CN112774704A - Foam nickel self-supporting FeCo phosphide electrocatalyst and preparation method and application thereof - Google Patents
Foam nickel self-supporting FeCo phosphide electrocatalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN112774704A CN112774704A CN201911086064.7A CN201911086064A CN112774704A CN 112774704 A CN112774704 A CN 112774704A CN 201911086064 A CN201911086064 A CN 201911086064A CN 112774704 A CN112774704 A CN 112774704A
- Authority
- CN
- China
- Prior art keywords
- feco
- supporting
- self
- salt
- foamed 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 78
- 229910002546 FeCo Inorganic materials 0.000 title claims abstract description 63
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 41
- 239000006260 foam Substances 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 20
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011574 phosphorus Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 18
- 239000007864 aqueous solution Substances 0.000 claims abstract description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000008367 deionised water Substances 0.000 claims abstract description 10
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 10
- 239000001301 oxygen Substances 0.000 claims abstract description 10
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 10
- 150000001868 cobalt Chemical class 0.000 claims abstract description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 38
- 229910001868 water Inorganic materials 0.000 claims description 14
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 13
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 13
- 239000004202 carbamide Substances 0.000 claims description 13
- 229910052742 iron Inorganic materials 0.000 claims description 13
- 229910017052 cobalt Inorganic materials 0.000 claims description 12
- 239000010941 cobalt Substances 0.000 claims description 12
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 12
- 239000007789 gas Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical group O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 229910021205 NaH2PO2 Inorganic materials 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000012360 testing method Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 230000002441 reversible effect Effects 0.000 claims description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 3
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 239000003792 electrolyte Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical group O.O.O.O.O.O.O.O.O.[Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O SZQUEWJRBJDHSM-UHFFFAOYSA-N 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 229910000406 trisodium phosphate Inorganic materials 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 229940075397 calomel Drugs 0.000 claims description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 claims description 2
- 238000011056 performance test Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 2
- 239000003054 catalyst Substances 0.000 abstract description 16
- 230000003197 catalytic effect Effects 0.000 abstract description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 7
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 abstract description 3
- 229910000510 noble metal Inorganic materials 0.000 abstract description 3
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 230000007774 longterm Effects 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract description 2
- 239000010453 quartz Substances 0.000 abstract 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 150000002505 iron Chemical class 0.000 abstract 1
- 238000009210 therapy by ultrasound Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 description 6
- 238000003760 magnetic stirring Methods 0.000 description 6
- 238000007664 blowing Methods 0.000 description 4
- 229910001873 dinitrogen Inorganic materials 0.000 description 4
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 4
- 239000002064 nanoplatelet Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical group [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000005520 cutting process Methods 0.000 description 2
- 230000001351 cycling effect Effects 0.000 description 2
- 238000003487 electrochemical reaction Methods 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 229910052755 nonmetal Inorganic materials 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- 239000003245 coal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000011787 zinc oxide Substances 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
-
- B01J35/33—
-
- 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
-
- 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 foam nickel self-supporting FeCo phosphide electrocatalyst, a preparation method and application thereof, wherein foam nickel is subjected to ultrasonic treatment sequentially through hydrochloric acid, deionized water and absolute ethyl alcohol, and is dried for later use; mixing soluble cobalt salt and soluble iron salt to obtain an aqueous solution, vertically putting foamed nickel into a polytetrafluoroethylene container for hydrothermal reaction to obtain FeCo hydroxide; FeCo hydroxide and salt for providing element phosphorus are placed in a quartz boat, and the quartz boat is placed in a tube furnace for phosphating treatment to obtain the foamed nickel self-supporting FeCo phosphide catalytic material. The catalyst prepared by the invention realizes 50mA/cm in electrocatalytic oxygen production reaction2The current density of (a) requires an overpotential of only 205-250mv,compared with other traditional non-noble metal catalysts, the catalyst has better catalytic activity and excellent long-term stability, and the preparation method has the advantages of simple and convenient operation, short time consumption, and better economical efficiency and environmental protection.
Description
Technical Field
The invention relates to the technical field of electrocatalysis, in particular to a foamed nickel self-supporting FeCo phosphide electrocatalyst and a preparation method and application thereof.
Background
At present, the consumption of traditional non-renewable energy sources (petroleum, coal and the like) is increased, but the demand of people on energy sources is increased, and the attention of people on the problem of environmental pollution is paid recently, so that the exploration and development of new environment-friendly, high-efficiency and renewable energy sources become important in the research of modern energy sources. Among them, hydrogen energy has advantages of high energy density, being renewable, etc., and has become a research hotspot. Electrocatalytic water splitting is the simplest and most efficient method for preparing hydrogen energy. However, the Oxygen Evolution Reaction (OER) as a half reaction of hydrogen production by water electrolysis involves four-electron transfer, and the slow kinetic process thereof greatly limits the application of water electrolysis, so that the design of an efficient, stable and low-cost OER catalyst has important significance for promoting water decomposition and obtaining hydrogen energy with high efficiency.
Transition metal elements (Fe, Co, Ni, etc.) are abundant in the earth and lower in cost than noble metals, and have been the main subject of research on electrocatalytic oxygen evolution reactions. Researches show that the OER catalytic performance and RuO catalytic performance of the nonmetal electrocatalyst prepared by the reasonably designed experimental scheme2And IrO2The catalyst was comparable or even better. Especially, the doping of two or more metal complexes and nonmetal elements (S, P and the like) can greatly improve the catalytic performance of the material, so that the synthesis of the transition metal phosphide with a proper doping ratio is very important for the OER catalytic performance.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a foam nickel self-supporting FeCo phosphide electrocatalyst and a preparation method and application thereof, the raw materials used in the method are low in price, the reaction condition is easy to realize, the operation process is extremely simple, the prepared catalyst is iron-cobalt bimetallic phosphide directly grown on foam nickel in situ, the prepared catalyst has larger specific surface area and better OER catalytic performance, and under the alkaline condition, the overpotential of only 208mv (relative to a reversible hydrogen electrode) can realize 50mA/cm2Shows excellent oxygen evolution catalytic performance.
The technical purpose of the invention is realized by the following technical scheme.
The foamed nickel self-supporting FeCo phosphide electrocatalyst and its preparation process includes the following steps:
in step 1, the soluble cobalt salt is cobalt nitrate hexahydrate, cobalt nitrate, cobalt chloride.
In step 1, the soluble ferric salt is ferric nitrate nonahydrate, ferric nitrate, ferric chloride, ferric sulfate.
In step 1, the molar ratio of the elements cobalt and iron is (3-4): 1.
in step 1, the molar ratio of the amount of total metal species consisting of the elements cobalt and iron, urea and ammonium fluoride is 2: (6-8): (7.5-8).
In the step 1, magnetic stirring is adopted for uniform dispersion, the magnetic stirring time is 0.5-2h, and the rotating speed is 300-500 rpm.
in the step 2, the hydrothermal reaction temperature is 130-150 ℃, and the reaction time is 6-8 h.
In step 3, the atmosphere of inert protective gas is nitrogen, helium or argon, and the gas flow rate is 15-30 mL/min.
In step 3, the temperature is raised to 300 +/-20 ℃ from the room temperature of 20-25 ℃ at the heating rate of 1-5 ℃/min, and the temperature is kept for 1-3 hours, and then the temperature is naturally reduced to the room temperature of 20-25 ℃.
In step 3, the salt of elemental phosphorus is provided as NaH2PO2·H2And O, the mass ratio of the self-supporting FeCo hydroxide of the foamed nickel to the salt for providing the element phosphorus is (3-5): 1500.
in the technical scheme of the invention, before use, the foam Nickel (NF) is pretreated: cutting foamed Nickel (NF) into 3 x 5cm, ultrasonically cleaning the foamed Nickel (NF) in 3M hydrochloric acid (aqueous hydrogen chloride solution), deionized water and absolute ethyl alcohol for 10 minutes, then placing the cleaned foamed Nickel (NF) in a vacuum drying oven, and drying the cleaned foamed Nickel (NF) for 12 hours for later use at 60 ℃.
The application of the foamed nickel self-supporting FeCo phosphide electrocatalyst in the electrolytic water oxygen evolution reaction is characterized in that an electrochemical workstation is used for carrying out OER performance test, a three-electrode system is adopted, the foamed nickel self-supporting FeCo phosphide electrocatalyst is used as a working electrode, a calomel electrode is used as a reference electrode, a platinum sheet is used as a counter electrode, 1mol/L potassium hydroxide aqueous solution is adopted as an electrolyte, and the LSV test is carried out to realize the current density of 50mA/cm2The overpotential is 205-250mv (205 mv compared with reversible hydrogen electrode).
The invention has the beneficial effects that: the electrocatalysts with different morphologies are obtained by adjusting the proportion, and the prepared catalyst realizes 50mA/cm in the electrocatalytic oxygen production reaction (OER)2The required overpotential of the current density is 205-250mv (relative to a reversible hydrogen electrode), and the catalyst has better catalytic activity and excellent long-term stability compared with other traditional non-noble metal catalystsThe preparation method has the advantages of simple operation, short time consumption, and good economical efficiency and environmental protection.
Drawings
FIG. 1 is an XRD diffraction pattern of a foamed nickel self-supporting FeCo phosphide electrocatalyst prepared in example 1 of the present invention.
FIG. 2 is a SEM-EDS photograph of a foamed nickel self-supporting FeCo phosphide electrocatalyst prepared in example 1 of the present invention.
FIG. 3 is a SEM-EDS photograph of a foamed nickel self-supporting FeCo phosphide electrocatalyst prepared in example 2 of the present invention.
FIG. 4 is a SEM-EDS photograph of a foamed nickel self-supporting FeCo phosphide electrocatalyst prepared in example 3 of the present invention.
FIG. 5 is a SEM-EDS photograph of a foamed nickel self-supporting FeCo phosphide electrocatalyst prepared in example 4 of the present invention.
FIG. 6 is a linear sweep voltammogram of a foamed nickel self-supporting FeCo phosphide electrocatalyst prepared according to the present invention.
FIG. 7 is a Tafel plot of a foamed nickel self-supporting FeCo phosphide electrocatalyst prepared according to the present invention.
FIG. 8 is a graph showing the stability test of the nickel foam self-supporting FeCo phosphide electrocatalyst prepared in example 1 of the present invention.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
The nickel foams used in the examples were all treated as follows: cutting foamed Nickel (NF) into 3 x 5cm for treatment, ultrasonically cleaning NF in 3M hydrochloric acid, deionized water and absolute ethyl alcohol for 10 minutes, then placing the NF in a vacuum drying oven, and drying for later use at 60 ℃ for 12 hours.
Example 1
1.6 mmol of urea, 7.5mmol of ammonium fluoride, 436.545mg of cobalt nitrate hexahydrate and 202mg of iron nitrate nonahydrate (Co/Fe is 3:1) are weighed into a beaker, 40 ml of deionized water are added, and the magnetic stirring time is 1h and the rotating speed is 400 rpm.
2. And (3) putting the prepared aqueous solution into a 50ml polytetrafluoroethylene reaction kettle, vertically putting the pretreated foamed nickel into the reaction kettle, and putting the reaction kettle into an air-blowing drying oven to perform hydrothermal reaction for 8 hours at the temperature of 120 ℃.
3. Weighing 1.2 g of NaH2PO 2. H2O, placing the NaH2PO 2. H2O and 3mg of FeCo/NF obtained in the step 2 into two boats respectively, placing the two boats into a tube furnace, adjusting the flow rate of nitrogen gas to be 15-30mL/min, raising the temperature to 300 ℃ at the rate of 2 ℃/min, preserving the temperature for 2H, and naturally cooling to obtain the foamed nickel self-supporting FeCo phosphide electrocatalyst (Fe phosphide)1Co3-P/NF)。
Example 2
1.6 mmol of urea, 7.5mmol of ammonium fluoride, 291.03mg of cobalt nitrate hexahydrate and 404mg of iron nitrate nonahydrate (Co/Fe is 1:1) are weighed into a beaker, 40 ml of deionized water are added, and the magnetic stirring time is 1h and the rotating speed is 400 rpm.
2. And (3) putting the prepared aqueous solution into a 50ml polytetrafluoroethylene reaction kettle, vertically putting the pretreated foamed nickel into the reaction kettle, and putting the reaction kettle into an air-blowing drying oven to perform hydrothermal reaction for 8 hours at the temperature of 120 ℃.
3, weighing 1.2 g of NaH2PO 2. H2O, respectively placing the NaH2PO 2. H2O and 5mg of FeCo/NF obtained in the step 2 into two boats, placing the boats into a tubular furnace, adjusting the flow rate of nitrogen gas to be 15-30mL/min, raising the temperature to 300 ℃ at the rate of 2 ℃/min, preserving the temperature for 2H, and naturally cooling to obtain the foamed nickel self-supporting FeCo phosphide electrocatalyst (Fe phosphide)1Co1-P/NF)。
Example 3
1.6 mmol of urea, 7.5mmol of ammonium fluoride, 388.04mg of cobalt nitrate hexahydrate and 269.3mg of iron nitrate nonahydrate (Co/Fe is 2:1) are weighed into a beaker, 40 ml of deionized water are added, and the magnetic stirring time is 1h and the rotating speed is 400 rpm.
2. And (3) putting the prepared aqueous solution into a 50ml polytetrafluoroethylene reaction kettle, vertically putting the pretreated foamed nickel into the reaction kettle, and putting the reaction kettle into an air-blowing drying oven to perform hydrothermal reaction for 8 hours at the temperature of 120 ℃.
3, weighing 1.2 g of NaH2PO 2. H2O, respectively placing the NaH2PO 2. H2O and 4mg of FeCo/NF obtained in the step 2 into two boats, placing the boats into a tubular furnace, adjusting the flow rate of nitrogen gas to be 15-30mL/min, raising the temperature to 300 ℃ at the rate of 2 ℃/min, preserving the temperature for 2H, and naturally cooling to obtain the foam nickel self-supporting FeCo phosphide electrocatalysisAgent (Fe)1Co2-P/NF)。
Example 4
1.6 mmol of urea, 7.5mmol of ammonium fluoride, 465.648mg of cobalt nitrate hexahydrate and 161.6mg of iron nitrate nonahydrate (Co/Fe is 4:1) are weighed into a beaker, 40 ml of deionized water are added, and the magnetic stirring time is 1h and the rotating speed is 400 rpm.
2. And (3) putting the prepared aqueous solution into a 50ml polytetrafluoroethylene reaction kettle, vertically putting the pretreated foamed nickel into the reaction kettle, and putting the reaction kettle into an air-blowing drying oven to perform hydrothermal reaction for 8 hours at the temperature of 120 ℃.
3, weighing 1.2 g of NaH2PO 2. H2O, putting the NaH2PO 2. H2O and 3mg of FeCo/NF obtained in the step 2 into two boats respectively, putting the two boats into a tubular furnace, adjusting the flow rate of nitrogen gas to be 15-30mL/min, heating to 300 ℃ at the heating rate of 2 ℃/min, preserving heat for 2H, and naturally cooling to obtain the foamed nickel self-supporting FeCo phosphide electrocatalyst (Fe phosphide)1Co4-P/NF)。
The resulting product was subjected to XRD testing in order to determine the structure and composition of the catalyst. As shown in fig. 1, the strongest diffraction peaks at diffraction angles 2 θ of 44.6 °, about 52.1 ° and about 76.5 ° correspond to the (111), (200) and (220) crystal planes of nickel, respectively, Fe1Co3The (101), (200) and (131) crystal plane diffraction peaks of the-P/NF sample are consistent with the XED result, and the successful synthesis of the foamed nickel self-supporting FeCo phosphide electrocatalyst is proved. From FIG. 2, Fe can be seen1Co3The P/NF catalyst is uniformly loaded on the foam nickel framework like a nanometer needle, and the special structure is very beneficial to the electrocatalytic oxygen evolution reaction. The scanning electron microscope image of example 2 is shown in fig. 3, the microscopic morphology of the nanoplatelets is interlamellar staggered, the scanning electron microscope image of example 3 is shown in fig. 4, the morphology of the nanoplatelets and the nanoneedles are staggered and mainly grow, fig. 5 is the scanning electron microscope image of example 4, and the morphology of the nanoplatelets is similar to that of example 3, but mainly the nanoneedles are used, and the interlamellar staggered nanoplatelets cannot be obviously observed. From XRD, SEM and EDS, the catalyst prepared by the present invention enables in situ growth of iron-cobalt bimetallic phosphide directly on foamed nickel.
The sample of the example was used as a working electrode, a platinum sheet electrode as a counter electrode, and a zinc oxide as a counter electrodeThe mercury electrode is used as a reference electrode, 1mol/L potassium hydroxide aqueous solution is used as electrolyte, the overpotential of the sample in the embodiment of the invention is tested, and a chenghua 660E electrochemical workstation is used for testing. The electrocatalytic oxygen production linear sweep voltammogram of the sample of example 1 is shown in figure 6. As can be seen from FIG. 6, when the current density was 50mA/cm2The overpotentials required by the samples of each example are respectively 208mv, 220mv, 230mv and 250mv (with the current density of 50 mA/cm)2The corresponding voltage value was subtracted by 1.23V to obtain the overpotential), Fe prepared in example 11Co3The P/NF sample showed lower overpotential, which indicates that the example 1 of the present invention has more excellent electrocatalytic oxygen evolution performance. Tafel curve measurement is performed according to the test result of FIG. 6, and as shown in FIG. 7, the nickel foam self-supporting FeCo phosphide electrocatalyst (Fe) prepared in example 1 of the present invention1Co3-P/NF) sample has smaller Tafel slope compared with other samples, the Tafel slope can be used for judging the difficulty of electrochemical reaction, the smaller the slope, the easier the electrochemical reaction is, therefore, the nickel foam self-supporting FeCo phosphide electrocatalyst (Fe) prepared in example 11Co3P/NF) has faster OER kinetics than the other example catalysts of the invention. The stability of the catalyst determines the service life of the catalyst in practical application, fig. 8 is an LSV polarization curve before and after CV cycling of the nickel foam self-supporting FeCo phosphide electrocatalyst, and from the LSV polarization curve before and after 1000 cycles of cycling almost coincide, which shows that the catalyst has relatively stable OER catalytic performance under alkaline conditions.
The preparation of the nickel foam self-supporting FeCo phosphide electrocatalyst can be realized by adjusting the process parameters according to the content of the invention, and the test shows that the performance is basically consistent with the invention. The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. A foamed nickel self-supporting FeCo phosphide electrocatalyst is characterized by being prepared by the following steps:
step 1, placing soluble cobalt salt, soluble ferric salt, urea and ammonium fluoride in deionized water and uniformly dispersing to obtain a mixed aqueous solution, wherein the molar ratio of element cobalt to iron is (1-4): 1, the amount of total metal species consisting of the elements cobalt and iron, the molar ratio between urea and ammonium fluoride being (2-3): (6-10): (7-8);
step 2, soaking the foamed nickel in the mixed aqueous solution prepared in the step 1 for soaking, and then carrying out hydrothermal reaction for 5-10 hours at 120-150 ℃ to obtain foamed nickel self-supporting FeCo hydroxide;
step 3, respectively loading the foamed nickel self-supporting FeCo hydroxide prepared in the step 2 and salt for providing element phosphorus into two boats, placing the two boats in a tubular furnace, heating the mixture to 300 +/-20 ℃ from the room temperature of 20-25 ℃ in the atmosphere of inert protective gas, preserving the heat for 1-5 hours, and naturally cooling the mixture to the room temperature of 20-25 ℃ to obtain the foamed nickel self-supporting FeCo phosphide electrocatalyst; providing the salt of elemental phosphorus as NaH2PO2、Na3PO4、Na2HPO2、NaH2PO3、NaH2PO4、Na2HPO3、Na2HPO4And their hydrated salts; the mass ratio of the foam nickel self-supporting FeCo hydroxide to the salt for providing the element phosphorus is (1-5): (1000-1500) providing a salt of elemental phosphorus upstream of a nickel foam self-supporting FeCo hydroxide in an inert shielding gas flow.
2. The foamed nickel self-supporting FeCo phosphide electrocatalyst according to claim 1, wherein in step 1, the soluble cobalt salt is cobalt nitrate hexahydrate, cobalt nitrate, cobalt chloride; the soluble ferric salt is ferric nitrate nonahydrate, ferric nitrate, ferric chloride and ferric sulfate.
3. The foamed nickel self-supporting FeCo phosphide electrocatalyst according to claim 1, characterized in that in step 1 the molar ratio of elemental cobalt to iron is (3-4): 1; the amount of total metal species consisting of the elements cobalt and iron, the molar ratio of urea to ammonium fluoride is 2: (6-8): (7.5-8).
4. The self-supported foamed nickel FeCo phosphide electrocatalyst according to claim 1, wherein in step 2, the hydrothermal reaction temperature is 130 to 150 ℃ and the reaction time is 6 to 8 h.
5. The foamed nickel self-supporting FeCo phosphide electrocatalyst according to claim 1, wherein in step 3, the inert shielding gas atmosphere is nitrogen, helium or argon, and the gas flow rate is 15-30 mL/min; heating to 300 +/-20 ℃ from the room temperature of 20-25 ℃ at the heating rate of 1-5 ℃/min, preserving the temperature for 1-3 hours, and naturally cooling to the room temperature of 20-25 ℃; providing the salt of elemental phosphorus as NaH2PO2·H2And O, the mass ratio of the self-supporting FeCo hydroxide of the foamed nickel to the salt for providing the element phosphorus is (3-5): 1500.
6. the preparation method of the foam nickel self-supporting FeCo phosphide electrocatalyst is characterized by comprising the following steps of:
step 1, placing soluble cobalt salt, soluble ferric salt, urea and ammonium fluoride in deionized water and uniformly dispersing to obtain a mixed aqueous solution, wherein the molar ratio of element cobalt to iron is (1-4): 1, the amount of total metal species consisting of the elements cobalt and iron, the molar ratio between urea and ammonium fluoride being (2-3): (6-10): (7-8);
step 2, soaking the foamed nickel in the mixed aqueous solution prepared in the step 1 for soaking, and then carrying out hydrothermal reaction for 5-10 hours at 120-150 ℃ to obtain foamed nickel self-supporting FeCo hydroxide;
step 3, respectively loading the foamed nickel self-supporting FeCo hydroxide prepared in the step 2 and salt for providing element phosphorus into two boats, placing the two boats in a tubular furnace, heating the mixture to 300 +/-20 ℃ from the room temperature of 20-25 ℃ in the atmosphere of inert protective gas, preserving the heat for 1-5 hours, and naturally cooling the mixture to the room temperature of 20-25 ℃ to obtain the foamed nickel self-supporting FeCo phosphide electrocatalyst; providing the salt of elemental phosphorus as NaH2PO2、Na3PO4、Na2HPO2、NaH2PO3、NaH2PO4、Na2HPO3、Na2HPO4And their hydrated salts; the mass ratio of the foam nickel self-supporting FeCo hydroxide to the salt for providing the element phosphorus is (1-5): (1000-1500) providing a salt of elemental phosphorus upstream of a nickel foam self-supporting FeCo hydroxide in an inert shielding gas flow.
7. The method for preparing a self-supported FeCo phosphide electrocatalyst with foamed nickel according to claim 6, wherein in step 1, the soluble cobalt salt is cobalt nitrate hexahydrate, cobalt nitrate, cobalt chloride; the soluble ferric salt is ferric nitrate nonahydrate, ferric nitrate, ferric chloride and ferric sulfate; the molar ratio of the elements cobalt and iron is (3-4): 1; the amount of total metal species consisting of the elements cobalt and iron, the molar ratio of urea to ammonium fluoride is 2: (6-8): (7.5-8).
8. The method for preparing a self-supported FeCo phosphide electrocatalyst with foamed nickel as claimed in claim 6, wherein in step 2, the hydrothermal reaction temperature is 130-150 ℃ and the reaction time is 6-8 h.
9. The method for preparing a self-supported FeCo phosphide electrocatalyst with foamed nickel according to claim 6, wherein in step 3, the inert shielding gas atmosphere is nitrogen, helium or argon, and the gas flow rate is 15-30 mL/min; heating to 300 +/-20 ℃ from the room temperature of 20-25 ℃ at the heating rate of 1-5 ℃/min, preserving the temperature for 1-3 hours, and naturally cooling to the room temperature of 20-25 ℃; providing the salt of elemental phosphorus as NaH2PO2·H2And O, the mass ratio of the self-supporting FeCo hydroxide of the foamed nickel to the salt for providing the element phosphorus is (3-5): 1500.
10. use of a foamed nickel self-supporting FeCo phosphide electrocatalyst according to any one of claims 1 to 5 for catalysing the oxygen evolution reaction from electrolysis water by means of electrochemistryThe workstation carries out OER performance test, adopts a three-electrode system, takes a foam nickel self-supporting FeCo phosphide electrocatalyst as a working electrode, a calomel electrode as a reference electrode, a platinum sheet as a counter electrode and an electrolyte adopting 1mol/L potassium hydroxide solution, and realizes the current density of 50mA/cm through LSV test2The overpotential is 205-250mv (relative to the reversible hydrogen electrode).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911086064.7A CN112774704A (en) | 2019-11-07 | 2019-11-07 | Foam nickel self-supporting FeCo phosphide electrocatalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911086064.7A CN112774704A (en) | 2019-11-07 | 2019-11-07 | Foam nickel self-supporting FeCo phosphide electrocatalyst and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN112774704A true CN112774704A (en) | 2021-05-11 |
Family
ID=75748241
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911086064.7A Pending CN112774704A (en) | 2019-11-07 | 2019-11-07 | Foam nickel self-supporting FeCo phosphide electrocatalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112774704A (en) |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113564627A (en) * | 2021-08-24 | 2021-10-29 | 青岛科技大学 | Ni2-xCoxP quantum dot/N, O codoped carbon/NF electrode material and preparation method thereof |
| CN113637997A (en) * | 2021-08-11 | 2021-11-12 | 广西师范大学 | Co2P/CuP2Preparation method of/NF hydrogen evolution and oxygen evolution electrocatalyst |
| CN113684494A (en) * | 2021-09-15 | 2021-11-23 | 吉林大学 | Ternary transition metal electrolysis water hydrogen evolution catalyst composite material and preparation method thereof |
| CN114150344A (en) * | 2021-12-23 | 2022-03-08 | 北京中海前沿材料技术有限公司 | Cobalt nitride/iron phosphide self-supporting electrode for water decomposition and preparation method thereof |
| CN114411189A (en) * | 2021-12-22 | 2022-04-29 | 西安理工大学 | Preparation method of layered double hydroxide catalyst modified by CoSe |
| CN114408886A (en) * | 2022-01-26 | 2022-04-29 | 青岛科技大学 | Preparation of porous iron nickel phosphide doped with noble metal |
| CN114481208A (en) * | 2022-02-11 | 2022-05-13 | 合肥国轩高科动力能源有限公司 | Bimetal phosphide nitrogen-doped carbon material composite oxygen catalyst and synthesis method thereof |
| CN114622217A (en) * | 2021-08-06 | 2022-06-14 | 广东工业大学 | Iron-cobalt phosphide catalyst and preparation method and application thereof |
| CN114855205A (en) * | 2022-04-11 | 2022-08-05 | 浙江理工大学 | Preparation method of ternary metal sulfide three-dimensional electrode with multilevel structure |
| CN115010220A (en) * | 2022-06-17 | 2022-09-06 | 南通大学 | Electrode with phosphide and hydroxide heterostructure and preparation method thereof |
| CN115029721A (en) * | 2022-05-06 | 2022-09-09 | 海南大学 | Self-supporting partial sulfur substituted Co 3 O 4 Preparation method and application of nanowire array catalyst |
| CN116062722A (en) * | 2023-02-24 | 2023-05-05 | 海卓动力(北京)能源科技有限公司 | Catalyst and preparation method and application thereof |
| 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 |
|---|---|---|---|---|
| CN105720278A (en) * | 2016-03-31 | 2016-06-29 | 华中科技大学 | High-efficiency multi-element transition metal phosphide hydrogen-evolution catalyst and preparation method thereof |
| US20170218528A1 (en) * | 2016-01-29 | 2017-08-03 | Bo Zhang | Homogeneously dispersed multimetal oxy-hydroxide catalysts |
| CN109423660A (en) * | 2017-09-01 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of water oxygen elctro-catalyst and preparation method thereof for electrocatalytic decomposition water |
| CN109821561A (en) * | 2019-03-22 | 2019-05-31 | 黑龙江大学 | A kind of preparation method of self-supporting phosphatization ferro-cobalt nanosphere elctro-catalyst |
-
2019
- 2019-11-07 CN CN201911086064.7A patent/CN112774704A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170218528A1 (en) * | 2016-01-29 | 2017-08-03 | Bo Zhang | Homogeneously dispersed multimetal oxy-hydroxide catalysts |
| CN105720278A (en) * | 2016-03-31 | 2016-06-29 | 华中科技大学 | High-efficiency multi-element transition metal phosphide hydrogen-evolution catalyst and preparation method thereof |
| CN109423660A (en) * | 2017-09-01 | 2019-03-05 | 中国科学院大连化学物理研究所 | A kind of water oxygen elctro-catalyst and preparation method thereof for electrocatalytic decomposition water |
| CN109821561A (en) * | 2019-03-22 | 2019-05-31 | 黑龙江大学 | A kind of preparation method of self-supporting phosphatization ferro-cobalt nanosphere elctro-catalyst |
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114622217A (en) * | 2021-08-06 | 2022-06-14 | 广东工业大学 | Iron-cobalt phosphide catalyst and preparation method and application thereof |
| CN114622217B (en) * | 2021-08-06 | 2023-04-18 | 广东工业大学 | Iron-cobalt phosphide catalyst and preparation method and application thereof |
| CN113637997B (en) * | 2021-08-11 | 2023-01-31 | 广西师范大学 | Co 2 P/CuP 2 Preparation method of/NF hydrogen evolution and oxygen evolution electrocatalyst |
| CN113637997A (en) * | 2021-08-11 | 2021-11-12 | 广西师范大学 | Co2P/CuP2Preparation method of/NF hydrogen evolution and oxygen evolution electrocatalyst |
| CN113564627A (en) * | 2021-08-24 | 2021-10-29 | 青岛科技大学 | Ni2-xCoxP quantum dot/N, O codoped carbon/NF electrode material and preparation method thereof |
| CN113564627B (en) * | 2021-08-24 | 2022-06-10 | 青岛科技大学 | Ni2-xCoxP quantum dot/N, O codoped carbon/NF electrode material and preparation method thereof |
| CN113684494A (en) * | 2021-09-15 | 2021-11-23 | 吉林大学 | Ternary transition metal electrolysis water hydrogen evolution catalyst composite material and preparation method 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 |
| 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 |
| CN114411189A (en) * | 2021-12-22 | 2022-04-29 | 西安理工大学 | Preparation method of layered double hydroxide catalyst modified by CoSe |
| CN114150344A (en) * | 2021-12-23 | 2022-03-08 | 北京中海前沿材料技术有限公司 | Cobalt nitride/iron phosphide self-supporting electrode for water decomposition and preparation method thereof |
| CN114408886A (en) * | 2022-01-26 | 2022-04-29 | 青岛科技大学 | Preparation of porous iron nickel phosphide doped with noble metal |
| CN114408886B (en) * | 2022-01-26 | 2023-12-22 | 青岛科技大学 | Preparation of noble metal doped porous iron-nickel phosphide |
| CN114481208A (en) * | 2022-02-11 | 2022-05-13 | 合肥国轩高科动力能源有限公司 | Bimetal phosphide nitrogen-doped carbon material composite oxygen catalyst and synthesis method thereof |
| CN114855205A (en) * | 2022-04-11 | 2022-08-05 | 浙江理工大学 | Preparation method of ternary metal sulfide three-dimensional electrode with multilevel structure |
| CN114855205B (en) * | 2022-04-11 | 2024-02-09 | 浙江理工大学 | Preparation method of three-dimensional electrode of ternary metal sulfide with multilevel structure |
| CN115029721A (en) * | 2022-05-06 | 2022-09-09 | 海南大学 | Self-supporting partial sulfur substituted Co 3 O 4 Preparation method and application of nanowire array catalyst |
| CN115010220A (en) * | 2022-06-17 | 2022-09-06 | 南通大学 | Electrode with phosphide and hydroxide heterostructure and preparation method thereof |
| CN115010220B (en) * | 2022-06-17 | 2023-12-01 | 南通大学 | Electrode with phosphide synergistic hydroxide heterostructure and preparation method thereof |
| CN116062722A (en) * | 2023-02-24 | 2023-05-05 | 海卓动力(北京)能源科技有限公司 | Catalyst and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112774704A (en) | Foam nickel self-supporting FeCo phosphide electrocatalyst and preparation method and application thereof | |
| CN108671953B (en) | Transition metal nitride/carbon electrocatalyst and preparation and application thereof | |
| CN110479329B (en) | Preparation and application of phosphorus-doped cobalt telluride nano material | |
| CN108714429B (en) | Rod-shaped CoP/CoP2Preparation method of nano composite electrocatalyst | |
| CN112941559B (en) | Fe-Co bimetallic phosphide electrode material and preparation and application thereof | |
| CN110813350B (en) | Carbon-based composite electrocatalyst and preparation method and application thereof | |
| CN110075853B (en) | Electrocatalytic fully-decomposed water CoZn-LDHs-ZIF @ C composite structure material, and preparation method and application thereof | |
| CN110512228B (en) | Preparation method of nickel phosphide/nickel foam electrochemical functional hydrogen evolution material | |
| CN108048868B (en) | Molybdenum nitride nanorod electrode material and preparation method and application thereof | |
| CN109628951B (en) | Nickel sulfide hydrogen evolution electrocatalyst and preparation method and application thereof | |
| CN110484934B (en) | Preparation method of nickel-phosphorus/nickel phosphide-carbon cloth three-dimensional self-supporting hydrogen evolution electrode material | |
| CN112481653B (en) | Defect-rich molybdenum-doped cobalt selenide/nano carbon electrocatalyst and preparation method and application thereof | |
| CN109898093B (en) | 3D structure composite hydrogen evolution electrode and preparation method thereof | |
| CN112058293B (en) | Preparation method of nitrogen-phosphorus-codoped foam carbon nanosheet loaded NiCo nanoparticle composite material, product and application thereof | |
| CN113105645B (en) | Preparation method, product and application of nickel-based metal organic framework compound | |
| CN110534755A (en) | A kind of preparation method and application of zinc-base metal-organic framework material and its nitrogen co-doped carbon-based oxygen reduction electro-catalyst of iron | |
| CN110983360A (en) | Porous nitrogen-doped graphene composite cobalt phosphide nanosheet and preparation method and application thereof | |
| CN111701607A (en) | MnCo2O4@Ni2P/NF difunctional full-hydrolysis catalyst and preparation method and application thereof | |
| CN112663085A (en) | Preparation method and application of high-performance cobalt-based oxygen evolution electrocatalytic nanomaterial | |
| CN111957336A (en) | Preparation method of ZIF-8-derived Fe-N-C oxygen reduction electrocatalyst | |
| CN109585861B (en) | Preparation method of dual-functional cobalt monoxide and nitrogen-doped carbon in-situ composite electrode | |
| CN106972177B (en) | A kind of CoO/Co/C trielement composite material and its preparation method and application | |
| CN113832494A (en) | Preparation method and application of transition/rare earth multi-metal co-doped phosphide | |
| CN113881964A (en) | Non-acid medium preparation method of flaky nickel phosphide array electrode material | |
| CN113774428A (en) | Preparation method of efficient cobalt rhodium hydroxide nanoparticle/carbon cloth electrode, product and application thereof |
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: 20210511 |