CN112981441A - Preparation method and application of self-supporting type iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode - Google Patents
Preparation method and application of self-supporting type iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode Download PDFInfo
- Publication number
- CN112981441A CN112981441A CN202110159597.4A CN202110159597A CN112981441A CN 112981441 A CN112981441 A CN 112981441A CN 202110159597 A CN202110159597 A CN 202110159597A CN 112981441 A CN112981441 A CN 112981441A
- Authority
- CN
- China
- Prior art keywords
- iron
- oxygen evolution
- self
- aqueous solution
- nickel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title description 59
- 239000001301 oxygen Substances 0.000 title description 59
- 229910052760 oxygen Inorganic materials 0.000 title description 59
- QHASIAZYSXZCGO-UHFFFAOYSA-N selanylidenenickel Chemical compound [Se]=[Ni] QHASIAZYSXZCGO-UHFFFAOYSA-N 0.000 title description 36
- 239000002131 composite material Substances 0.000 title description 35
- CUPCBVUMRUSXIU-UHFFFAOYSA-N [Fe].OOO Chemical compound [Fe].OOO CUPCBVUMRUSXIU-UHFFFAOYSA-N 0.000 title description 26
- 229910021519 iron(III) oxide-hydroxide Inorganic materials 0.000 title description 26
- 238000002360 preparation method Methods 0.000 title description 15
- 230000003197 catalytic effect Effects 0.000 description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 27
- 238000000034 method Methods 0.000 description 24
- 239000007864 aqueous solution Substances 0.000 description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 16
- 238000001027 hydrothermal synthesis Methods 0.000 description 15
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical class [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 11
- 229910052759 nickel Inorganic materials 0.000 description 10
- 229910002588 FeOOH Inorganic materials 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 8
- 238000005868 electrolysis reaction Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000002184 metal Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- -1 Iron ions Chemical class 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 6
- 229910052753 mercury Inorganic materials 0.000 description 6
- 229910000474 mercury oxide Inorganic materials 0.000 description 6
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 6
- 238000004832 voltammetry Methods 0.000 description 6
- 239000011230 binding agent Substances 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- 239000012279 sodium borohydride Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000011161 development Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 239000006260 foam Substances 0.000 description 4
- 229910052697 platinum Inorganic materials 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052711 selenium Inorganic materials 0.000 description 3
- 239000011669 selenium Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- DKAGJZJALZXOOV-UHFFFAOYSA-N hydrate;hydrochloride Chemical compound O.Cl DKAGJZJALZXOOV-UHFFFAOYSA-N 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000005381 potential energy Methods 0.000 description 1
- 238000002407 reforming Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
- 238000001075 voltammogram Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- 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
- C25B9/00—Cells or assemblies of cells; Constructional parts of cells; Assemblies of constructional parts, e.g. electrode-diaphragm assemblies; Process-related cell features
-
- 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
Landscapes
- 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)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Electrodes For Compound Or Non-Metal Manufacture (AREA)
Abstract
本发明公开了属于电解水制取氢气和氧气技术领域的一种自支撑型羟基氧化铁与铁掺杂硒化镍的复合析氧电极的制备方法和应用。包括以下步骤：(1)将泡沫镍铁置于无水乙醇中；(2)将硒粉、硼氢化钠溶于去离子水得到水溶液，将所述水溶液和步骤(1)所得溶液混合，利用水热反应过程制备自支撑结构的纳米催化析氧电极。本发明所述技术方法与合成工艺简单，原料价格低廉，制备的自支撑型铁镍硒三元复合析氧电极，用于电解氢氧化钾水溶液制备氢气和氧气，析氧活性高。
The invention discloses a preparation method and application of a composite oxygen evolution electrode of self-supporting iron oxyhydroxide and iron-doped nickel selenide, belonging to the technical field of electrolysis of water to produce hydrogen and oxygen. The method includes the following steps: (1) placing the foamed nickel iron in absolute ethanol; (2) dissolving selenium powder and sodium borohydride in deionized water to obtain an aqueous solution, mixing the aqueous solution with the solution obtained in step (1), and using Nano-catalyzed oxygen evolution electrode with self-supporting structure prepared by hydrothermal reaction process. The technical method and synthesis process of the invention are simple, the raw materials are cheap, and the prepared self-supporting iron-nickel-selenium ternary composite oxygen evolution electrode is used for electrolyzing potassium hydroxide aqueous solution to prepare hydrogen and oxygen, and has high oxygen evolution activity.
Description
Technical Field
The invention belongs to the technical field of hydrogen and oxygen preparation by electrolyzing water, and particularly relates to a preparation method and application of a self-supporting type iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode.
Background
In the face of the rapid increase of world energy demand, the fossil fuel as the main energy source is limited in total amount, and causes environmental problems such as greenhouse effect and air pollution, so that people are urgently required to develop a green and clean energy source to replace the fossil fuel. The hydrogen is considered to be a potential energy carrier in the future due to the advantages of high calorific value, wide source, no pollution of combustion reaction products and the like. However, at present, most hydrogen comes from the reforming process of natural gas or coal and petroleum, and a large amount of environmental pollutant emission is generated. Therefore, the development of a zero-carbon-emission hydrogen production technology by water electrolysis is one of the most potential hydrogen production technologies in the future. The existing water electrolysis hydrogen production process has high energy consumption and high cost, and blocks the large-scale industrial application of water electrolysis hydrogen production. The development of hydrogen evolution catalyst and oxygen evolution catalyst with high catalytic activity is an effective method for reducing energy consumption in the water electrolysis process. Iridium dioxide or ruthenium dioxide are the best catalysts for oxygen evolution reactions. Because the metal elements are low in the crust and expensive, the metal elements cannot be popularized and applied in the field of commercial electrolyzed water. Therefore, the development of the oxygen evolution catalyst with low price, simple preparation process and high activity is very important.
At present, in the research and development of the hydrogen production process by water electrolysis, most of the processes use powdery electrocatalysts, and materials with catalytic activity need to be fixed on a current collector by using a binder and the like, so that the processes have obvious defects. Firstly, the catalytic active sites are easily covered by the binder, reducing the catalytic activity; secondly, the introduction of the adhesive can cause extra resistance, which leads to the increase of the working voltage; thirdly, the use of the binder not only increases the preparation cost, but also has a very complicated preparation process.
In order to overcome the defects of the prior art, people actively develop a self-supporting catalytic electrode, namely, a substance with a catalytic function directly grows on the surface of a metal wire mesh by a certain process method. On one hand, the binder is not used any more, the problem that the binder covers the catalytic active sites is eliminated, on the other hand, the interface resistance between the catalytic component and the matrix material is reduced, the bonding strength is improved, and obvious beneficial effects are obtained. The technical methods adopted by (Chun Tang et al, Angew. chem.2015,127, 9483-9487; Yunxiao Li et al, J.Mater. chem.A,2017,5,25494) comprise electrochemical deposition (Chinese patent CN 110205636B; CN 108193227A; CN 110656348A) and hydrothermal synthesis technology (CN 110354862A), so that the catalytic activity and stability of the oxygen evolution electrode are obviously improved. However, in order to meet the requirement of corrosion resistance in the alkaline aqueous solution of potassium hydroxide, the matrix materials adopted in the method are all single-kind metals, including metallic nickel mesh and foamed nickel. Iron ions and nickel ions have to be additionally introduced in the preparation process to grow iron-nickel compounds on the surface of the metal nickel net or the foamed nickel and play a role in catalyzing oxygen evolution. Because iron ions are introduced from the outside, the bonding degree between the catalytic component and the matrix material is weak in the growth process, the long-term use stability of the catalytic electrode is directly influenced, and the industrial application requirements are difficult to meet. In addition, the additional introduction of iron ions increases the complexity of the raw material components due to problems such as lattice dislocation, which degrades the catalytic performance.
Disclosure of Invention
In order to solve the defects of the prior art, the invention provides a self-source growth concept, namely, an iron-nickel binary alloy is used for replacing the original single kind of metal nickel, so that the matrix material contains the iron element required by the growth of the iron oxyhydroxide. Therefore, under the premise of not introducing any foreign species, the iron oxyhydroxide compound can grow on the surface of the conductive metal current collector in situ, the interface resistance between the current collector and the catalytic site is reduced, the catalytic activity and the bonding strength are enhanced, and the stability of the catalytic electrode is improved. On the basis, selenium element is further introduced, and a nickel selenide nanowire is generated through a hydrothermal reaction process to form the composite oxygen evolution electrode of the iron oxyhydroxide and the iron-doped nickel selenide. The coordination of the iron-nickel binary metal and the nonmetal selenium is utilized to adjust the valence state structure of the metal, improve the activity of the electrocatalytic oxygen evolution reaction, reduce the overpotential and achieve the purpose of reducing the energy consumption in the water electrolysis process. The invention aims to provide a preparation method and application of a self-supporting type composite oxygen evolution electrode of hydroxyl iron oxide and iron-doped nickel selenide, and the specific technical scheme is as follows:
the invention provides a preparation method of a self-supporting type hydroxyl ferric oxide and iron-doped nickel selenide composite oxygen evolution electrode, which comprises the following steps:
(1) placing the foamed nickel iron into absolute ethyl alcohol;
(2) dissolving selenium powder and sodium borohydride in deionized water to obtain an aqueous solution, and mixing the aqueous solution and the solution obtained in the step (1) to perform hydrothermal reaction.
In the step (1), the foamed nickel iron is washed by hydrochloric acid aqueous solution, acetone and deionized water in advance, preferably under ultrasonic wave. Among them, the concentration of the aqueous hydrochloric acid solution is preferably 2 mol/L.
The mass ratio of iron to nickel in the foam nickel iron in the step (1) is (3-9) to (1-7).
And (2) mixing the aqueous solution and the solution obtained in the step (1) under an inert atmosphere, and then carrying out hydrothermal reaction. The specific operation is that the clean foam nickel iron is firstly put into absolute ethyl alcohol, inert gas is introduced, and under the inert atmosphere, the water solution dissolved with selenium powder and sodium borohydride is injected into the absolute ethyl alcohol.
The molar ratio of the selenium powder to the sodium borohydride in the step (2) is 0.5: 1-2: 1.
The hydrothermal reaction in the step (2) is carried out in an inert atmosphere, the reaction temperature is 100-180 ℃, and the reaction time is 3-30 hours.
And (3) after the hydrothermal reaction in the step (2) is finished, washing the obtained product by using ethanol and deionized water, and drying the obtained product in the air to obtain the self-supporting FeOOH and Fe-doped nickel selenide composite oxygen evolution electrode.
The invention provides an application method, and the self-supporting iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode prepared by the preparation method is used for preparing hydrogen and oxygen by electrolyzing alkaline aqueous solution. The alkaline aqueous solution may be a potassium hydroxide aqueous solution or a sodium hydroxide aqueous solution, and the concentration of the alkaline aqueous solution is 1 to 7 mol/L.
In a third aspect the invention provides a method of producing a batteryThe electrolytic cell is prepared by using the self-supporting FeOOH and iron-doped nickel selenide composite oxygen evolution electrode prepared by the preparation method. High electrocatalytic activity, and the platinum sheet is used as a counter electrode, and the current density is 10mA cm-2When the voltage is higher than the predetermined value, the overpotential is only 224-245.81 mV, and the Tafel slope is 52.67-63.58 mV dec-1. The overpotential of the electrode reaction is far lower than that of similar oxygen evolution electrodes, and the electrode prepared by the method has excellent oxygen evolution catalytic activity and is suitable for running under high current density.
The invention has the beneficial effects that:
(1) the invention provides a preparation method of a self-supporting type FeOOH and iron-doped nickel selenide composite oxygen evolution electrode (FeOOH @ Fe-NiSe @ NiFe), which has the advantages of simple synthesis process and low raw material price, and the self-supporting type FeOOH and iron-doped nickel selenide composite oxygen evolution electrode with high oxygen evolution activity can be prepared by only one-step hydrothermal reaction.
(2) The method prepares the oxygen evolution reaction catalytic electrode through self-source growth, and the catalytic active sites are directly connected with the foam ferronickel in the self-source growth process, so that the electronic on-resistance is effectively reduced; the electrocatalyst and the current collector are combined into a whole, the binding force between the catalytic active component and the matrix is strong, the catalyst is not easy to fall off in the using process, the electrode preparation cost can be reduced, and the structural stability of the catalytic activity can be improved. The prepared electrode can be used in the hydrogen and oxygen production process by water electrolysis, the catalytic oxygen evolution function is exerted, and the energy consumption and the production cost of water electrolysis are effectively reduced.
Drawings
Fig. 1 is a linear voltammetry scan curve of the composite oxygen evolution electrode of self-supporting iron oxyhydroxide and iron-doped nickel selenide obtained in example 1.
Fig. 2 is a surface topography of the composite oxygen evolution electrode of the self-supporting iron oxyhydroxide and the iron-doped nickel selenide obtained in example 1.
Fig. 3 is a transmission electron microscope image of the iron oxyhydroxide group in the self-supporting iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode obtained in example 1.
FIG. 4 is a comparison of linear voltammetry scan curves of the self-supporting iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode obtained in examples 1-3, comparative example 1 and comparative example 2.
FIG. 5 is a comparison of the linear voltammetry scan curves of the self-supporting iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode obtained in examples 1 and 4-6.
Fig. 6 shows the stability of the self-supporting oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode obtained in example 1.
Detailed Description
The invention provides a preparation method and application of a self-supporting type composite oxygen evolution electrode of iron oxyhydroxide and iron-doped nickel selenide, and the invention is further explained by combining embodiments and drawings.
The method for preparing the self-supporting type composite oxygen evolution electrode of the hydroxyl ferric oxide and the iron-doped nickel selenide comprises the following steps:
(1) cleaning foamed nickel iron with 2mol/L hydrochloric acid water solution, acetone and water in sequence under the action of ultrasonic waves, then placing the cleaned foamed nickel iron in absolute ethyl alcohol, and introducing nitrogen; the foam iron-nickel alloy is used as a base material, and the mass ratio of iron to nickel elements is (3-9) to (1-7).
(2) Adding deionized water into a mixture of selenium powder and sodium borohydride in a molar ratio of 0.5: 1-2: 1 for dissolving, adding the obtained water solution into the absolute ethyl alcohol obtained in the step (1), and carrying out hydrothermal reaction at 100-180 ℃ for 3-30 hours so as to complete selenium element doping on the surface of the foamed nickel iron; preferably, the hydrothermal reaction is carried out at 140 ℃ for 12 hours.
(3) And after the hydrothermal reaction is finished, taking out the foamed nickel iron, cleaning the surface by using ethanol and deionized water, and drying in the air to obtain the self-supporting FeOOH and Fe-doped nickel selenide composite oxygen evolution electrode.
The self-supporting FeOOH and iron-doped nickel selenide composite oxygen evolution electrode prepared by the method can be used for preparing hydrogen and oxygen by electrolyzing alkaline aqueous solution. The alkaline aqueous solution may be a potassium hydroxide aqueous solution or a sodium hydroxide aqueous solution, and the concentration of the potassium hydroxide aqueous solution or the sodium hydroxide aqueous solution is 1 to 7 mol/L.
The composite oxygen evolution electrode of the self-supporting iron oxyhydroxide and the iron-doped nickel selenide prepared by the method is used as a working electrode, a platinum sheet is used as a counter electrode, mercury/mercury oxide is used as a reference electrode, and the catalytic oxygen evolution performance of the composite oxygen evolution electrode of the self-supporting iron oxyhydroxide and the iron-doped nickel selenide is represented by utilizing a linear volt-ampere scanning curve in a 1mol/L potassium hydroxide aqueous solution.
Example 1
Preparing a self-supporting composite oxygen evolution electrode of hydroxyl iron oxide and iron-doped nickel selenide by using foamed nickel iron with the mass ratio of iron to nickel being 3:7 as a base material:
(1) cleaning the matrix material in an ultrasonic generator by respectively using 2mol/L hydrochloric acid aqueous solution, acetone and water, then placing the matrix material in absolute ethyl alcohol and introducing nitrogen;
(2) dissolving the mixture of selenium powder and sodium borohydride in deionized water, injecting the obtained water solution into the absolute ethyl alcohol in the step (1), and carrying out hydrothermal reaction for 12 hours at 140 ℃.
(3) And (3) taking out the foamed nickel iron after the hydrothermal reaction is finished, cleaning the surface by using ethanol and deionized water, and drying in the air to obtain the self-supporting FeOOH and Fe-doped nickel selenide composite oxygen evolution electrode.
The catalytic oxygen evolution performance of the self-supporting iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode is represented by a linear voltammetry scanning curve in a 1mol/L potassium hydroxide aqueous solution by using the self-supporting iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode prepared in the example 1 as a working electrode, a platinum sheet as a counter electrode and mercury/mercury oxide as a reference electrode. As shown in FIG. 1, at a current density of 10mA cm-2When the electrode is used, the overpotential of the electrode is 224mV, which is much lower than that of the similar oxygen evolution electrode, and the electrode prepared in the example 1 has excellent oxygen evolution catalytic activity.
Fig. 2 is a Scanning Electron Microscope (SEM) image of the self-supporting iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode prepared in example 1, from which it can be clearly seen that the electrode surface exhibits a uniformly distributed nanowire morphology, and fig. 3 is a transmission electron microscope image of the iron oxyhydroxide in the self-supporting iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode prepared in example 1, from which it can be seen that the iron oxyhydroxide is amorphous.
Example 2
In contrast to example 1, foamed nickel iron with a mass ratio of iron to nickel of 5:5 was used as matrix material.
Example 3
In contrast to example 1, foamed nickel iron with a mass ratio of iron to nickel of 9:1 was used as matrix material.
Example 4
Unlike example 1, the hydrothermal reaction time in step (2) was 6 hours.
Example 5
Unlike example 1, the hydrothermal reaction time in step (2) was 18 hours.
Example 6
Unlike example 1, the hydrothermal reaction time in step (2) was 24 hours.
Comparative example 1
In contrast to example 1, foamed iron was used as the matrix material.
Comparative example 2
In contrast to example 1, foamed nickel was used as matrix material.
The catalytic oxygen evolution performance of the self-supporting iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode is represented by a linear voltammetry scanning curve in a 1mol/L potassium hydroxide aqueous solution by taking the self-supporting iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode obtained in the examples 1-3, the comparative example 1 and the comparative example 2 as a working electrode, a graphite sheet as a counter electrode and mercury/mercury oxide as a reference electrode. Fig. 4 shows the catalytic oxygen evolution performance of the self-supporting iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrodes obtained in examples 1 to 3, comparative examples 1 and 2, and it can be seen that the catalytic electrode prepared in example 1 has the best performance.
The catalytic oxygen evolution performance of the self-supporting FeOOH and iron-doped nickel selenide composite oxygen evolution electrode is characterized by utilizing a linear voltammetry scanning curve in a 1mol/L potassium hydroxide aqueous solution by taking the electrode obtained in the embodiment 1 and the embodiments 4-6 as a working electrode, a platinum sheet as a counter electrode and mercury/mercury oxide as a reference electrode. FIG. 5 is a graph showing the linear voltammograms of the electrodes obtained in examples 1 and 4 to 6.
Example 7
In order to illustrate the stability of the prepared electrode in the using process, the self-supporting type iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode prepared by the method described in example 1 is used as a working electrode, a graphite sheet is used as a counter electrode, mercury/mercury oxide is used as a reference electrode, and a constant current oxygen evolution experiment is carried out in a 1mol/L potassium hydroxide aqueous solution. The current density was set to 500mA cm-2And continuously running for 100000 seconds to examine the change condition of the oxygen evolution rate. The results are shown in FIG. 6 at current densities up to 500mA cm-2In the case, the electrode potential (relative to the mercury/mercury oxide reference electrode) is always stable around 0.98V, which indicates that the composite oxygen evolution electrode of the self-supporting iron oxyhydroxide and the iron-doped nickel selenide obtained in example 1 has good stability and is suitable for industrial development and manufacturing.
Claims (10)
1. A preparation method of a self-supporting FeOOH and iron-doped nickel selenide composite oxygen evolution electrode is characterized in that,
the method comprises the following steps:
(1) placing the foamed nickel iron into absolute ethyl alcohol;
(2) dissolving selenium powder and sodium borohydride in deionized water to prepare an aqueous solution, mixing the aqueous solution with the solution obtained in the step (1), and carrying out hydrothermal reaction.
2. The method for preparing the nickel-iron foam according to the claim 1, wherein the nickel-iron foam is washed by hydrochloric acid aqueous solution, acetone and deionized water respectively in advance.
3. The method according to claim 1, wherein in the step (1), the mass ratio of iron to nickel in the foamed nickel-iron is (3-9) to (1-7).
4. The method according to claim 1, wherein the step (2) of mixing the aqueous solution with the solution obtained in the step (1) under an inert atmosphere and then performing a hydrothermal reaction.
5. The preparation method according to claim 1, wherein the molar ratio of the selenium powder to the sodium borohydride in the step (2) is 0.5: 1-2: 1.
6. The preparation method according to claim 1, wherein the hydrothermal reaction in the step (2) is carried out at a temperature of 100 to 180 ℃ for 3 to 30 hours.
7. The preparation method according to claim 1, wherein after the hydrothermal reaction in the step (2) is completed, the self-supporting FeOOH and iron-doped Nickel selenide composite oxygen evolution electrode is obtained by washing with ethanol and deionized water and drying in air.
8. The application of the self-supporting combined oxygen evolution electrode of the iron-doped nickel selenide and the iron-based iron oxyhydroxide prepared by the preparation method of any one of claims 1 to 7 is characterized in that the self-supporting combined oxygen evolution electrode of the iron-doped nickel selenide and the iron-doped iron oxyhydroxide is used for preparing hydrogen and oxygen by electrolyzing an alkaline aqueous solution.
9. The use according to claim 8, wherein the concentration of the alkaline aqueous solution is 1 to 7 mol/L.
10. An electrolytic cell, characterized in that the electrolytic cell is prepared by using the self-supporting FeOOH prepared by the preparation method of claims 1-7 and an iron-doped Nickel selenide composite oxygen evolution electrode.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110159597.4A CN112981441A (en) | 2021-02-05 | 2021-02-05 | Preparation method and application of self-supporting type iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110159597.4A CN112981441A (en) | 2021-02-05 | 2021-02-05 | Preparation method and application of self-supporting type iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112981441A true CN112981441A (en) | 2021-06-18 |
Family
ID=76347635
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110159597.4A Pending CN112981441A (en) | 2021-02-05 | 2021-02-05 | Preparation method and application of self-supporting type iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112981441A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113529133A (en) * | 2021-07-30 | 2021-10-22 | 清华大学 | Preparation method of self-supporting type bifunctional catalytic electrode |
| CN113774404A (en) * | 2021-10-09 | 2021-12-10 | 华中科技大学 | A core-shell chain nickel-based selenide/iron oxyhydroxide composite catalyst and its preparation method and application |
| CN114774976A (en) * | 2022-05-04 | 2022-07-22 | 台州学院 | Spherical S-doped CoSe2/CoOOH and preparation method thereof |
| CN114807956A (en) * | 2022-04-11 | 2022-07-29 | 西南石油大学 | Preparation method of in-situ growth nano array catalyst applied to hydrogen sulfide hydrogen production |
| CN115627497A (en) * | 2022-12-21 | 2023-01-20 | 广东工业大学 | A kind of preparation method and application of NiFeSe/NF catalyst |
| CN115786970A (en) * | 2022-10-12 | 2023-03-14 | 电子科技大学长三角研究院(湖州) | Rapid preparation method of iron-doped nickel selenide and application of iron-doped nickel selenide in electrolytic water cathode |
| CN116180102A (en) * | 2021-12-03 | 2023-05-30 | 青岛绿色发展研究院有限公司 | Supported nickel-iron-based oxygen evolution electrode and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109954503A (en) * | 2019-03-28 | 2019-07-02 | 浙江大学 | A kind of nickel selenide and ternary nickel-iron selenide composite electrocatalyst and preparation method and application |
| CN110938831A (en) * | 2019-11-14 | 2020-03-31 | 湖南理工学院 | Foam alloy-based iron-doped NiSe microsphere electrocatalytic material and preparation method thereof |
| CN111111707A (en) * | 2019-12-31 | 2020-05-08 | 山东大学 | A selenium-doped nickel-iron spinel/nickel oxyhydroxide composite electrocatalyst material and its preparation method and application |
| CN112064060A (en) * | 2020-09-21 | 2020-12-11 | 陕西科技大学 | Nickel selenide/nickel iron substrate material and preparation method and application thereof |
-
2021
- 2021-02-05 CN CN202110159597.4A patent/CN112981441A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109954503A (en) * | 2019-03-28 | 2019-07-02 | 浙江大学 | A kind of nickel selenide and ternary nickel-iron selenide composite electrocatalyst and preparation method and application |
| CN110938831A (en) * | 2019-11-14 | 2020-03-31 | 湖南理工学院 | Foam alloy-based iron-doped NiSe microsphere electrocatalytic material and preparation method thereof |
| CN111111707A (en) * | 2019-12-31 | 2020-05-08 | 山东大学 | A selenium-doped nickel-iron spinel/nickel oxyhydroxide composite electrocatalyst material and its preparation method and application |
| CN112064060A (en) * | 2020-09-21 | 2020-12-11 | 陕西科技大学 | Nickel selenide/nickel iron substrate material and preparation method and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| CHUN TANG ET. AL: "Highly-active oxygen evolution electrocatalyzed by a Fe-doped NiSe nanoflake array electrode", 《CHEM. COMMUN.》 * |
| W.-H. HUNG ET. AL.: "A highly active selenized nickeleiron electrode with layered double hydroxide for electrocatalytic water splitting in saline electrolyte", 《MATERIALS TODAY ENERGY》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113529133A (en) * | 2021-07-30 | 2021-10-22 | 清华大学 | Preparation method of self-supporting type bifunctional catalytic electrode |
| CN113774404A (en) * | 2021-10-09 | 2021-12-10 | 华中科技大学 | A core-shell chain nickel-based selenide/iron oxyhydroxide composite catalyst and its preparation method and application |
| CN116180102A (en) * | 2021-12-03 | 2023-05-30 | 青岛绿色发展研究院有限公司 | Supported nickel-iron-based oxygen evolution electrode and preparation method and application thereof |
| CN116180102B (en) * | 2021-12-03 | 2024-02-23 | 青岛绿色发展研究院有限公司 | Supported nickel-iron-based oxygen evolution electrode and preparation method and application thereof |
| CN114807956A (en) * | 2022-04-11 | 2022-07-29 | 西南石油大学 | Preparation method of in-situ growth nano array catalyst applied to hydrogen sulfide hydrogen production |
| CN114807956B (en) * | 2022-04-11 | 2024-05-17 | 西南石油大学 | Preparation method of in-situ grown nanoarray catalyst for hydrogen production from hydrogen sulfide |
| CN114774976A (en) * | 2022-05-04 | 2022-07-22 | 台州学院 | Spherical S-doped CoSe2/CoOOH and preparation method thereof |
| CN115786970A (en) * | 2022-10-12 | 2023-03-14 | 电子科技大学长三角研究院(湖州) | Rapid preparation method of iron-doped nickel selenide and application of iron-doped nickel selenide in electrolytic water cathode |
| CN115627497A (en) * | 2022-12-21 | 2023-01-20 | 广东工业大学 | A kind of preparation method and application of NiFeSe/NF catalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112981441A (en) | Preparation method and application of self-supporting type iron oxyhydroxide and iron-doped nickel selenide composite oxygen evolution electrode | |
| CN109659143B (en) | Nickel hydroxide/trinickel disulfide/foamed nickel compound and preparation method and application thereof | |
| CN109954503B (en) | Nickel selenide and ternary nickel-iron selenide composite electrocatalyst, preparation method and application | |
| CN110947387B (en) | Preparation method and application of nickel-iron double metal hydroxide nano film material | |
| CN110280249B (en) | Preparation method of non-precious metal NiCoFe/NF electrocatalyst and application of oxygen evolution | |
| CN110314690B (en) | Bimetallic sulfide Ni3S2/FeS composites with heterogeneous interfacial coupling and their preparation methods and applications | |
| CN108097270A (en) | A kind of elctro-catalyst for being catalyzed water decomposition production hydrogen and its preparation method and application | |
| CN111111707A (en) | A selenium-doped nickel-iron spinel/nickel oxyhydroxide composite electrocatalyst material and its preparation method and application | |
| CN105858815A (en) | Preparation method of core-shell structure NiCo2S4 @NiCo2O4 nanoneedle composite catalytic electrode | |
| CN110681402A (en) | A carbon paper supported Fe-NiCoP heterostructure and its preparation method and application | |
| CN110306204A (en) | A kind of layered nickel hydroxide composite electrode material doped with silver and its preparation method and application | |
| Liu et al. | Facile construction Co-doped and CeO2 heterostructure modified NiS2 grown on foamed nickel for high-performance bifunctional water electrolysis catalysts | |
| CN112921351B (en) | A kind of preparation method and application of self-supporting catalytic electrode | |
| CN113201752B (en) | Preparation method and application of a heterojunction-rich CoNiP-P nanocatalyst | |
| CN118441301A (en) | Nickel-based hydrogen evolution catalyst and preparation method and application thereof | |
| CN118345429A (en) | Nitrogen-doped carbon-modified self-supporting La-doped Co3O4Preparation method of oxygen evolution catalyst | |
| CN114807970B (en) | A nitrogen-doped carbon-based Co/Ni12P5 oxygen evolution catalyst and its preparation method and application | |
| CN116657186A (en) | A heterogeneous catalytic electrode for seawater full electrolysis hydrogen production and its preparation method and application | |
| CN113249752B (en) | Fe2P-WOxPreparation method of oxygen evolution electrocatalyst | |
| CN113293407B (en) | Iron-rich nanobelt oxygen evolution electrocatalyst and preparation method thereof | |
| CN113584515A (en) | Based on CoxP/FeP electrode material as working electrode for electrocatalytic hydrogen evolution | |
| CN116926957B (en) | Preparation method and application of dysprosium-doped nickel-metal organic frame composite material | |
| CN114990619B (en) | An amorphous NiOOH/Ni3S2 heterostructure nickel-based composite catalyst and its preparation method and application | |
| CN117535677B (en) | A N, P co-doped Co9S8 integrated water splitting electrocatalyst and its preparation method and application | |
| CN113604831B (en) | Co 4 S 3 -WS 2 Preparation method of oxygen evolution hydrogen evolution electrocatalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20210618 |