CN114196971A - Preparation method of noble metal doped double-metal phosphide catalyst for electrochemical full-hydrolysis - Google Patents
Preparation method of noble metal doped double-metal phosphide catalyst for electrochemical full-hydrolysis Download PDFInfo
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- CN114196971A CN114196971A CN202210000853.XA CN202210000853A CN114196971A CN 114196971 A CN114196971 A CN 114196971A CN 202210000853 A CN202210000853 A CN 202210000853A CN 114196971 A CN114196971 A CN 114196971A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 19
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- 238000006460 hydrolysis reaction Methods 0.000 title abstract description 13
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- 239000000463 material Substances 0.000 claims abstract description 94
- 239000010948 rhodium Substances 0.000 claims abstract description 57
- 229910052703 rhodium Inorganic materials 0.000 claims abstract description 47
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims abstract description 46
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- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 15
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000004202 carbamide Substances 0.000 claims abstract description 9
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 claims abstract description 5
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims abstract description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 229910052573 porcelain Inorganic materials 0.000 claims description 12
- 239000002904 solvent Substances 0.000 claims description 10
- 150000001868 cobalt Chemical class 0.000 claims description 9
- 150000003283 rhodium Chemical class 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 239000012046 mixed solvent Substances 0.000 claims description 6
- -1 polytetrafluoroethylene Polymers 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000011144 upstream manufacturing Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 150000002505 iron Chemical class 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 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 2
- 239000010970 precious metal Substances 0.000 claims 2
- 150000004679 hydroxides Chemical class 0.000 claims 1
- 239000002243 precursor Substances 0.000 abstract description 9
- 230000002378 acidificating effect Effects 0.000 abstract description 8
- SZQUEWJRBJDHSM-UHFFFAOYSA-N iron(3+);trinitrate;nonahydrate Chemical compound 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 abstract description 5
- 230000001588 bifunctional effect Effects 0.000 abstract description 3
- 239000002131 composite material Substances 0.000 abstract description 3
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000012299 nitrogen atmosphere Substances 0.000 abstract description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- 239000002994 raw material Substances 0.000 abstract 1
- WGDMDZWCFNRYNZ-UHFFFAOYSA-N [Rh].[Fe].[Co] Chemical compound [Rh].[Fe].[Co] WGDMDZWCFNRYNZ-UHFFFAOYSA-N 0.000 description 29
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 238000012360 testing method Methods 0.000 description 18
- 239000000243 solution Substances 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- 238000000840 electrochemical analysis Methods 0.000 description 11
- 229910017052 cobalt Inorganic materials 0.000 description 9
- 239000010941 cobalt Substances 0.000 description 9
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 9
- 238000004502 linear sweep voltammetry Methods 0.000 description 9
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 8
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 229910021607 Silver chloride Inorganic materials 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 230000007062 hydrolysis Effects 0.000 description 6
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000004108 freeze drying Methods 0.000 description 5
- 238000010335 hydrothermal treatment Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 238000013507 mapping Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
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- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000004098 selected area electron diffraction Methods 0.000 description 2
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- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- 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
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Abstract
The invention discloses a preparation method of a noble metal doped double-metal phosphide catalyst for electrochemical full-hydrolysis. Wherein the noble metal is rhodium, and the bimetallic phosphide is cobalt iron phosphide. According to the preparation method, cobalt nitrate hexahydrate, ferric nitrate nonahydrate, rhodium trichloride and urea are used as raw materials, a rhodium-doped cobalt iron double hydroxide precursor is obtained by a glycol-assisted hydrothermal method, and then the rhodium-doped cobalt iron double hydroxide precursor and sodium hypophosphite are annealed in a nitrogen atmosphere to obtain the petal-shaped rhodium-doped cobalt iron phosphide nano material. The material can reach 10 mA cm only by 76 mV overpotential in HER under acidic reaction condition‑2The current density of (1). In 1M KOH, when the current density reaches 10 mA cm‑2The overpotentials for HER and OER were 48 mV and 303 mV, respectively. Rh doped Co when used as a bifunctional electrode for bulk water splitting2Fe-P composite in 1M KOH onlyThe battery voltage can reach 10 mA cm by requiring 1.54V‑2And the current density is maintained stable for not less than 30 hours. Meanwhile, the preparation method is simple and easy, the cost is low, the performance can be comparable to that of a commercial noble metal catalyst, and the application prospect is good.
Description
Technical Field
The invention relates to a preparation method of a noble metal doped double-metal phosphide catalyst for electrochemical full-hydrolysis, belonging to the technical field of electrochemistry.
Background
The excessive consumption of non-renewable energy sources and the consequent environmental pollution problems compel us to find and develop renewable clean energy sources that can replace non-renewable energy sources. Hydrogen energy is considered to be one of the most promising clean energy sources in the 21 st century, as a new clean, efficient, safe and sustainable energy source. The hydrogen production by water electrolysis is an effective way to solve the current dilemma. The electrolyzed water is divided into two half reactions, namely a hydrogen evolution reaction and an oxygen evolution reaction. The total reaction efficiency of water electrolysis depends on the efficiency of two half reactions, which are difficult to occur in a conventional state and need to overcome a certain activation barrier with the aid of a catalyst, so that a high-activity bifunctional catalyst needs to be developed to reduce the overpotential of the water decomposition reaction, thereby improving the energy conversion efficiency. The existing electrocatalysts are various, and the high-efficiency electrocatalysts are still mainly made of rare and expensive noble metal-based materials, which is not beneficial to large-scale application in industry. Therefore, there is an urgent need to develop a low overpotential and inexpensive electrocatalyst to improve reaction kinetics and water electrolysis efficiency. .
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a preparation method and application of a noble metal doped double-metal phosphide catalyst for electrochemical full-hydrolysis, which are used for solving the problem of low activity of an electrocatalyst material in an electrocatalytic full-hydrolysis reaction in the prior art.
The invention provides a preparation method of a bimetallic phosphide electrocatalytic material for electrocatalytic hydrogen evolution, which comprises the following steps:
preparing rhodium-doped cobalt-iron double hydroxide by using an ethylene glycol-assisted hydrothermal method;
and annealing the rhodium-doped cobalt iron double hydroxide and sodium hypophosphite in nitrogen to obtain the noble metal-doped bimetallic phosphide material.
Further, the preparation of the rhodium-doped cobalt iron double hydroxide by using a solvothermal method comprises the following steps:
dissolving soluble cobalt salt, soluble ferric salt, soluble rhodium salt and urea in a solvent according to a certain molar ratio to obtain a solution, wherein the solvent is a mixed solvent of ethylene glycol and water in a certain volume ratio;
stirring the solution at normal temperature for 30min, pouring the solution into a polytetrafluoroethylene lining, placing the lining in a stainless steel hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 12 h;
after the reaction is finished, cooling to room temperature, centrifuging the product, washing with water, and freeze-drying to obtain the rhodium-doped cobalt-iron double hydroxide.
Further, annealing the rhodium-doped cobalt iron double hydroxide and sodium hypophosphite in nitrogen to obtain the noble metal-doped bimetallic phosphide material, wherein the noble metal-doped bimetallic phosphide material comprises the following steps:
and putting the rhodium-doped cobalt iron double hydroxide into a porcelain boat, putting sodium hypophosphite into another porcelain boat at the upstream of the horizontal tube furnace, and heating for 1-3 h in nitrogen at 350 ℃ to obtain the noble metal-doped bimetallic phosphide. .
Further, the cobalt salt is cobalt nitrate hexahydrate, the iron salt is ferric nitrate nonahydrate, and the rhodium salt is rhodium trichloride.
Further, the cobalt salt: iron salt: rhodium salts: the molar ratio of urea is 2:1: (0.1-0.3): 4. the volume mass ratio of the solvent to the cobalt salt is 40 mL: 0.291 g.
Further, the solvent ethylene glycol: the volume ratio of the deionized water is 3: 1;
further, the mass of the rhodium-doped cobalt iron double hydroxide is 10-20 mg; the mass of the sodium hypophosphite is 100-200 mg.
Preferably, the rhodium-doped cobalt iron double hydroxide and the sodium hypophosphite are heated in nitrogen for 2 hours.
A noble metal doped double-metal phosphide material for electrocatalytic total hydrolysis is prepared by any one of the preparation methods.
The invention has the following positive effects:
the method comprises the steps of obtaining a rhodium-doped cobalt iron double hydroxide precursor by an ethylene glycol-assisted hydrothermal method, and annealing the rhodium-doped cobalt iron double hydroxide precursor and sodium hypophosphite in a nitrogen atmosphere to obtain the petal-shaped rhodium-doped cobalt iron phosphide nano material. The material can reach 10 mA cm only by 76 mV overpotential in HER under acidic reaction condition-2The current density of (1). In 1M KOH, when the current density reaches 10 mA cm-2The overpotentials for HER and OER were 48 mV and 303 mV, respectively. Rh doped Co when used as a bifunctional electrode for bulk water splitting2The Fe-P composite material can reach 10 mA cm in 1M KOH only by low cell voltage of 1.54V-2Current density of (A) andthe stability is maintained for not less than 30 hours. Meanwhile, the preparation method is simple and easy, the cost is low, the performance can be comparable to that of a commercial noble metal catalyst, and the application prospect is good.
Drawings
Fig. 1A is an X-ray diffraction pattern of rhodium-doped cobalt iron double hydroxide and pure cobalt iron double hydroxide precursors with cobalt iron rhodium ratios of 2:1:0.1 and 2:1:0.3 provided in examples 1, 2, and 3 of the present invention.
FIG. 1B is an X-ray diffraction pattern of rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2 and 3 of the present invention at a ratio of cobalt iron to rhodium of 2:1:0.1 and 2:1: 0.3.
Fig. 2A is a Scanning Electron Microscope (SEM) image of a rhodium-doped cobalt iron double hydroxide precursor with a cobalt iron rhodium ratio of 2:1:0.3 according to example 2 of the present invention.
Fig. 2B is a Scanning Electron Microscope (SEM) image of a rhodium-doped cobalt iron phosphide material with a cobalt iron rhodium ratio of 2:1:0.3 provided in example 2 of the present invention.
FIG. 2C is a Transmission Electron Microscope (TEM) image of a rhodium-doped CoFeP material with a CoFeRh ratio of 2:1:0.3, provided in example 2 of the present invention.
Figure 2D is a high resolution tem (hrtem) image of a rhodium doped cobalt iron phosphide material having a ratio of cobalt iron to rhodium of 2:1:0.3 provided in example 2 of the present invention.
FIGS. 2E-I are HAADF-STEM images and in-situ EDX element Mapping (Mapping) images of rhodium-doped cobalt phosphide with a cobalt-iron-rhodium ratio of 2:1:0.3 provided in example 2 of the present invention.
FIG. 3A is a high resolution XPS spectrum of Co 2p for a rhodium doped cobalt iron phosphide material having a ratio of cobalt iron to rhodium of 2:1:0.3 as provided in example 2 of the present invention.
FIG. 3B is a high resolution XPS spectrum of Fe 2p for a rhodium doped cobalt iron phosphide material having a ratio of cobalt iron to rhodium of 2:1:0.3 as provided in example 2 of the present invention.
Figure 3C is a high resolution XPS spectrum of Rh 3d from a rhodium doped cobalt iron phosphide material having a cobalt iron rhodium ratio of 2:1:0.3 as provided in example 2 of the present invention.
FIG. 3D is a high resolution XPS spectrum of P2P for a rhodium doped cobalt iron phosphide material having a ratio of cobalt iron to rhodium of 2:1:0.3 as provided in example 2 of the present invention.
FIG. 4A is a HER Linear Sweep Voltammetry (LSV) polarization curve for rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2 and 3 of the present invention at a ratio of cobalt iron to rhodium of 2:1:0.1 and 2:1:0.3 under acidic conditions.
FIG. 4B is a Tafel slope of HER for rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2 and 3 of the present invention at cobalt iron rhodium ratios of 2:1:0.1 and 2:1:0.3 under acidic conditions.
Figure 4C is a nyquist plot (EIS) of HER under acidic conditions for rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2, 3 of the present invention at cobalt iron rhodium ratios of 2:1:0.1 and 2:1: 0.3.
Fig. 4D is a HER stability test of a rhodium-doped cobalt iron phosphide material with a cobalt iron rhodium ratio of 2:1:0.3 provided in example 2 of the present invention under acidic conditions.
FIG. 5A is a HER Linear Sweep Voltammetry (LSV) polarization curve for rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2 and 3 of the present invention at a ratio of cobalt iron to rhodium of 2:1:0.1 and 2:1:0.3 under alkaline conditions.
FIG. 5B is a Tafel slope of HER of rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2 and 3 of the present invention at cobalt iron rhodium ratios of 2:1:0.1 and 2:1:0.3 under alkaline conditions.
Figure 5C is a nyquist plot (EIS) of HER under alkaline conditions for rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2, 3 of the present invention at cobalt iron rhodium ratios of 2:1:0.1 and 2:1: 0.3.
Fig. 5D is a HER stability test of a rhodium-doped cobalt phosphide material with a cobalt-iron-rhodium ratio of 2:1:0.3 provided in example 2 of the present invention under alkaline conditions.
FIG. 6A is an OER Linear Sweep Voltammetry (LSV) polarization curve of a rhodium-doped cobalt iron phosphide and a pure cobalt iron phosphide material provided in examples 1, 2 and 3 of the present invention at a ratio of cobalt iron to rhodium of 2:1:0.1 and 2:1:0.3 under alkaline conditions.
FIG. 6B is a Tafel slope of OER under alkaline conditions for rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2 and 3 of the present invention at cobalt iron rhodium ratios of 2:1:0.1 and 2:1: 0.3.
FIG. 6C is a Nyquist plot (EIS) of OER under alkaline conditions for rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2, 3 of the present invention at cobalt-iron-rhodium ratios of 2:1:0.1 and 2:1: 0.3.
FIG. 6D is an OER stability test of a Rh-doped CoFeP material with a ratio of Co to Fe to Rh of 2:1:0.3 in accordance with example 2 of the present invention under alkaline conditions.
FIG. 7A is a Linear Sweep Voltammetry (LSV) polarization curve for total hydrolysis of rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials in 1M KOH solutions provided in examples 1, 2, and 3 of the present invention at a ratio of cobalt iron to rhodium of 2:1:0.1 and 2:1: 0.3.
FIG. 7B shows the stability test of the total hydrolysis of a Rh-doped CoFeP material with a ratio of Co to Fe to Rh of 2:1:0.3 according to example 2 of the present invention.
Detailed Description
The endpoints of the ranges and any values presented herein are not limited to the precise range or value.
The present invention will be described in detail below by way of examples of implementation. In the following examples, X-ray diffractometers were purchased from Dnah instruments Inc., of Dandong, and the model number is DX-2700; the Transmission Electron Microscope (TEM) is model number Talos F200X. Scanning Electron Microscope (SEM) a Helios G4 UC field emission scanning electron microscope was used. The electrochemical workstation is purchased from Shanghai Chenghua instruments Inc., and has the model number of CHI760 e; all reagents used were analytical reagents.
Preparation example 1
The preparation method is used for explaining a preparation method of a noble metal doped double-metal phosphide material for electrocatalytic total hydrolysis, and the method comprises the following steps:
and 102, annealing the rhodium-doped cobalt iron double hydroxide and sodium hypophosphite in nitrogen to obtain the noble metal-doped bimetallic phosphide material.
Specifically, the step 101 of preparing the rhodium-doped cobalt iron double hydroxide by using an ethylene glycol-assisted hydrothermal method comprises the following steps:
dissolving soluble cobalt salt, soluble ferric salt, soluble rhodium salt and urea in a solvent according to a certain molar ratio to obtain a solution, wherein the solvent is a mixed solvent of ethylene glycol and water in a certain volume ratio;
stirring the solution at normal temperature for 30min, pouring the solution into a polytetrafluoroethylene lining, placing the lining in a stainless steel hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 12 h;
after the reaction is finished, cooling to room temperature, centrifuging the product, washing with water, and freeze-drying to obtain the rhodium-doped cobalt-iron double hydroxide.
Specifically, in step 102, annealing the rhodium-doped cobalt iron double hydroxide and sodium hypophosphite in nitrogen to obtain the noble metal-doped bimetallic phosphide material comprises:
and putting the rhodium-doped cobalt iron double hydroxide into a porcelain boat, putting sodium hypophosphite into another porcelain boat at the upstream of the horizontal tube furnace, and heating for 1-3 h in nitrogen at 350 ℃ to obtain the noble metal-doped bimetallic phosphide material.
Example 1: preparation of rhodium-doped cobalt iron phosphide with cobalt iron rhodium ratio of 2:1:0.1
(1) Dissolving 0.291 g of cobalt nitrate hexahydrate, 0.202 g of ferric nitrate nonahydrate, 10.46 mg of rhodium trichloride and 120 mg of urea into a mixed solvent of 10 ml of deionized water and 30 ml of ethylene glycol, and stirring for 30 min;
(2) pouring the mixed solution into a polytetrafluoroethylene lining, placing the lining into a stainless steel hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 12 hours;
(3) after cooling to room temperature, centrifuging, washing and freeze-drying the product to obtain the rhodium-doped cobalt-iron double hydroxide;
(4) putting the 10 mg of rhodium-doped cobalt iron double hydroxide obtained in the step (3) into a porcelain boat, putting 100 mg of sodium hypophosphite into another porcelain boat at the upstream of a horizontal tube furnace, and annealing the material at 350 ℃ for 2 h at a heating speed of 2 ℃/min under nitrogen flow to obtain the rhodium-doped cobalt iron phosphide with the ratio of cobalt, iron and rhodium being 2:1: 0.1.
Example 2: preparation of rhodium-doped cobalt iron phosphide with cobalt iron rhodium ratio of 2:1:0.3
(1) Dissolving 0.291 g of cobalt nitrate hexahydrate, 0.202 g of ferric nitrate nonahydrate, 31.38 mg of rhodium trichloride and 120 mg of urea into a mixed solvent of 10 ml of deionized water and 30 ml of ethylene glycol, and stirring for 30 min;
(2) pouring the mixed solution into a polytetrafluoroethylene lining, placing the lining into a stainless steel hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 12 hours;
(3) after cooling to room temperature, centrifuging, washing and freeze-drying the product to obtain the rhodium-doped cobalt-iron double hydroxide;
(4) putting the 10 mg of rhodium-doped cobalt iron double hydroxide obtained in the step (3) into a porcelain boat, putting 100 mg of sodium hypophosphite into another porcelain boat at the upstream of a horizontal tube furnace, and annealing the material at 350 ℃ for 2 h at a heating speed of 2 ℃/min under nitrogen flow to obtain the rhodium-doped cobalt iron phosphide with the ratio of cobalt, iron and rhodium being 2:1: 0.3.
Example 3: preparation of cobalt iron phosphide with cobalt iron ratio of 2:1
(1) Dissolving 0.291 g of cobalt nitrate hexahydrate, 0.202 g of ferric nitrate nonahydrate and 120 mg of urea into a mixed solvent of 10 ml of deionized water and 30 ml of ethylene glycol, and stirring for 30 min;
(2) pouring the mixed solution into a polytetrafluoroethylene lining, placing the lining into a stainless steel hydrothermal kettle, and carrying out hydrothermal treatment at 120 ℃ for 12 hours;
(3) after cooling to room temperature, centrifuging, washing and freeze-drying the product to obtain the cobalt-iron double hydroxide;
(4) putting the 10 mg of cobalt-iron double hydroxide obtained in the step (3) into a porcelain boat, putting 100 mg of sodium hypophosphite into another porcelain boat at the upstream of a horizontal tube furnace, and annealing the materials at 350 ℃ for 2 h at a heating speed of 2 ℃/min under nitrogen flow to obtain the cobalt-iron phosphide with the cobalt-iron ratio of 2: 1.
Test example 1
This test serves to illustrate the crystal structure of the noble metal doped double metal hydroxides and phosphides of the present invention.
Fig. 1A is an X-ray diffraction pattern of rhodium-doped cobalt iron double hydroxide and pure cobalt iron double hydroxide precursors with cobalt iron rhodium ratios of 2:1:0.1 and 2:1:0.3 provided in examples 1, 2, and 3 of the present invention. The diffraction peak of the corresponding Co2The (003), (006), (012), (015), (018), (110) and (113) planes of Fe-LDH (PDF card number 50-0235).
FIG. 1B is an X-ray diffraction pattern of rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2 and 3 of the present invention at a ratio of cobalt iron to rhodium of 2:1:0.1 and 2:1: 0.3. The diffraction peaks of the crystal face are well corresponding to the (011), (111), (211) and (013) crystal faces of CoP (PDF card No. 89-4862), and Fe2The (111) and (210) crystal planes of P (PDF card number 83-2337).
Test example 2
This test serves to illustrate the microscopic morphology of the noble metal-doped bimetallic phosphide material of the present invention.
Fig. 2A is a Scanning Electron Microscope (SEM) image of a rhodium-doped cobalt iron double hydroxide precursor with a cobalt iron rhodium ratio of 2:1:0.3 according to embodiment 2 of the present invention, which proves that the rhodium-doped cobalt iron double hydroxide precursor is a sheet-like structure.
Fig. 2B is a Scanning Electron Microscope (SEM) image of a rhodium-doped cobalt iron phosphide material with a cobalt iron rhodium ratio of 2:1:0.3 provided in example 2 of the present invention, demonstrating that the material after phosphating still maintains the original sheet structure and sharpness, with the only difference being surface roughness.
FIG. 2C is a Transmission Electron Microscopy (TEM) image of a rhodium-doped CoFeP material with a ratio of CoFeRh to Rh of 2:1:0.3 provided in example 2 of the present invention, with a very low diffraction contrast clearly indicating the ultrathin flake nature of the sample. The embedded Selected Area Electron Diffraction (SAED) image exhibits a series of diffraction rings, which can be indexed to the (011), (111), (211), and (013) planes of CoP, and Fe, respectively2The (111) plane of P.
Figure 2D is a high resolution tem (hrtem) image of a rhodium doped cobalt iron phosphide material having a ratio of cobalt iron to rhodium of 2:1:0.3 provided in example 2 of the present invention. The lattice fringes are measured and found: lattice spacings of 0.28 and 0.18 nm may be designated as (011) and (2) of CoP, respectively11) And (4) a plane. While 0.22 nm can be designated as Fe2P (111) plane.
FIGS. 2E-I are HAADF-STEM images and in-situ EDX element Mapping (Mapping) images of rhodium-doped cobalt phosphide with a cobalt-iron-rhodium ratio of 2:1:0.3 provided in example 2 of the present invention. It reveals the uniform distribution of Fe, Co, P and Rh elements in the composite material, and also demonstrates the successful uniform doping of Rh elements.
Test example 3
This test serves to illustrate the valence and bonding mode of the surface elements of the noble metal doped bimetallic phosphide material of the present invention.
FIG. 3A is a high resolution XPS spectrum of Co 2p for a rhodium doped cobalt iron phosphide material having a ratio of cobalt iron to rhodium of 2:1:0.3 as provided in example 2 of the present invention. There are 6 binding energy peaks, of which the two main peaks at 778.9 and 781.3 eV are assigned to Co 2p3/2Region, accompanied by a satellite peak at 785.2 eV, at Co 2p1/2The two main peaks of the region are located at 793.9 and 797.9 eV, respectively, with the satellite peak located at 803.1 eV.
FIG. 3B is a high resolution XPS spectrum of Fe 2p for a rhodium doped cobalt iron phosphide material having a ratio of cobalt iron to rhodium of 2:1:0.3 as provided in example 2 of the present invention. It also gives six peaks, with binding energy peaks at about 711.1 and 724.4 eV designated as Fe 3+2p of3/2And 2p1/2Are associated with satellite peaks of 714.1 and 726.3 eV, respectively. While the peaks at 707.2 and 720.1 eV are associated with Fe-P bonds.
Figure 3C is a high resolution XPS spectrum of Rh 3d from a rhodium doped cobalt iron phosphide material having a cobalt iron rhodium ratio of 2:1:0.3 as provided in example 2 of the present invention. Binding energy peaks at 307.9 and 312.7 eV, which can be well designated as Rh 3+3d of5/2And 3d3/2。
FIG. 3D is a high resolution XPS spectrum of P2P for a rhodium doped cobalt iron phosphide material having a ratio of cobalt iron to rhodium of 2:1:0.3 as provided in example 2 of the present invention. Deconvolution peaks at 129.8 and 130.8 eV, respectively, reflecting P2P3/2And 2p1/2The binding energy of (1). Furthermore, the peak at 133.9 eV is attributable to the oxidized form of phosphide due to exposure to airTo form a phosphate-like structure.
Test example 4
This test is intended to illustrate the performance of the noble metal-doped bimetallic phosphide material of the present invention in electrocatalytic hydrogen evolution under acidic conditions.
The electrochemical test adopts a three-electrode system, and the electrochemical test is carried out by a CHI760e electrochemical analyzer workstation, wherein the GCE loaded with the catalyst is used as a working electrode, a carbon rod electrode is used as a counter electrode, and a silver/silver chloride electrode (Ag/AgCl) is used as a reference electrode. Electrochemical test electrolyte was 0.5M H2SO4And (4) introducing nitrogen into the solution for 10 min before testing to remove air in the electrolyte.
FIG. 4A is a Linear Sweep Voltammetry (LSV) polarization curve for rhodium doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2 and 3 of the present invention at a ratio of cobalt iron to rhodium of 2:1:0.1 and 2:1: 0.3. As can be seen from the measurement in the range of the cathode potential of 0.05 to-0.5V, the current density gradually increased with the increase of the voltage, and examples 1, 2 and 3 of the present invention were 10 mA cm-2The overpotentials at the current densities of (a) are 93 mV, 76 mV and 120 mV, respectively. The rhodium-doped cobalt iron phosphide provided in embodiment 2 of the invention has the smallest voltage required for doping cobalt iron phosphide in a ratio of 2:1:0.3, i.e. the material has the strongest activity in HER reaction.
FIG. 4B is a Tafel slope for rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2 and 3 of the present invention at cobalt iron rhodium ratios of 2:1:0.1 and 2:1: 0.3. The slope of the graph represents the catalytic kinetics of the material, with lower slopes favoring more gas generation at a certain overpotential. As can be seen from the figure, the Tafel slope of the rhodium-doped cobalt iron phosphide provided by the invention in the embodiment 2 with the ratio of cobalt, iron and rhodium being 2:1:0.3 is the lowest, namely the material has better activity when being used as a catalyst.
FIG. 4C is a Nyquist plot (EIS) of rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2, and 3 of the present invention at cobalt-iron-rhodium ratios of 2:1:0.1 and 2:1: 0.3. The semi-circular diameter of the graph represents the charge transfer resistance of the material, with smaller diameters favoring charge transfer. As can be seen from the figure, the impedance of the rhodium-doped cobalt iron phosphide provided by the embodiment 2 of the invention with the ratio of cobalt iron to rhodium of 2:1:0.3 is the minimum, and the value is 7.5 omega, namely the material has better activity when being used as a catalyst.
Fig. 4D is a HER stability test of a rhodium-doped cobalt iron phosphide material with a cobalt iron rhodium ratio of 2:1:0.3 provided in example 2 of the present invention. It can be seen from the figure that the LSV curve of the material measured after 1000 cycles almost overlaps the initial curve, indicating excellent HER stability. Although the chronoamperometry measurement shows a small rise, the current density can still be kept at 10 mA cm-2About more than 24 hours, further confirming its outstanding long-term durability under acidic conditions.
Test example 5
This test is intended to illustrate the performance of the noble metal-doped bimetallic phosphide material of the present invention in electrocatalytic hydrogen evolution under alkaline conditions.
The electrochemical test adopts a three-electrode system, and the electrochemical test is carried out by a CHI760e electrochemical analyzer workstation, wherein the GCE loaded with the catalyst is used as a working electrode, a carbon rod electrode is used as a counter electrode, and a silver/silver chloride electrode (Ag/AgCl) is used as a reference electrode. The electrolyte for electrochemical test is 1M KOH solution, and nitrogen is introduced into the solution for 10 min before the test to remove air in the electrolyte.
FIG. 5A is a Linear Sweep Voltammetry (LSV) polarization curve for rhodium doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2 and 3 of the present invention at a ratio of cobalt iron to rhodium of 2:1:0.1 and 2:1: 0.3. As can be seen from the figure, the current invention in examples 1, 2 and 3 was operated at 10 mA · cm-2The overpotential at the current density of (a) is 122 mV, 48 mV and 176 mV, respectively. The rhodium-doped cobalt iron phosphide provided in embodiment 2 of the invention has the smallest voltage required for doping cobalt iron phosphide in a ratio of 2:1:0.3, i.e. the material has the strongest activity in HER reaction.
FIG. 5B is a Tafel slope for rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2 and 3 of the present invention at cobalt iron rhodium ratios of 2:1:0.1 and 2:1: 0.3. The slope of the graph represents the catalytic kinetics of the material, with lower slopes favoring more gas generation at a certain overpotential. As can be seen from the figure, the Tafel slope of the rhodium-doped cobalt iron phosphide provided by the invention in the embodiment 2 with the ratio of cobalt, iron and rhodium being 2:1:0.3 is the lowest, namely the material has better activity when being used as a catalyst.
FIG. 5C is a Nyquist plot (EIS) of rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2, and 3 of the present invention at cobalt-iron-rhodium ratios of 2:1:0.1 and 2:1: 0.3. The semi-circular diameter of the graph represents the charge transfer resistance of the material, with smaller diameters favoring charge transfer. As can be seen from the figure, the impedance of the rhodium-doped cobalt iron phosphide provided by the embodiment 2 of the invention with the ratio of cobalt iron to rhodium of 2:1:0.3 is the minimum, and the value is 8.1 omega, namely the material has better activity when being used as a catalyst.
Fig. 5D is a HER stability test of a rhodium-doped cobalt iron phosphide material with a cobalt iron rhodium ratio of 2:1:0.3 provided in example 2 of the present invention. It can be seen from the figure that the overpotential measured for the material after 1000 cycles only slightly increased, indicating excellent HER stability. The current density can be kept at 10 mA cm by current-timing method-2About more than 15 hours, it was further confirmed that it has significant long-term durability in 1M KOH.
Test example 6
This test is intended to illustrate the performance of the noble metal-doped bimetallic phosphide material of the present invention in electrocatalytic oxygen evolution under alkaline conditions.
The electrochemical test adopts a three-electrode system, and the electrochemical test is carried out by a CHI760e electrochemical analyzer workstation, wherein the GCE loaded with the catalyst is used as a working electrode, a carbon rod electrode is used as a counter electrode, and a silver/silver chloride electrode (Ag/AgCl) is used as a reference electrode. The electrolyte for electrochemical test was 1M KOH solution, and oxygen was introduced into the solution for 10 min to remove air from the electrolyte before testing.
FIG. 6A is a Linear Sweep Voltammetry (LSV) polarization curve for rhodium doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2 and 3 of the present invention at a ratio of cobalt iron to rhodium of 2:1:0.1 and 2:1: 0.3. As can be seen from the figure, the current invention in examples 1, 2 and 3 was operated at 10 mA · cm-2The overpotentials at current densities of (a) were 320 mV, 303 mV and 367 mV, respectively. The voltage required by doping the cobalt iron phosphide with rhodium in the ratio of 2:1:0.3 of cobalt iron rhodium provided in the embodiment 2 of the invention is the minimum, namely, the material has the strongest activity in the OER reaction.
FIG. 6B is a Tafel slope for rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2 and 3 of the present invention at cobalt iron rhodium ratios of 2:1:0.1 and 2:1: 0.3. The slope of the graph represents the catalytic kinetics of the material, with lower slopes having higher catalytic activity. As can be seen from the figure, the Tafel slope of the rhodium-doped cobalt iron phosphide provided by the invention in the embodiment 2 with the ratio of cobalt, iron and rhodium being 2:1:0.3 is the lowest, namely the material has better activity when being used as a catalyst.
FIG. 6C is a Nyquist plot (EIS) of rhodium-doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2, and 3 of the present invention at cobalt-iron-rhodium ratios of 2:1:0.1 and 2:1: 0.3. The semi-circular diameter of the graph represents the charge transfer resistance of the material, with smaller diameters favoring charge transfer. As can be seen from the figure, the impedance of the rhodium-doped cobalt iron phosphide provided by the embodiment 2 of the invention with the ratio of cobalt iron to rhodium of 2:1:0.3 is the minimum, and the impedance is 6.3 omega, namely the material has better activity when being used as a catalyst.
FIG. 6D is an OER stability test of a rhodium-doped CoFeP material provided in example 2 of the present invention with a ratio of CoFeRh to CoFeRh of 2:1: 0.3. It can be seen from the figure that the overpotential measured after 1000 cycles of the material almost overlaps the initial value, indicating that the OER stability is excellent. The current density can be kept at 10 mA cm by current-timing method-2About over 12 hours, it was further confirmed that it has significant long-term durability in 1M KOH.
Test example 7
This test is intended to illustrate the performance of the noble metal-doped bimetallic phosphide material of the present invention in electrocatalytic total hydrolysis under alkaline conditions.
The electrochemical test adopts a two-electrode system, and the two GCEs loaded with the catalyst are respectively used as a cathode and an anode through the test of a CHI760e electrochemical analyzer workstation. The electrochemical test electrolyte was a 1M KOH solution.
FIG. 7A is a Linear Sweep Voltammetry (LSV) polarization curve for rhodium doped cobalt iron phosphide and pure cobalt iron phosphide materials provided in examples 1, 2 and 3 of the present invention at a ratio of cobalt iron to rhodium of 2:1:0.1 and 2:1: 0.3. As can be seen from the figures, examples 1 of the present invention,2. 3 to 10 mA cm-2The required cell voltages were 1.63V, 1.54V and 1.70V, respectively. The battery voltage required by the rhodium-doped cobalt iron phosphide provided by the embodiment 2 of the invention with the ratio of cobalt, iron and rhodium of 2:1:0.3 is the lowest, namely, the material has the strongest activity in the full-hydrolysis reaction.
FIG. 7B shows the stability test of the total hydrolysis of a Rh-doped CoFeP material with a ratio of Co to Fe to Rh of 2:1:0.3 according to example 2 of the present invention. As can be seen, the whole water decomposition process is 10 mA cm-2Can be maintained at a current density of at least 30 hours without any significant decay, which also demonstrates the excellent stability of the catalyst.
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| WO2024255512A1 (en) * | 2023-06-16 | 2024-12-19 | 中国科学院宁波材料技术与工程研究所 | Catalyst and anode for electrolytic production of hydrogen, and preparation methods therefor, activation methods therefor and use thereof |
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| CN114686915A (en) * | 2022-03-30 | 2022-07-01 | 上海工程技术大学 | Cobalt-iron bimetallic phosphide nanosphere derived from metal organic framework and preparation method and application thereof |
| CN114686915B (en) * | 2022-03-30 | 2023-09-05 | 上海工程技术大学 | Metal-organic framework-derived cobalt-iron bimetallic phosphide nanospheres, preparation method and application thereof |
| WO2024255512A1 (en) * | 2023-06-16 | 2024-12-19 | 中国科学院宁波材料技术与工程研究所 | Catalyst and anode for electrolytic production of hydrogen, and preparation methods therefor, activation methods therefor and use thereof |
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