catalyst, which comprises the following steps: and modifying the foam nickel by utilizing water plasma to obtain the foam nickel-based electrolytic water oxygen evolution catalyst. The invention adopts the water plasma treatment method, can quickly and conveniently form nickel/iron hydroxide oxide on the surface of the foam nickel, improves the oxygen evolution reaction activity of the foam nickel, and obtains the high-efficiency foam nickel-based electrocatalyst, the treatment process is simple and convenient, a large amount of solvents are not needed, no waste liquid is generated, the treatment time is short, and the treatment time is far less than more than ten hours in the prior art. And the hydroxide generated on the surface of the foam nickel can change the wettability to water.
Description
Technical Field
The invention relates to the technical field of hydrogen production by water electrolysis, in particular to a preparation method of a foam nickel-based water electrolysis oxygen evolution catalyst.
Background
The hydrogen production by water electrolysis is a key technology for realizing green hydrogen energy, the slow dynamics of the cathodic hydrogen evolution reaction and the anodic oxygen evolution reaction are key problems for limiting the development of the cathodic hydrogen evolution reaction and the anodic oxygen evolution reaction, and the development of an efficient electrode catalyst is an important way for promoting the large-scale application of the hydrogen production by water electrolysis. It is a significant challenge how to increase the electrocatalytic activity of the oxygen evolution reaction, with higher overpotential for the anodic oxygen evolution reaction than for the cathodic hydrogen evolution reaction. The foam nickel has better electrocatalytic activity due to the three-dimensional self-supporting porous structure, and is widely applied to electrode materials for hydrogen production by alkaline water electrolysis. The foam nickel can also be used as a supporting material, and the surface of the foam nickel can be modified or loaded with other catalysts to prepare the foam nickel-based composite material with higher electrochemical activity.
The nickel-iron double metal hydroxide and the derivative thereof (NiFe-LDH/NF) loaded on the foam nickel are common composite materials, and have the advantages of high catalytic activity of oxygen evolution reaction, easy preparation, adjustable structure and the like. Currently, it is mainly prepared by hydrothermal method, electrochemical deposition method and dipping method. The hydrothermal method is to soak foam nickel in the solution of the precursor to carry out hydrothermal reaction, so that the catalyst grows or deposits on the surface of the foam nickel; the electrochemical deposition method is to electrolytically deposit a precursor in the electrolyte to the surface of the foam nickel; the impregnation method is to directly impregnate the foam nickel into a precursor solution and deposit a catalyst on the surface of the foam nickel through chemical reaction. The method can prepare NiFe-LDH/NF catalysts with different components, and can regulate and control the structure and morphology of the catalysts.
However, the existing preparation method of NiFe-LDH/NF has complex treatment process and longer reaction time, and a large amount of waste liquid is necessarily generated after the reaction is finished, so that the cost of waste treatment is increased.
Disclosure of Invention
In view of the above, the invention aims to provide a preparation method of a foam nickel-based electrolytic water oxygen evolution catalyst. The invention can form nickel or nickel/iron hydroxide on the surface of foam nickel rapidly and conveniently, without needing a large amount of solvent and generating waste liquid.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a foam nickel-based electrolytic water oxygen evolution catalyst, which comprises the following steps:
and modifying the foam nickel by utilizing water plasma to obtain the foam nickel-based electrolytic water oxygen evolution catalyst.
Preferably, the water plasma is derived from a radio frequency plasma source.
Preferably, the power of the radio frequency plasma source is 0-500W, the power of the radio frequency plasma source is not 0, and the frequency of the radio frequency plasma source is 13.56MHz.
Preferably, the preparation parameters of the water plasma include: the pressure of the cavity is 10-50 Pa, the gas atmosphere is a mixed gas of argon and steam, the volume content of the steam in the mixed gas is 2-100%, and the flow of the argon is 10-30 sccm.
Preferably, the modification time is 1 to 60 minutes.
Preferably, the foam nickel further comprises pretreatment before modification, wherein the pretreatment comprises ultrasonic treatment with an acidic solution, water and absolute ethyl alcohol in sequence and then drying.
Preferably, the acidic solution is a dilute hydrochloric acid solution, and the mass fraction of the dilute hydrochloric acid solution is 1% -10%.
Preferably, the nickel foam further comprises a supported iron oxide prior to modification, the supported iron oxide comprising the steps of:
immersing the foam nickel in a soluble ferric salt solution and then drying to obtain the foam nickel with ferric salt loaded on the surface;
and calcining the foam nickel with the ferric salt loaded on the surface to obtain the foam nickel with the ferric oxide loaded on the surface.
Preferably, the calcination temperature is 200-600 ℃ and the time is 0.5-2 h.
Preferably, the soluble iron salt in the soluble iron salt solution comprises ferric nitrate or ferric chloride.
The invention provides a preparation method of a foam nickel-based electrolytic water oxygen evolution catalyst, which comprises the following steps: and modifying the foam nickel by utilizing water plasma to obtain the foam nickel-based electrolytic water oxygen evolution catalyst.
The invention adopts the water plasma treatment method, can quickly and conveniently form nickel or nickel/iron hydroxide oxide on the surface of the foam nickel, improves the oxygen evolution reaction activity of the foam nickel, and obtains the high-efficiency foam nickel-based electrocatalyst, which has simple treatment process, no need of a large amount of solvents, no waste liquid generation, short treatment time and much less than ten hours in the prior art. And the hydroxide generated on the surface of the foam nickel can change the wettability to water.
The invention utilizes water plasma to treat foam nickel to prepare Ni (O) OH/NF catalyst, and further, can also obtain (Fe/Ni) (O) OH/NF catalyst.
Furthermore, the invention has different power of the radio frequency plasma source, different species and ionization degree for generating the water plasma, and can regulate and control the proportion of hydroxide and oxyhydroxide in the (Fe/Ni) (O) OH/NF catalyst by regulating and controlling the water plasma treatment parameter and the Fe/Ni proportion of the precursor, thereby further improving the oxygen evolution reaction activity of the foam nickel-based catalyst.
Drawings
FIG. 1 is a schematic diagram of a water plasma apparatus for preparing an electrocatalyst;
FIG. 2 is a graph showing the effect of water plasma treatment on NF surface morphology, wherein a is a scanning electron micrograph of NF that has not been subjected to water plasma treatment, and b is a scanning electron micrograph of Ni (O) OH/NF;
FIG. 3 is a graph showing the effect of water plasma treatment on the surface morphology of FeNi bi-component, wherein a is a scanning electron micrograph of FeOx/NF and b is a scanning electron micrograph of (Fe/Ni) (O) OH/NF;
FIG. 4 is the effect of water plasma treatment on surface hydrophilicity, where a is the contact angle of NF that has not been subjected to water plasma treatment, and b is the contact angle of Ni (O) OH/NF catalyst;
FIG. 5 shows OER performance of an electrocatalyst prepared by the water plasma method, wherein a is NF and the oxygen evolution activity curve of Ni (O) OH/NF catalyst, and b is FeO x Oxygen evolution activity curve of the (Fe/Ni) (O) OH/NF catalyst.
Detailed Description
The invention provides a preparation method of a foam nickel-based electrolytic water oxygen evolution catalyst, which comprises the following steps:
and modifying the foam nickel by utilizing water plasma to obtain the foam nickel-based electrolytic water oxygen evolution catalyst.
In the present invention, the water plasma is obtained from a radio frequency plasma source.
In the invention, the radio frequency plasma source is preferably generated by the principle of inductive coupling, a quartz tube is used as a sample processing chamber, and a copper coil is wound outside the quartz tube.
In the present invention, the power of the rf plasma source is preferably 0 to 500W, more preferably 100 to 300W, and the power of the rf plasma source is not 0, and the frequency of the rf plasma source is preferably 13.56MHz.
In the invention, the preparation parameters of the water plasma comprise: the pressure of the cavity is preferably 10-50 Pa, more preferably 20-30 Pa, the gas atmosphere is preferably a mixed gas of argon and steam, the volume content of the steam in the mixed gas is preferably 2-100%, and the flow rate of the argon is preferably 10-30 sccm.
In the specific embodiment of the invention, the water plasma is preferably generated by a device shown in fig. 1, a quartz tube is used as a sample processing chamber, a copper coil is wound outside the quartz tube, a radio frequency plasma is generated by utilizing an inductive coupling principle, a mechanical pump is used for vacuumizing at the downstream of the quartz tube, argon is filled into the upstream of the quartz tube, the argon passes through a tank filled with purified water before being filled into the quartz tube, the temperature of a water storage tank is controlled to be 20-100 ℃, the argon is used as carrier gas to bring water vapor into the quartz tube, the flow rate of the argon and the temperature of the water storage tank are controlled, the pressure in the quartz tube is controlled to be 10-50 Pa, the radio frequency power supply is utilized to generate the water plasma, the volume content of the water vapor is 2-100 percent, and the power of the radio frequency power supply is adjusted to change the state of the water plasma.
In the present invention, the time for the modification is preferably 1 to 60 minutes, more preferably 10 to 30 minutes.
In the present invention, the nickel foam preferably further comprises a pretreatment before modification, and the pretreatment preferably comprises ultrasonic treatment with an acidic solution, water and absolute ethyl alcohol in sequence and then drying.
In the invention, the acidic solution is preferably a dilute hydrochloric acid solution, and the mass fraction of the dilute hydrochloric acid solution is preferably 1-10%.
In the present invention, the time of the ultrasonic treatment is preferably 15 minutes, and the ultrasonic treatment serves to remove impurities from the surface of the nickel foam.
In the present invention, the temperature of the drying is preferably 60℃and the time is preferably 2 hours.
In the present invention, the nickel foam preferably further comprises a supported iron oxide prior to modification, the supported iron oxide preferably comprising the steps of:
immersing the foam nickel in a soluble ferric salt solution and then drying to obtain the foam nickel with ferric salt loaded on the surface;
calcining the foam nickel with the surface loaded with ferric salt to obtain foam nickel (FeO) with the surface loaded with iron oxide x /NF)。
In the present invention, the nickel foam is preferably further subjected to pretreatment before being impregnated, and the pretreatment is preferably consistent with the above scheme, which is not described herein.
In the present invention, the soluble iron salt in the soluble iron salt solution preferably comprises ferric nitrate or ferric chloride.
In the present invention, the concentration of the soluble iron salt solution is preferably 1mol/L.
In the present invention, the time of the impregnation is preferably 20 minutes.
In the present invention, the temperature of the drying is preferably 60℃and the time is preferably 8 hours.
In the present invention, the temperature of the calcination is preferably 200 to 600 ℃, more preferably 400 ℃, and the time is preferably 0.5 to 2 hours, more preferably 1 hour.
The application of the foam nickel-based electrolytic water oxygen evolution catalyst is not particularly limited, and the method is well known to those skilled in the art.
In order to further illustrate the present invention, the following describes in detail the preparation of the foamed nickel-based electrolyzed water oxygen evolution catalyst provided by the present invention in conjunction with the examples, which should not be construed as limiting the scope of the present invention.
Example 1
(1) Foam nickel pretreatment:
the foam nickel is treated by dilute hydrochloric acid solution with the mass fraction of 1%, water and absolute ethyl alcohol for 15 minutes in sequence, and then dried in an oven at 60 ℃ for 2 hours to obtain clean foam nickel.
(2) Water plasma generation (device see fig. 1):
a. the quartz tube is used as a sample processing chamber, a copper coil is wound outside the quartz tube, and radio frequency plasma is generated by utilizing the principle of inductive coupling.
b. The mechanical pump vacuumizes the downstream of the quartz tube, argon is filled into the upstream of the quartz tube, the flow rate of the argon is 10-30 sccm, the argon passes through a tank filled with purified water before being filled into the quartz tube, the temperature of the water storage tank is controlled to be 20-100 ℃, and the argon is used as carrier gas to bring water vapor into the quartz tube. Controlling the flow of argon and the temperature of the water storage tank to ensure that the pressure in the quartz tube is 10-50 Pa.
c. The method comprises the steps of generating plasma by using a radio frequency power supply of 13.56MHz, generating water plasma by using a mixed gas of argon and water vapor in a quartz tube, wherein the volume content of the water vapor is 2%, and adjusting the power of the radio frequency power supply to change the state of the water plasma, wherein the power range is 0-500W.
(3) Water plasma treatment of samples:
a. the pretreated foam nickel is placed in a quartz tube at the position of a coil.
b. Vacuumizing, loading water vapor, and switching on a radio frequency power supply to generate water plasma. The power of the radio frequency power supply is 300W, the argon flow is 30ccm, the cavity pressure is 50Pa, and the treatment time is 1min.
c. And (3) after the clean foam nickel treatment is finished, obtaining the Ni (O) OH/NF catalyst.
The Ni (O) OH/NF catalyst prepared by the method is subjected to morphology analysis, hydrophilicity analysis and oxygen evolution performance test.
The morphology structure is shown in fig. 2, and fig. 2 shows the influence of water plasma treatment on the surface morphology of NF, wherein a is a scanning electron microscope photograph of NF which is not subjected to water plasma treatment, and the surface is smooth; b is a scanning electron microscope photograph of Ni (O) OH/NF, and a large number of nano particles exist on the surface. Through scanning electron microscope photo analysis, after clean foam nickel is treated by water plasma, the foam nickel still maintains a three-dimensional framework structure, and a large amount of nano particles are loaded on the smooth surface of the foam nickel.
The hydrophilicity analysis is shown in fig. 4, wherein a is the contact angle of NF which is not subjected to water plasma treatment, is 118 degrees, has certain hydrophobicity, b is the contact angle of Ni (O) OH/NF catalyst, the contact angle is 0 degrees, and the hydrophilicity is obviously improved.
The oxygen evolution performance test is shown in FIG. 5, wherein a is the oxygen evolution activity curve of NF and Ni (O) OH/NF catalyst, and it is known that the Ni (O) OH/NF catalyst obtained after water plasma treatment is 10 mA.cm -2 The overpotential at current density was 400mV and Ni (O) OH/NF was reduced by 92mV from the untreated foam nickel overpotential.
Example 2
(1) Foam nickel pretreatment:
a. the foam nickel is treated by dilute hydrochloric acid solution with the mass fraction of 1%, water and absolute ethyl alcohol for 15 minutes in sequence, and then dried in an oven at 60 ℃ for 2 hours to obtain clean foam nickel.
b. Putting clean foam nickel into 20mL of 1M ferric nitrate solution, immersing for 20min, taking out, drying in an oven at 60 ℃ for 8h to obtain foam nickel with ferric salt loaded on the surface, calcining at 400 ℃ for 1h to obtain foam nickel (FeO) with iron oxide loaded on the surface x /NF)。
(2) Water plasma generation (device see fig. 1):
a. the quartz tube is used as a sample processing chamber, a copper coil is wound outside the quartz tube, and radio frequency plasma is generated by utilizing the principle of inductive coupling.
b. The mechanical pump vacuumizes the downstream of the quartz tube, argon is filled into the upstream of the quartz tube, the flow rate of the argon is 10-30 sccm, the argon passes through a tank filled with purified water before being filled into the quartz tube, the temperature of the water storage tank is controlled to be 20-100 ℃, and the argon is used as carrier gas to bring water vapor into the quartz tube. Controlling the flow of argon and the temperature of the water storage tank to ensure that the pressure in the quartz tube is 10-50 Pa.
c. The method comprises the steps of generating plasma by using a radio frequency power supply of 13.56MHz, generating water plasma by using a mixed gas of argon and water vapor in a quartz tube, wherein the volume content of the water vapor is 2%, and adjusting the power of the radio frequency power supply to change the state of the water plasma, wherein the power range is 0-500W.
(3) Water plasma treatment of samples:
a. foam nickel (FeO) loaded with iron oxide x /NF) is placed in the quartz tube at the location of the coil.
b. Vacuumizing, loading water vapor, and switching on a radio frequency power supply to generate water plasma. The power of the radio frequency power supply is 300W, the argon flow is 30ccm, the cavity pressure is 50Pa, and the treatment time is 1min.
c. After the treatment of the foam nickel loaded with the ferric oxide is finished, the (Fe/Ni) (O) OH/NF catalyst is obtained.
FIG. 3 is a graph showing the effect of water plasma treatment on FeNi bicomponent surface morphology, wherein a is FeO x Scanning electron microscope photograph of/NF, the surface is the structure formed by the rugged particle; b is a scanning electron microscope photograph of (Fe/Ni) (O) OH/NF, the surface is of a large number of sheet structures, after the foam nickel loaded with ferric oxide is treated by water plasma, the foam nickel still maintains a three-dimensional framework structure, and a large number of sheet structures exist on the surface.
Oxygen evolution performance test was carried out on the (Fe/Ni) OOH/NF catalyst prepared by the method, and the (Fe/Ni) (O) OH/NF catalyst obtained by water plasma treatment is 10 mA.cm in FIG. 5 b -2 The overpotential at current density was 246mV, and the (Fe/Ni) (O) OH/NF catalyst was reduced by 97mV from the foam nickel overpotential of the iron oxide-loaded prior to water plasma treatment.
Example 3
(1) Foam nickel pretreatment:
a. the foam nickel is treated by dilute hydrochloric acid solution with the mass fraction of 1%, water and absolute ethyl alcohol for 15 minutes in sequence, and then dried in an oven at 60 ℃ for 2 hours to obtain clean foam nickel.
b. Putting clean foam nickel into 20mL of 1M ferric nitrate solution, immersing for 20min, taking out, drying in an oven at 60 ℃ for 8h to obtain foam nickel with ferric salt loaded on the surface, calcining at 400 ℃ for 1h to obtain foam nickel (FeO) with iron oxide loaded on the surface x /NF)。
(2) Water plasma generation (device see fig. 1):
a. the quartz tube is used as a sample processing chamber, a copper coil is wound outside the quartz tube, and radio frequency plasma is generated by utilizing the principle of inductive coupling.
b. The mechanical pump vacuumizes the downstream of the quartz tube, argon is filled into the upstream of the quartz tube, the flow rate of the argon is 10-30 sccm, the argon passes through a tank filled with purified water before being filled into the quartz tube, the temperature of the water storage tank is controlled to be 20-100 ℃, and the argon is used as carrier gas to bring water vapor into the quartz tube. Controlling the flow of argon and the temperature of the water storage tank to ensure that the pressure in the quartz tube is 10-50 Pa.
c. The method comprises the steps of generating plasma by using a radio frequency power supply of 13.56MHz, generating water plasma by using a mixed gas of argon and water vapor in a quartz tube, wherein the volume content of the water vapor is 10%, and adjusting the power of the radio frequency power supply to change the state of the water plasma, wherein the power range is 0-500W.
(3) Water plasma treatment of samples:
a. foam nickel (FeO) loaded with iron oxide x /NF) is placed in the quartz tube at the location of the coil.
b. Vacuumizing, loading water vapor, and switching on a radio frequency power supply to generate water plasma. The power of the radio frequency power supply is 300W, the argon flow is 30ccm, the cavity pressure is 50Pa, and the treatment time is 60min.
c. After the treatment of the foam nickel loaded with the ferric oxide is finished, the (Fe/Ni) (O) OH/NF catalyst is obtained.
Oxygen evolution performance test is carried out on the (Fe/Ni) (O) OH/NF catalyst prepared by the method, and the (Fe/Ni) (O) OH/NF catalyst obtained after water plasma treatment is 10 mA.cm -2 Overpotential at current densityThe (Fe/Ni) OOH/NF catalyst had a 63mV reduction in the nickel overpotential of the iron oxide-loaded foam prior to water plasma treatment of 280 mV.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the foam nickel-based electrolytic water oxygen evolution catalyst is characterized by comprising the following steps of:
and modifying the foam nickel by utilizing water plasma to obtain the foam nickel-based electrolytic water oxygen evolution catalyst.
2. The method of claim 1, wherein the water plasma is derived from a radio frequency plasma source.
3. The method according to claim 2, wherein the power of the rf plasma source is 0 to 500W, the power of the rf plasma source is not 0, and the frequency of the rf plasma source is 13.56MHz.
4. The method according to claim 1 or 2, wherein the parameters of the water plasma preparation include: the pressure of the cavity is 10-50 Pa, the gas atmosphere is a mixed gas of argon and steam, the volume content of the steam in the mixed gas is 2-100%, and the flow of the argon is 10-30 sccm.
5. The method according to claim 1, wherein the modification time is 1 to 60 minutes.
6. The method of claim 1, wherein the nickel foam further comprises a pretreatment prior to modification, the pretreatment comprising ultrasonic treatment with an acidic solution, water and absolute ethanol followed by drying.
7. The preparation method according to claim 6, wherein the acidic solution is a dilute hydrochloric acid solution, and the mass fraction of the dilute hydrochloric acid solution is 1% -10%.
8. The method of claim 1, wherein the nickel foam further comprises a supported iron oxide prior to modification, the supported iron oxide comprising the steps of:
immersing the foam nickel in a soluble ferric salt solution and then drying to obtain the foam nickel with ferric salt loaded on the surface;
and calcining the foam nickel with the ferric salt loaded on the surface to obtain the foam nickel with the ferric oxide loaded on the surface.
9. The method according to claim 8, wherein the calcination is carried out at a temperature of 200 to 600 ℃ for a time of 0.5 to 2 hours.
10. The method of claim 8, wherein the soluble iron salt in the soluble iron salt solution comprises ferric nitrate or ferric chloride.
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| CN116043256A (en) * | 2022-11-11 | 2023-05-02 | 石河子大学 | Preparation method for in-situ synthesis of hydroxyl oxide by solution plasma |
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| CN116043256A (en) * | 2022-11-11 | 2023-05-02 | 石河子大学 | Preparation method for in-situ synthesis of hydroxyl oxide by solution plasma |
| CN116043256B (en) * | 2022-11-11 | 2024-05-07 | 石河子大学 | Preparation method for in-situ synthesis of hydroxyl oxide by solution plasma |
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