CN112007647A - Nano nickel iron hydroxide film and preparation method and application thereof - Google Patents
Nano nickel iron hydroxide film and preparation method and application thereof Download PDFInfo
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- CN112007647A CN112007647A CN202010824158.6A CN202010824158A CN112007647A CN 112007647 A CN112007647 A CN 112007647A CN 202010824158 A CN202010824158 A CN 202010824158A CN 112007647 A CN112007647 A CN 112007647A
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 235000014413 iron hydroxide Nutrition 0.000 title claims abstract description 18
- 229910000990 Ni alloy Inorganic materials 0.000 claims abstract description 31
- 229910003298 Ni-Ni Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 27
- 239000002086 nanomaterial Substances 0.000 claims abstract description 26
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 14
- 150000002505 iron Chemical class 0.000 claims abstract description 10
- 230000001590 oxidative effect Effects 0.000 claims abstract description 10
- AZCFACRUWNEBDG-UHFFFAOYSA-N gallium nickel Chemical compound [Ni].[Ga] AZCFACRUWNEBDG-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 239000000126 substance Substances 0.000 claims abstract description 5
- 239000010408 film Substances 0.000 claims description 79
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- 229910052759 nickel Inorganic materials 0.000 claims description 23
- 230000007797 corrosion Effects 0.000 claims description 19
- 238000005260 corrosion Methods 0.000 claims description 19
- 238000000137 annealing Methods 0.000 claims description 18
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 11
- 229910052733 gallium Inorganic materials 0.000 claims description 11
- QJSRJXPVIMXHBW-UHFFFAOYSA-J iron(2+);nickel(2+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Fe+2].[Ni+2] QJSRJXPVIMXHBW-UHFFFAOYSA-J 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000011248 coating agent Substances 0.000 claims description 7
- 238000000576 coating method Methods 0.000 claims description 7
- 239000012535 impurity Substances 0.000 claims description 7
- 239000010409 thin film Substances 0.000 claims description 7
- 239000012670 alkaline solution Substances 0.000 claims description 5
- 239000011148 porous material Substances 0.000 claims description 5
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 2
- 230000008018 melting Effects 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 6
- -1 nickel hydroxide nickel iron Chemical compound 0.000 abstract 2
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 19
- 239000000243 solution Substances 0.000 description 17
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical class [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 15
- 229910021641 deionized water Inorganic materials 0.000 description 15
- 235000019441 ethanol Nutrition 0.000 description 15
- 239000007788 liquid Substances 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- 238000005406 washing Methods 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 11
- 238000007254 oxidation reaction Methods 0.000 description 11
- 239000002184 metal Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052742 iron Inorganic materials 0.000 description 6
- 239000007769 metal material Substances 0.000 description 6
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 238000007605 air drying Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 238000010408 sweeping Methods 0.000 description 5
- 229910052723 transition metal Inorganic materials 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000004502 linear sweep voltammetry Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006056 electrooxidation reaction Methods 0.000 description 2
- 239000007783 nanoporous material Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical class [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical class [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Chemical class 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical class [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical class [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000010949 copper Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000000157 electrochemical-induced impedance spectroscopy Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 239000011572 manganese Chemical class 0.000 description 1
- 229910052748 manganese Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 150000003346 selenoethers Chemical class 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- B01J35/23—
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/023—Coating using molten compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- 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
Abstract
The invention discloses a nanometer nickel hydroxide nickel iron film and a preparation method and application thereof, wherein the nanometer nickel hydroxide nickel iron film is distributed with a porous structure and has a chemical component of NixFey(OH)2(ii) a Wherein x is>0，y>0. The preparation method comprises the following steps: s1, preparing gallium-nickel alloy; s2, preparing the Ni film with the surface containing the nano-structure Ni from the gallium-nickel alloy prepared in the step S1 by a dealloying method, and oxidizing the nano-structure Ni on the surface into Ni (OH) by cyclic voltammetry2Obtaining Ni-Ni (OH)2A film; s3, mixing the Ni-Ni (OH) prepared in the step S22And placing the film in an iron salt solution, and reacting to obtain the nano nickel iron hydroxide film, wherein the nano Ni has a three-dimensional and bicontinuous structure. The material contains a plurality of active sites, the preparation process is simple, the requirement on the preparation process is low, the product structure is stable, and the process is green and pollution-free.
Description
Technical Field
The invention relates to the technical field of electrochemical catalytic oxidation, in particular to a nano nickel iron hydroxide film and a preparation method and application thereof.
Background
Due to rapid development of industry and agriculture, petroleum and coal resources are gradually exhausted, and combustible energy (petroleum and coal) cannot solve the problem of pollution and damage to human living environment in the combustion process. The development of a clean combustible energy with high energy is imminent, and among various new energy sources, hydrogen energy is one of the most promising alternative energy sources for reducing the use of fossil energy. Currently, the main routes for producing hydrogen energy are three categories, thermochemical reforming, electrolysis of water and photolysis of water, where electrochemical decomposition of water is considered to be one of the most promising technologies that produce clean hydrogen energy and can be continuously developed. In the whole water decomposition process, in order to improve the reaction rate and the energy conversion efficiency, it is critical to improve the Oxygen evolution reaction at the anode and the hydrogen evolution reaction efficiency at the cathode, and the overall reaction rate is more dependent on the Oxygen Evolution Reaction (OER) catalyst. The oxygen evolution reaction needs to be carried out at a large overpotential, which would result in a large energy loss if a suitable catalyst were absent during the reaction.
The nano porous metal material has received wide attention in various fields because of the advantages of both nano materials and porous materials, such as significant surface effect, high specific surface area, high porosity, low density, stable structure, corrosion resistance and fatigue resistance. In recent years, nanoporous metallic materials have been increasingly usedIn the fields of energy storage, catalysis and the like. Nanoporous metallic materials can be classified into noble metal-based materials (such as RuO) and non-noble metal-based materials according to the properties of the metal2And IrO2Etc.) are generally used as standard electrocatalysts for oxygen evolution reactions due to their excellent catalytic properties, but their scarcity and high cost also greatly limit their applications. Therefore, the research and development of non-noble metal base materials with abundant reserves, high catalytic efficiency and stable performance on the earth as the oxygen evolution reaction catalyst has important significance. In the non-noble metal base material, the first series of transition metals have abundant reserves and low cost, and simultaneously have catalytic activity for oxygen evolution reaction, so the first series of transition metals have good application prospect in the development process of the non-noble metal base material. Among the first series of transition metals, iron, cobalt, nickel, copper and manganese are the most widely studied transition metal-based catalysts, and for example, oxides, sulfides, selenides, phosphides, etc. thereof have been demonstrated to have excellent catalytic performance in oxygen evolution reactions. However, the non-noble metal-based materials of the prior art have limited catalytic activity due to their single composition.
In the prior art, methods for preparing nano-porous metal mainly comprise a template method and a dealloying method. Wherein the template method is to deposit the target metal into the pores of the template by physical or chemical methods, and then remove the template by etching, dissolving, annealing, etc. to obtain an inverse replica corresponding to the template material (Velev, O.D. et al. Nature 389, 447-. According to the selected template, the material with highly ordered structure can be prepared, but the structure and the appearance of the material are limited by the selected template, and the material has the disadvantages of complex process, more variables and poor controllability. The dealloying method is to selectively remove one or more components in the alloy by free etching or electrochemical etching by utilizing the chemical property difference of different metals in the alloy to form the nano-porous material (J.Erlebacher, et al./Nature,2001,401, 450-. Compared with the template method, the dealloying method has the advantages of simple operation, good repeatability, uniform product structure and high specific surface area. During the corrosion process, the unetched metal components form a three-dimensional continuous network porous structure through diffusion, migration, aggregation and the like.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the invention provides the nano nickel iron hydroxide film which has more active sites and has important popularization and application values in the field of electrocatalysis.
The invention also provides a preparation method of the nano nickel iron hydroxide film.
The invention also provides an application of the film.
According to the nano nickel hydroxide iron film of the first embodiment of the invention, the nano nickel hydroxide iron film is distributed with a three-dimensional and bicontinuous pore structure and has a chemical component of NixFey(OH)2(ii) a Wherein x + y is 1, x>0，y>0。
The nanometer nickel iron hydroxide film according to the embodiment of the invention has at least the following beneficial effects: the ferronickel hydroxide with the pore structure has more active sites, so that the reaction efficiency of the OER is improved; the nano-pore structure is combined with the nickel-iron hydroxide, and the performance and structural advantages of the nickel-iron hydroxide and the nano-porous metal are utilized to generate the electrocatalysis synergistic effect, so that the high-efficiency OER electrocatalyst is developed; compared with single nickel, iron and cobalt hydroxides in the prior art, the transition metal hydroxide containing nickel and iron has higher catalytic activity of oxygen evolution reaction.
The preparation method according to the second aspect embodiment of the present invention comprises the steps of:
s1, preparing gallium-nickel alloy;
s2, preparing the Ni film with the surface containing the nano-structure Ni from the gallium-nickel alloy prepared in the step S1 by a dealloying method, and oxidizing the nano-structure Ni on the surface into Ni (OH) by cyclic voltammetry2Obtaining Ni-Ni (OH)2A film;
s3, mixing the Ni-Ni (OH) prepared in the step S22And placing the film in an iron salt solution, and reacting to obtain the nano nickel iron hydroxide film, wherein the nano Ni has a three-dimensional and bicontinuous structure.
According to some embodiments of the present invention, the preparing of the gallium-nickel alloy in step S1 specifically includes: melting gallium, coating the melted gallium on a nickel sheet, and performing annealing treatment at 100-250 ℃ to obtain Ga-Ni alloy; preferably, the gallium on the surface of the nickel sheet is coated; more preferably, the volume of the molten gallium coated on the surface of each gram of gallium is 0.5-50 ml.
According to some embodiments of the invention, the time of the fallback processing is 1-6 h.
According to some embodiments of the invention, the dealloying in step S2 comprises the steps of: placing the Ga-Ni alloy in an alkaline solution for corrosion treatment for 2-10 h; preferably 6 h; preferably, the addition amount of the alkaline solution is 25-2000 ml per gram of nickel.
According to some embodiments of the invention, the pH of the alkaline solution is ≧ 13.
According to some embodiments of the invention, the cyclic voltammetry in step S2 comprises the steps of: under alkaline environment, taking a Ni film with a nano structure Ni on the surface as a working electrode, and oxidizing the porous nano structure Ni on the surface into Ni (OH) within the voltage range of 1.0-1.6V2。
According to some embodiments of the present invention, the alkaline environment is 0.1 to 1.5mol/L of a strong alkaline solution (such as a potassium hydroxide solution); preferably, the strong base solution has OH-The concentration of (2) is 1 mol/L.
According to some embodiments of the invention, the cyclic voltammetry is performed at a scanning speed of 20-100 mV/s for 10-100 cycles; preferably, the scanning speed is 20-80 mV/s.
According to some embodiments of the invention, the Fe in the iron salt in step S33+The concentration of (a) is between 0.1 and 1 mol/L; preferably, the addition amount of the iron salt is 25-2000 ml of iron salt solution added per gram of nickel.
According to some embodiments of the invention, the iron salt is selected from FeCl3Or Fe2(SO4)3。
According to some embodiments of the present invention, the,the step S3 further comprises mixing Ni-Ni (OH)2And placing the film in absolute ethyl alcohol, removing impurities by ultrasonic treatment, and then placing the film in an iron salt solution.
According to some embodiments of the present invention, the reaction time in the step S3 is 3-12 h.
According to some embodiments of the invention, the sonication time is 30-60 min.
The method according to the embodiment of the invention has at least the following beneficial effects: the preparation method is simple and convenient to operate, does not need toxic organic reagents in the preparation process, and is green and environment-friendly; combining the metal with the nanometer structure with the nickel-iron hydroxide, and generating the electrocatalysis synergistic effect by utilizing the properties and the structure advantages of the nickel-iron hydroxide and the nanometer porous metal, thereby developing the high-efficiency OER electrocatalyst; the preparation method of the scheme of the invention has the advantages of mild reaction conditions, low requirements on preparation process, stable product structure and good application prospect.
According to the application of the third aspect of the embodiment of the invention, the nanometer nickel iron hydroxide film is applied to the preparation of the oxygen evolution reaction catalyst.
According to some embodiments of the invention, the nano nickel iron hydroxide film is used in hydrogen gas preparation.
The application of the embodiment of the invention has at least the following beneficial effects: the nanometer nickel iron hydroxide film of the embodiment of the invention can be used as an OER electrocatalyst with excellent performance and has good application prospect in the field of hydrogen preparation.
Additional aspects and advantages of the invention will be set forth in part in the description which follows and, in part, will be obvious from the description, or may be learned by practice of the invention.
Drawings
FIG. 1 is an SEM image of a Ni film containing nano-structured Ni obtained after dealloying in example 2 of the present invention;
FIG. 2 is an XRD pattern of a Ni film containing nanostructured Ni obtained after dealloying in example 2 of the present invention;
FIG. 3 shows Ni-Ni (OH) produced in example 2 of the present invention2XRD pattern of the film;
FIG. 4 shows Ni-Ni (OH) after electrochemical oxidation for 100 cycles in example 2 of the present invention2SEM picture of (1);
FIG. 5 is the LSV curves of the nano-sized nickel iron hydroxide film obtained in example 2 of the present invention and the nickel hydroxide film obtained in comparative example 1;
FIG. 6 is a PEIS curve of the nano nickel iron hydroxide film obtained in example 2 of the present invention and the nickel hydroxide film obtained in comparative example 1.
Detailed Description
In order to explain technical contents, achieved objects, and effects of the present invention in detail, the following description is made with reference to the accompanying drawings in combination with the embodiments. The test methods used in the examples are all conventional methods unless otherwise specified; the materials, reagents and the like used are commercially available reagents and materials unless otherwise specified.
The first embodiment of the invention is as follows: nixFey(OH)2The preparation method comprises the following steps:
(1) heating Ga at 40 ℃ to obtain 5ml of liquid Ga, uniformly coating the liquid Ga on 2g of nickel sheets (namely completely covering the Ni sheets), and naturally air-drying the liquid Ga overnight to obtain a Ga-coated nickel film;
(2) putting the Ga-coated nickel film into a vacuum drying oven for annealing treatment, wherein the annealing temperature is 120 ℃, and the annealing time is 6 hours, so as to obtain the Ga-Ni alloy;
(3) putting the Ga-Ni alloy obtained in the step (2) into 200ml of 0.2M NaOH corrosion solution for dealloying corrosion, wherein the dealloying corrosion time is 6h, then washing the Ga-Ni alloy with ethanol and deionized water for three times respectively, and drying the washed Ga-Ni alloy to obtain the Ni film with the surface containing the nano-structure Ni;
(4) oxidation of Ni films with nanostructured Ni on their surface to Ni-Ni (OH) by repeated cyclic voltammetry2: oxidizing the Ni film with the surface containing the nano-structure Ni obtained in the step (3) as a working electrode in a 1M KOH solution; the sweeping speed is 50mV s-1Voltage interval is 1-1.6V, number of turns is 100, after oxidation is finished, washing with ethanol and deionized water for three times respectively to obtain Ni-Ni (OH)2；
(5) The Ni-Ni (OH) obtained in the step (4)2Placing in absolute ethyl alcohol (the dosage needs to be over Ni-Ni (OH))2Generally using 20-100 ml, 50ml in the embodiment) for 30min to remove surface impurities;
(6) placing the film obtained in the step (5) in 0.5M FeCl3Reacting in 200ml of solution at room temperature for 6h, washing with ethanol and deionized water for three times respectively to obtain NixFey(OH)2。
The second embodiment of the invention is as follows: nixFey(OH)2The preparation method comprises the following steps:
(1) heating Ga at 40 ℃ to obtain 1ml of liquid Ga, uniformly coating the liquid Ga on 0.1g of nickel sheets (namely completely covering the Ni sheets), and naturally air-drying the liquid Ga overnight to obtain a Ga-coated nickel film;
(2) putting the Ga-coated nickel film into a vacuum drying oven for annealing treatment, wherein the annealing temperature is 150 ℃, and the annealing time is 6 hours, so as to obtain the Ga-Ni alloy;
(3) and (3) putting the Ga-Ni alloy obtained in the step (2) into 50ml of 0.2M NaOH corrosion solution for dealloying corrosion, wherein the dealloying corrosion time is 6h, then washing the Ga-Ni alloy with ethanol and deionized water for three times respectively, and drying the washed Ga-Ni alloy to obtain the Ni film with the surface containing the nano-structure Ni.
(4) Oxidation of Ni films with nanostructured Ni on their surface to Ni-Ni (OH) by repeated cyclic voltammetry2: oxidizing the Ni film with the surface containing the nano-structure Ni obtained in the step (3) as a working electrode in a 1M KOH solution; the sweeping speed is 50mV s-1Voltage interval is 1-1.6V, number of turns is 100, after oxidation is finished, washing with ethanol and deionized water for three times respectively to obtain Ni-Ni (OH)2。
(5) The Ni-Ni (OH) obtained in the step (4)2Ultrasonic treating in anhydrous alcohol (20 ml in this example) for 30min to remove surface impurities;
(6) placing the film obtained in the step (5) in 0.5M FeCl3Reacting in 50ml of solution at room temperature for 6h, washing with ethanol and deionized water for three times respectively to obtain NixFey(OH)2。
The third implementation of the invention is as follows: nixFey(OH)2The preparation method comprises the following steps:
(1) heating Ga to 40 ℃ to obtain 2.5ml of liquid Ga, uniformly coating the liquid Ga on a 1g nickel sheet, and naturally air-drying the liquid Ga overnight to obtain a Ga-coated nickel film;
(2) putting the Ga-coated nickel film into a vacuum drying oven for annealing treatment, wherein the annealing temperature is 180 ℃, and the annealing time is 6 hours, so as to obtain the Ga-Ni alloy;
(3) putting the Ga-Ni alloy obtained in the step (2) into 100ml of 0.2M NaOH corrosion solution for dealloying corrosion, wherein the dealloying corrosion time is 6h, then washing the Ga-Ni alloy with ethanol and deionized water for three times respectively, and drying to obtain the Ni film with the surface containing the nano-structure Ni;
(4) oxidation of Ni films with nanostructured Ni on their surface to Ni-Ni (OH) by repeated cyclic voltammetry2: oxidizing the Ni film with the surface containing the nano-structure Ni obtained in the step (3) as a working electrode in a 1M KOH solution; the sweeping speed is 50mV s-1Voltage interval is 1-1.6V, number of turns is 100, after oxidation is finished, washing with ethanol and deionized water for three times respectively to obtain the Ni-Ni (OH) with the nano structure2；
(5) The Ni-Ni (OH) obtained in the step (4)2Ultrasonic treating in anhydrous ethanol (80 ml in this example) for 30min to remove surface impurities;
(6) placing the film obtained in the step (5) in 0.5M FeCl3Reacting for 6 hours at room temperature in 100ml of solution, washing with ethanol and deionized water for three times respectively to obtain NixFey(OH)2。
The fourth embodiment of the invention is as follows: nixFey(OH)2The preparation method comprises the following steps:
(1) heating Ga to 40 ℃ to obtain 1.5ml of liquid Ga, uniformly coating the liquid Ga on a 0.5g nickel sheet, and naturally air-drying the liquid Ga overnight to obtain a Ga-coated nickel film;
(2) putting the Ga-coated nickel film into a vacuum drying oven for annealing treatment, wherein the annealing temperature is 150 ℃, and the annealing time is 6 hours, so as to obtain the Ga-Ni alloy;
(3) putting the Ga-Ni alloy obtained in the step (2) into 75ml of 0.2M NaOH corrosion solution for dealloying corrosion, wherein the dealloying corrosion time is 6h, then washing the Ga-Ni alloy with ethanol and deionized water for three times respectively, and drying the washed Ga-Ni alloy to obtain the Ni film with the surface containing the nano-structure Ni;
(4) oxidation of Ni films with nanostructured Ni on their surface to Ni-Ni (OH) by repeated cyclic voltammetry2: oxidizing the Ni film with the surface containing the nano-structure Ni obtained in the step (3) as a working electrode in a 1M KOH solution; the sweeping speed is 50mV s-1Voltage interval is 1-1.6V, number of turns is 100, after oxidation is finished, washing with ethanol and deionized water for three times respectively to obtain the Ni-Ni (OH) with the nano structure2；
(5) The Ni-Ni (OH) obtained in the step (4)2Ultrasonic treating in anhydrous alcohol (100 ml in this example) for 30min to remove surface impurities;
(6) placing the film obtained in the step (5) in 0.5M FeCl375ml of the solution reacts for 3 hours at room temperature, and is washed three times by ethanol and deionized water respectively to obtain NixFey(OH)2。
The fifth embodiment of the invention is as follows: nixFey(OH)2The preparation method comprises the following steps:
(1) heating Ga at 40 ℃ to obtain 3ml of liquid gallium, uniformly coating the liquid gallium on a 1.2g nickel sheet, and naturally air-drying the liquid gallium overnight to obtain a Ga-coated nickel film;
(2) putting the Ga-coated nickel film into a vacuum drying oven for annealing treatment, wherein the annealing temperature is 150 ℃, and the annealing time is 6 hours, so as to obtain the Ga-Ni alloy;
(3) putting the Ga-Ni alloy obtained in the step (2) into 150ml of 0.2M NaOH corrosion solution for dealloying corrosion, wherein the dealloying corrosion time is 6h, then washing the Ga-Ni alloy with ethanol and deionized water for three times respectively, and drying the washed Ga-Ni alloy to obtain the Ni film with the surface containing the nano-structure Ni;
(4) oxidation of Ni films with nanostructured Ni on their surface to Ni-Ni (OH) by repeated cyclic voltammetry2: oxidizing the Ni film with the surface containing the nano-structure Ni obtained in the step (3) as a working electrode in a 1M KOH solution; the sweeping speed is 50mV s-1Voltage interval is 1-1.6V, number of turns is 100, after oxidation is finished, washing with ethanol and deionized water for three times respectively to obtain the Ni-Ni (OH) with the nano structure2；
(5) The Ni-Ni (OH) obtained in the step (4)2Ultrasonic treating in anhydrous alcohol (60 ml in this example) for 30min to remove surface impurities;
(6) placing the film obtained in the step (5) in 0.5M FeCl3Reacting in 150ml of solution at room temperature for 12h, washing with ethanol and deionized water for three times respectively to obtain NixFey(OH)2。
And (3) obtaining the required working electrode, and testing the electrocatalysis performance by adopting a three-electrode system, wherein the counter electrode is a Pt sheet electrode, and the reference electrode is an Ag/AgCl electrode. Taking Ni film containing nanostructured Ni prepared in the above examples 1-5, Ni-Ni (OH)2Film and NixFey(OH)2Scanning Electron Microscope (SEM) analysis and X-ray powder diffractometer (XRD) analysis were performed on the film, wherein the SEM image of the Ni film containing nano-structure Ni prepared in example 2 is shown in FIG. 1, the XRD image is shown in FIG. 2, and Ni-Ni (OH)2The XRD pattern of the film is shown in figure 3; Ni-Ni (OH)2The SEM image of the film is shown in FIG. 4. The product structures of other embodiments are similar to those of embodiment 2, and are not described in detail herein to avoid redundancy. As can be seen in fig. 1, the structure after dealloying is a nanostructure; it can be seen from fig. 2 that after dealloying, gallium is completely corroded; as can be seen from fig. 3, a trace amount of nickel hydroxide was generated after electrochemical oxidation; from FIG. 4, it is clear that Ni (OH) is formed on the surface of nickel2。
The first comparative example of the invention is as follows: the preparation method of the nano nickel hydroxide film is different from the second embodiment in that: step (5) is not included.
The nano nickel hydroxide iron films obtained in the above examples 1 to 5 and the nano nickel hydroxide film obtained in the comparative example 1 were subjected to the following processesThe electrochemical performance of the product prepared in the above embodiment is tested by a three-electrode system by using a working electrode prepared by a conventional method, a saturated Ag/AgCl electrode as a reference electrode and a Pt sheet as an electrode pair electrode. The electrochemical test is carried out by an electrochemical workstation, oxygen is firstly introduced before the test, and the OER electrochemical performance test is carried out in 1mol/L KOH solution saturated by oxygen. In the test process, firstly, a Cyclic Voltammogram (CV) is scanned, the scanning interval is 1 to 1.6V vs. Ag/AgCl, and the scanning speed is 50 mV/s; and then carrying out linear sweep voltammetry test, wherein the sweep interval is 0.2-1.0V vs. Ag/AgCl, and the sweep rate is 5 mV/s. Wherein the Linear Sweep Voltammetry (LSV) curve and the electrochemical impedance spectroscopy (PEIS) curve of the working electrode prepared from the nickel hydroxide thin film prepared in the comparative example 1 and the nickel hydroxide thin film prepared in the example 2 are shown in FIGS. 5 and 6, and it can be seen from FIGS. 5 and 6 that the iron-doped nickel hydroxide thin film prepared by the embodiment of the present invention is significantly superior in catalysis to Ni-Ni (OH)2A film.
The room temperature refers to a condition without additional heating, and is preferably 20-30 ℃; the temperature adopted in the embodiment of the invention is 25 ℃, and the scheme of the invention can be realized in the room temperature range.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all equivalent changes made by using the contents of the present specification and the drawings, or applied directly or indirectly to the related technical fields, are included in the scope of the present invention.
Claims (10)
1. A nanometer nickel iron hydroxide film is characterized in that: the nano nickel hydroxide film is distributed with a three-dimensional and double-continuous pore structure and has a chemical component of NixFey(OH)2(ii) a Wherein x + y is 1, x>0，y>0。
2. A method for preparing a nano nickel iron hydroxide film according to claim 1, which is characterized by comprising the following steps: the method comprises the following steps:
s1, preparing gallium-nickel alloy;
s2, preparing the Ni film with the surface containing the nano-structure Ni from the gallium-nickel alloy prepared in the step S1 by a dealloying method, and oxidizing the nano-structure Ni on the surface into Ni (OH) by cyclic voltammetry2Obtaining Ni-Ni (OH)2A film;
s3, mixing the Ni-Ni (OH) prepared in the step S22And placing the film in an iron salt solution, and reacting to obtain the nano nickel iron hydroxide film, wherein the nano Ni has a three-dimensional and bicontinuous structure.
3. The method for preparing nano nickel iron hydroxide film according to claim 2, characterized in that: the preparation of the gallium-nickel alloy in the step S1 specifically includes: melting gallium, coating the melted gallium on a nickel sheet, and performing annealing treatment at 100-250 ℃ to obtain Ga-Ni alloy; preferably, the time of the withdrawal treatment is 1-6 h.
4. The method for preparing nano nickel iron hydroxide film according to claim 2, characterized in that: the dealloying method in the step S2 comprises the following steps: and placing the Ga-Ni alloy in an alkaline solution for corrosion treatment for 2-10 h.
5. The method for preparing a nano nickel iron hydroxide thin film according to any one of claims 2 to 4, characterized in that: the cyclic voltammetry in step S2 includes the following steps: under alkaline environment, taking a Ni film with a nano structure Ni on the surface as a working electrode, and oxidizing the porous nano structure Ni on the surface into Ni (OH) within the voltage range of 1.0-1.6V2。
6. The method for preparing nanometer nickel iron hydroxide film according to claim 5, characterized in that: the scanning speed in the cyclic voltammetry is 20-100 mV/s, and the number of cycle turns is 10-100; preferably, the scanning speed is 20-80 mV/s.
7. The method for preparing a nano nickel iron hydroxide thin film according to any one of claims 2 to 4, characterized in that: in the iron salt in the step S3Fe3+The concentration of (b) is between 0.1 and 1 mol/L.
8. The method for preparing a nano nickel iron hydroxide thin film according to any one of claims 2 to 4, characterized in that: the step S3 further comprises mixing Ni-Ni (OH)2Placing the film in absolute ethyl alcohol, removing impurities by ultrasonic treatment, and then placing the film in an iron salt solution; preferably, the ultrasonic time is 30-60 min.
9. Use of the nano nickel iron hydroxide thin film according to claim 1 in the preparation of an oxygen evolution reaction catalyst.
10. Use of the nano nickel iron hydroxide film according to claim 1 in hydrogen gas production.
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