CN112264017A - Transition metal iron-nickel nano powder catalyst modified by surface iron-nickel defect layer - Google Patents
Transition metal iron-nickel nano powder catalyst modified by surface iron-nickel defect layer Download PDFInfo
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- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 239000003054 catalyst Substances 0.000 title claims abstract description 54
- 230000007547 defect Effects 0.000 title claims abstract description 22
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 16
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 16
- 239000011858 nanopowder Substances 0.000 title claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 41
- 239000001301 oxygen Substances 0.000 claims abstract description 41
- 239000002105 nanoparticle Substances 0.000 claims abstract description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 20
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 238000001556 precipitation Methods 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000000034 method Methods 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 150000002431 hydrogen Chemical class 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 20
- 229910002555 FeNi Inorganic materials 0.000 description 19
- 238000003756 stirring Methods 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 5
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910002554 Fe(NO3)3·9H2O Inorganic materials 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 229910021397 glassy carbon Inorganic materials 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000010287 polarization Effects 0.000 description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 229910002588 FeOOH Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- 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
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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 Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
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Abstract
The invention discloses a transition metal iron-nickel nano powder catalyst modified by a surface iron-nickel defect layer. The iron-nickel atomic ratio is 1: 3 at the temperature of 250-350 ℃ in air or oxygen-containing atmosphere to obtain an iron-nickel-based nanoparticle precursor with oxidized surface, and then placing the precursor in a hydrogen atmosphere to carry out heat treatment at the temperature of 350-450 ℃ for a period of time to obtain the catalyst. The catalyst has high-efficiency water electrolysis oxygen precipitation activity; the oxygen precipitation activity of the catalyst is obviously better than that of transition metal iron-nickel nano powder which is not treated by hydrogen, and the preparation method is simple, low in cost and suitable for mass production.
Description
Background
Water electrolysis is used as a reliable clean energy source technology, and the energy consumption of unit hydrogen is the key of water electrolysis hydrogen production application. The energy consumption sources of water electrolysis mainly include anode oxygen evolution overpotential and cathode hydrogen evolution overpotential, wherein the anode oxygen evolution overpotential is higher, the energy consumption is larger, and the water electrolysis cost is directly increased. In addition, the anode end oxygen evolution catalyst generally adopts a noble metal (iridium/ruthenium) catalyst to reduce the overpotential, and the noble metal occupies most of the cost in the practical application of water electrolysis. At present, the core problems limiting the large-scale application of water electrolysis are high energy consumption cost and high cost of anode-end noble metal catalyst. Therefore, the development of high performance anodic oxygen evolution electrocatalysts, especially with easily synthesized base metal catalysts, is a key approach to solving these problems.
In the electrocatalytic oxygen evolution, the activity, stability, conductivity and the like of the material are key indexes influencing the oxygen evolution performance. The anode oxygen evolution transition metal electrocatalyst reported at present mainly comprises transition metal alloy (FeNi)3FeNi), oxide (Fe)2O3NiO), hydroxide (transition metal LDH, FeOOH, Ni (OH)2) And the like. The transition metal oxide has poor conductivity, is not beneficial to the electron conduction process in the oxygen precipitation reaction process, and has the problems of insufficient stability and the like in part of oxides. [ chem. mater. 29(1) 120-.](ii) a The transition metal iron-nickel alloy has good conductivity, and the surface of the transition metal iron-nickel alloy is generally converted into species such as oxide, hydroxide and the like after oxygen precipitation catalytic reaction. But the iron-nickel alloy powder catalyst has fewer surface active sites and lower catalytic activity.
Disclosure of Invention
The invention aims to provide a transition metal iron-nickel nano powder catalyst with a surface iron-nickel defect layer modified and application of the transition metal iron-nickel nano powder catalyst in water electrolysis oxygen evolution reaction. The powder catalyst has a transition metal iron-nickel nano powder structure with a surface iron-nickel defect layer modified, has rich and fully exposed catalytic reaction active sites in the water electrolysis anode oxygen precipitation reaction, and has high water electrolysis oxygen precipitation activity in application.
The technical solution for realizing the purpose of the invention is as follows: a transition metal iron-nickel nano powder catalyst modified by a surface iron-nickel defect layer is obtained by sequentially carrying out low-oxidation etching and low-temperature hydrogen calcination treatment on iron-nickel alloy nano particles, and the specific process is as follows:
the iron-nickel atomic ratio is 1: 3 at the temperature of 250-350 ℃ in air or oxygen-containing atmosphere to obtain an iron-nickel-based nanoparticle precursor with oxidized surface, and then placing the precursor in a hydrogen atmosphere to carry out heat treatment at the temperature of 350-450 ℃ for a period of time to obtain the catalyst.
Preferably, the particle size of the iron-nickel alloy nanoparticles is less than or equal to 300 nm.
Preferably, the temperature is maintained at 250-350 ℃ for 2 hours in air or oxygen-containing atmosphere.
Preferably, the mixture is placed in a hydrogen atmosphere and is subjected to heat treatment at 350-450 ℃ for 2 hours.
Compared with the prior art, the invention has the following advantages:
(1) compared with the surface oxidized iron-nickel powder catalyst, the FeNi-based powder catalyst modified by the surface iron-nickel defect layer has more catalytic active centers, higher catalytic activity and no foreign impurities.
(2) Compared with other nanometer shapes and synthesis methods, the method has the advantages of simple synthesis of the nanometer particles, simple operation, lower cost and favorable technical route for batch preparation.
Drawings
Fig. 1 is a TEM image of the FeNi-based powder catalyst with a modified surface iron-nickel defect layer prepared in example 1.
Fig. 2 is an XRD spectrum of the FeNi-based powder catalyst modified with a surface iron-nickel defect layer prepared in example 1.
Fig. 3 is an oxygen evolution performance curve of the FeNi-based powder catalyst modified with the surface iron-nickel defect layer prepared in example 2.
Fig. 4 is an oxygen evolution performance curve of the 250 degree oxidized FeNi-based powder catalyst prepared in comparative example 1.
Fig. 5 is an oxygen evolution performance curve of the 350 degree oxidized FeNi-based powder catalyst prepared in comparative example 2.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1
Preparing a FeNi-based powder catalyst with a surface modified by an iron-nickel defect layer: 4.8 g of NiCl2·6H2O、2.5 g FeCl2·4H2O, 100 mg CTAB added to 100 mL H2In O, stirring vigorously for 30 min, adding NH4OH adjusted the pH to 8. Slowly dripping 10 mL of hydrazine hydrate solution under vigorous stirring, stirring for 3 hours, standing for 3 hours, centrifuging, washing with water, and drying to obtain iron-nickel nano particles for later use.
Heating the iron-nickel nano particles to 350 ℃ in air atmosphere, and keeping the temperature for 2 hours to obtain the iron-nickel nano particles with oxidized surfaces. And then placing the iron-nickel nano particles with oxidized surfaces into a hydrogen atmosphere, and preserving the heat for 2 hours at 400 ℃ to obtain the FeNi-based powder catalyst with the iron-nickel defect layer modified surfaces. The structure and crystal structure of the crystal are shown in fig. 1 and fig. 2.
Example 2
The iron-nickel nano particles, the iron-nickel nano particles with oxidized surfaces and the FeNi-based powder catalyst modified by the iron-nickel defect layer prepared in the embodiment 1 are applied to the oxygen evolution end of the water electrolysis electric anode, and the specific process is as follows: 5 mg of catalyst is dispersed in 1 ml of ethanol and 50 mul of Nafion solution to prepare catalyst ink with good dispersibility, 5 mul of catalyst ink is dripped on the surface of a glassy carbon electrode, the catalyst ink is used for the oxygen evolution end of a water electrolysis anode after being dried, and the test process is carried out in a traditional three-electrode electrolytic cell. FIG. 3 is a performance curve of FeNi-based powder catalyst material with a surface iron-nickel defect layer modified in water electrolysis anode oxygen precipitation. As can be seen from the polarization curve diagram of the oxygen evolution reaction, the FeNi-based powder catalyst modified by the surface iron-nickel defect layer is applied to the oxygen evolution reaction, and shows excellent oxygen evolution performance at 10 mA cm-2When the surface oxidation is carried out, the potential is only 1.45V, and the activity is far higher than that of the iron-nickel nano particles and the iron-nickel nano particles with oxidized surfaces.
Example 3
Preparing a FeNi-based powder catalyst with a surface modified by an iron-nickel defect layer: adding 3 mmol of Ni (NO)3)2·6H2O、1 mmol Fe(NO3)3·9H2O, 0.1 mmol CTAB added to 100 mL of H2In O, stirring vigorously for 30 min, adding NH4OH adjusted the pH to 8. Slowly dripping 10 mL of hydrazine hydrate solution under vigorous stirring, stirring for 3 hours, standing for 3 hours, centrifuging, washing with water, and drying to obtain iron-nickel nano particles for later use. Heating the iron-nickel nano particles to 250 ℃ in air atmosphere, and keeping the temperature for 2 hours to obtain the iron-nickel nano particles with oxidized surfaces. And then placing the iron-nickel nano particles with oxidized surfaces into a hydrogen atmosphere, and preserving the heat for 2 hours at 350 ℃ to obtain the FeNi-based powder catalyst with the iron-nickel defect layer modified surfaces.
Example 4
Surface iron-nickel defect layer repairPreparation of decorated FeNi-based powder catalyst: adding 3 mmol of Ni (NO)3)2·6H2O、1 mmol Fe(NO3)3·9H2O, 0.1 mmol CTAB added to 100 mL of H2In O, stirring vigorously for 30 min, adding NH4OH adjusted the pH to 8. And slowly dropwise adding 12 mL of hydrazine hydrate solution under vigorous stirring, stirring for 3 hours, standing for 3 hours, centrifuging, washing with water, and drying to obtain iron-nickel nanoparticles for later use. Heating the iron-nickel nano particles to 250 ℃ in air atmosphere, and keeping the temperature for 2 hours to obtain the iron-nickel nano particles with oxidized surfaces. And then placing the iron-nickel nano particles with oxidized surfaces into a hydrogen atmosphere, and preserving the heat for 2 hours at 450 ℃ to obtain the FeNi-based powder catalyst with the iron-nickel defect layer modified surfaces.
Comparative example 1
Preparation of oxidation treatment FeNi-based powder catalyst: adding 3 mmol of Ni (NO)3)2·6H2O、1 mmol Fe(NO3)3·9H2O, 0.1 mmol CTAB added to 100 mL of H2In O, stirring vigorously for 30 min, adding NH4OH adjusted the pH to 8. And slowly dropwise adding 12 mL of hydrazine hydrate solution under vigorous stirring, stirring for 3 hours, standing for 3 hours, centrifuging, washing with water, and drying to obtain iron-nickel nanoparticles for later use. Heating the iron-nickel nano particles to 250 ℃ in air atmosphere, and keeping the temperature for 2 hours to obtain the iron-nickel nano particles with oxidized surfaces. The iron-nickel nanoparticle catalyst with oxidized surface is applied to the oxygen evolution end of the water electrolysis anode, and the specific process is as follows: 5 mg of catalyst is dispersed in 1 ml of ethanol and 50 mul of Nafion solution to prepare catalyst ink with good dispersibility, 5 mul of catalyst ink is dripped on the surface of a glassy carbon electrode, the catalyst ink is used for the oxygen evolution end of a water electrolysis anode after being dried, and the test process is carried out in a traditional three-electrode electrolytic cell. FIG. 4 is a graph of the performance of surface oxidized iron-nickel nanoparticles in water electrolysis anodic oxygen evolution. As can be seen from the polarization curve diagram of the oxygen evolution reaction, the iron-nickel nanoparticle catalyst with oxidized surface is applied to the oxygen evolution reaction, and shows lower oxygen evolution performance at 10 mA cm-2In this case, the potential is 1.56V.
Comparative example 2
Preparation of oxidation treatment FeNi-based powder catalyst: 4.8 g of NiCl2·6H2O、2.5 g FeCl2·4H2O, 100 mg CTAB added to 100 mL H2In O, stirring vigorously for 30 min, adding NH4OH adjusted the pH to 8. Slowly dripping 10 mL of hydrazine hydrate solution under vigorous stirring, stirring for 3 hours, standing for 3 hours, centrifuging, washing with water, and drying to obtain iron-nickel nano particles for later use. Heating the iron-nickel nano particles to 350 ℃ in air atmosphere, and keeping the temperature for 2 hours to obtain the iron-nickel nano particles with oxidized surfaces. The iron-nickel nanoparticle catalyst with oxidized surface is applied to the oxygen evolution end of the water electrolysis anode, and the specific process is as follows: 5 mg of catalyst is dispersed in 1 ml of ethanol and 50 mul of Nafion solution to prepare catalyst ink with good dispersibility, 5 mul of catalyst ink is dripped on the surface of a glassy carbon electrode, the catalyst ink is used for the oxygen evolution end of a water electrolysis anode after being dried, and the test process is carried out in a traditional three-electrode electrolytic cell. FIG. 5 is a graph of the performance of surface oxidized iron-nickel nanoparticles in water electrolysis anodic oxygen evolution. As can be seen from the polarization curve diagram of the oxygen evolution reaction, the iron-nickel nanoparticle catalyst with oxidized surface is applied to the oxygen evolution reaction, and shows lower oxygen evolution performance at 10 mA cm-2In this case, the potential is 1.57V.
Claims (6)
1. A preparation method of a transition metal iron-nickel nano powder catalyst modified by a surface iron-nickel defect layer is characterized in that the iron-nickel atomic ratio is 1: 3 at the temperature of 250-350 ℃ in air or oxygen-containing atmosphere to obtain an iron-nickel-based nanoparticle precursor with oxidized surface, and then placing the precursor in a hydrogen atmosphere to carry out heat treatment at the temperature of 350-450 ℃ for a period of time to obtain the catalyst.
2. The method of claim 1, wherein the iron-nickel alloy nanoparticles have a particle size of 300 nm or less.
3. The method of claim 1, wherein the temperature is maintained at 250-350 ℃ for 2 hours in air or an oxygen-containing atmosphere.
4. The method of claim 1, wherein the heat treatment is carried out in a hydrogen atmosphere at 350 ℃ to 450 ℃ for 2 hours.
5. The transition metal iron-nickel nano powder catalyst modified by the surface iron-nickel defect layer prepared by the method of any one of claims 1 to 4.
6. The application of the transition metal iron-nickel nano powder catalyst modified by the surface iron-nickel defect layer prepared by the method of any one of claims 1 to 4 in water electrolysis anode oxygen precipitation reaction.
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|---|---|---|---|---|
| JP2007111635A (en) * | 2005-10-20 | 2007-05-10 | Sumitomo Electric Ind Ltd | Metal catalyst and method for manufacturing the same |
| CN101332515A (en) * | 2008-08-05 | 2008-12-31 | 中南大学 | Preparation method of fibrous iron-nickel alloy powder |
| CN101822985A (en) * | 2009-03-04 | 2010-09-08 | 中国石油天然气股份有限公司 | Pretreatment method of nickel-based hydrogenation catalyst |
| CN103071794A (en) * | 2013-02-25 | 2013-05-01 | 苏州南航腾龙科技有限公司 | Breathing type reduction method of metal powder and sintered product thereof |
| US20130178357A1 (en) * | 2012-01-05 | 2013-07-11 | Brookhaven Science Associates, Llc | Method for Removing Strongly Adsorbed Surfactants and Capping Agents from Metal to Facilitate their Catalytic Applications |
| CN110538657A (en) * | 2019-09-16 | 2019-12-06 | 福州大学 | Iron-nickel layered double hydroxide and preparation method and application thereof |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2007111635A (en) * | 2005-10-20 | 2007-05-10 | Sumitomo Electric Ind Ltd | Metal catalyst and method for manufacturing the same |
| CN101332515A (en) * | 2008-08-05 | 2008-12-31 | 中南大学 | Preparation method of fibrous iron-nickel alloy powder |
| CN101822985A (en) * | 2009-03-04 | 2010-09-08 | 中国石油天然气股份有限公司 | Pretreatment method of nickel-based hydrogenation catalyst |
| US20130178357A1 (en) * | 2012-01-05 | 2013-07-11 | Brookhaven Science Associates, Llc | Method for Removing Strongly Adsorbed Surfactants and Capping Agents from Metal to Facilitate their Catalytic Applications |
| CN103071794A (en) * | 2013-02-25 | 2013-05-01 | 苏州南航腾龙科技有限公司 | Breathing type reduction method of metal powder and sintered product thereof |
| CN110538657A (en) * | 2019-09-16 | 2019-12-06 | 福州大学 | Iron-nickel layered double hydroxide and preparation method and application thereof |
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