CN113428847B - Nickel-molybdenum-copper ternary metal phosphide, preparation method and application thereof - Google Patents
Nickel-molybdenum-copper ternary metal phosphide, preparation method and application thereof Download PDFInfo
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- CN113428847B CN113428847B CN202110655721.6A CN202110655721A CN113428847B CN 113428847 B CN113428847 B CN 113428847B CN 202110655721 A CN202110655721 A CN 202110655721A CN 113428847 B CN113428847 B CN 113428847B
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 239000002184 metal Substances 0.000 title claims abstract description 34
- HMXCSHJQBPUTDP-UHFFFAOYSA-N [Mo].[Cu].[Ni] Chemical compound [Mo].[Cu].[Ni] HMXCSHJQBPUTDP-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 135
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 56
- 239000006260 foam Substances 0.000 claims abstract description 50
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000001257 hydrogen Substances 0.000 claims abstract description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 30
- 239000010949 copper Substances 0.000 claims abstract description 21
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 77
- 239000000463 material Substances 0.000 claims description 75
- 238000001035 drying Methods 0.000 claims description 58
- 239000008367 deionised water Substances 0.000 claims description 55
- 229910021641 deionized water Inorganic materials 0.000 claims description 55
- 239000011259 mixed solution Substances 0.000 claims description 33
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 26
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 239000004202 carbamide Substances 0.000 claims description 22
- 235000019441 ethanol Nutrition 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 229910017855 NH 4 F Inorganic materials 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 13
- -1 6mmoLNH 4 F Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000000919 ceramic Substances 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 11
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 11
- 229910001220 stainless steel Inorganic materials 0.000 claims description 11
- 239000010935 stainless steel Substances 0.000 claims description 11
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
- 238000011144 upstream manufacturing Methods 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 14
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 6
- 239000007769 metal material Substances 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 6
- 239000011206 ternary composite Substances 0.000 abstract description 6
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000001308 synthesis method Methods 0.000 abstract description 3
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 description 9
- 239000013078 crystal Substances 0.000 description 5
- 239000007772 electrode material Substances 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/08—Other phosphides
- C01B25/088—Other phosphides containing plural metal
-
- 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
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
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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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
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- Chemical & Material Sciences (AREA)
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
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Abstract
The invention discloses a nickel-molybdenum-copper ternary metal phosphide, a preparation method and application thereof, which are applied to the technical field of hydrogen production by water electrolysis. The ternary composite metal material is prepared by adopting metal Ni as a base and selecting Cu element and Mo element with good hydrogen evolution performance, and the catalytic performance of the ternary composite metal material is further improved by phosphating. The foam nickel is used as a substrate, and the catalyst is grown on the foam nickel substrate in situ by a hydrothermal method, so that the catalyst has excellent conductivity. The prepared catalyst has excellent hydrogen evolution catalytic activity and stability. The invention has the advantages of abundant raw materials and low cost. Meanwhile, the synthesis method used by the invention is simple to operate and easy to control, and can realize large-scale production.
Description
Technical Field
The invention relates to a preparation method of a novel nickel-molybdenum-copper ternary metal phosphide material, which is applied to the technical field of hydrogen production by water electrolysis.
Background
With the development of human society, energy problems are becoming more and more important. Fossil fuels such as petroleum, coal, etc. are increasingly exhausted as people exploit them. The rapid increase in energy consumption is driving the development of sustainable alternative energy sources. The energy sources currently used can be divided into three main categories. The first is fossil energy, including petroleum, coal, and natural gas. The second is nuclear energy, which is released by splitting heavy nuclei or fusing light nuclei. The third is renewable energy, including wind energy, solar energy, hydroelectric power, hydrogen energy, and the like. The hydrogen energy has the characteristics of high energy density and environmental friendliness, and is an ideal energy source for realizing sustainable energy economy.
Electrolysis of water is the most important method of obtaining hydrogen from water. The purity of the hydrogen prepared by the process can reach 99.999 percent after the hydrogen is deoxidized by drying. In one aspect, intermittent renewable and clean energy sources (e.g., wind, solar, tidal, geothermal) can be converted to stable hydrogen energy by Hydrogen Evolution Reactions (HER) and then utilized in the form of fuel cells. On the other hand, HER is an environment-friendly and sustainable hydrogen production method, and avoids pollution to the environment caused by using fossil fuel. However, the overpotential of the hydrogen evolution reaction is high and the kinetics are slow. Economical water splitting requires efficient and low cost electrocatalysts to promote the Hydrogen Evolution Reaction (HER) to occur. Up to now, platinum-based materials are the most effective, but cannot be widely used due to high cost and low reserves. The development of low cost, high efficiency electrocatalysts has become urgent. An effective electrocatalyst must have several key properties, such as good electrocatalytic activity, high stability and low cost.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to overcome the defects in the prior art and provide a nickel-molybdenum-copper ternary metal phosphide, a preparation method and application thereof. Meanwhile, the synthesis method used by the invention is simple to operate and easy to control, and can realize large-scale production.
In order to achieve the above object, the present invention adopts the following inventive concept:
the ternary composite metal material is prepared by adopting metal Ni as a base and selecting Cu element and Mo element with good hydrogen evolution performance, and the catalytic performance of the ternary composite metal material is further improved by phosphating. The catalyst synthesized by the method can effectively reduce the overpotential in the hydrogen evolution reaction process, can be well applied to the hydrogen production by water electrolysis, and reduces the energy loss in the hydrogen production by water electrolysis.
According to the inventive concept, the invention adopts the following technical scheme:
the preparation method of the nickel-molybdenum-copper ternary metal phosphide comprises the following steps:
(1) Placing the foam nickel into acetone for ultrasonic cleaning for at least 10 minutes, and then ultrasonic cleaning with hydrochloric acid with the concentration not lower than 3M for at least 10 minutes; then sequentially using ultrapure water and absolute ethyl alcohol to clean the surface, and putting the cleaned foam nickel into an oven at the temperature of not lower than 60 ℃ until the foam nickel is dried;
(2) 8mmol of urea, 6mmol of NH 4 F，Ni(NO 3 ) 2 ·6H 2 O and Cu (NO) 3 ) 2 ·3H 2 O is dissolved in at least 30mL of deionized water, and the molar ratio of Ni to Cu is (0.67-1.33): (1.33-0.67); obtaining a mixed solution; transferring the mixed solution and the foam nickel obtained in the step (1) into a reaction kettle, and drying in a drying box; then washing the dried material with deionized water and ethanol for at least three times respectively, and drying the obtained clean material in a vacuum oven at a temperature of not lower than 60 ℃ for at least 12 hours;
(3) 8mmol of urea and 4mmol of NH 4 F,2mmol of Ni (NO) 3 ) 2 ·5H 2 O,2mmol NaMoO 4 Dissolving in at least 30mL deionized water; transferring the mixed solution and the clean material prepared in the step (2) into a polytetrafluoroethylene stainless steel autoclave, and drying the sealed reactor in a drying oven; washing the prepared product with deionized water and ethanol for at least three times respectively; drying the product in a vacuum oven at a temperature of not less than 60 ℃ for at least 12 hours;
(4) Placing the material prepared in said step (3) in the center of a tube furnace to be charged with NaH 2 PO 2 A ceramic boat of powder is placed on the upstream side of the material prepared in the step (3); heating the material in Ar atmosphere at the temperature rising speed of not lower than 5 ℃/min and at the temperature of not lower than 350 ℃; the product was then collected after cooling to room temperature under Ar shielding gas and rinsed with deionized water.
Preferably, in the step (1), the acetone is used in an amount of not less than 20mL, and the hydrochloric acid is used in an amount of not less than 3mol/L, and the amount is at least 20mL.
Preferably, in the step (2), the total metal ion concentration of Ni and Cu is not less than 2mmol.
Preferably, in the step (2), the molar ratio of Ni to Cu is 0.67:1.33, 1:1 or 1.33:0.67, respectively.
Preferably, in the step (2), the oven temperature is not lower than 120 ℃ and the heating time is at least 6 hours.
Preferably, in the step (3), the oven temperature is not lower than 150 ℃ and the heating time is at least 7 hours.
Preferably, in the step (4), naH 2 PO 2 The powder consumption is at least 1g, and the heating time of the tube furnace is 1-3 hours.
The nickel-molybdenum-copper ternary metal phosphide is prepared by adopting the preparation method of the nickel-molybdenum-copper ternary metal phosphide.
The invention relates to an application of nickel-molybdenum-copper ternary metal phosphide, which is prepared by the preparation method of the nickel-molybdenum-copper ternary metal phosphide, and is used for producing hydrogen in water electrolysis.
Compared with the prior art, the invention has the following obvious prominent substantive features and obvious advantages:
1. the catalyst prepared by the method has lower hydrogen evolution overpotential and is 10mA/cm 2 Has an overpotential of only 119 mV; the catalyst prepared by the method has excellent stability, and the catalyst of the electrode material is kept unchanged after 2000 circles of cyclic voltammetry scanning;
2. the catalyst prepared by the method provided by the invention directly grows on the foam nickel substrate in situ, so that the material has excellent conductivity; the method has the advantages of cheap raw materials, high storage capacity, simple operation and large-scale production;
3. the method is simple and feasible, has low cost and is suitable for popularization and application.
Drawings
Fig. 1 is a scanning electron microscope image of a first embodiment of the present invention.
Fig. 2 is an X-ray diffraction pattern of a first embodiment of the present invention.
Fig. 3 is a polarization diagram of the first, second and third embodiments of the present invention.
Fig. 4 is a polarization diagram of the first, fourth and fifth embodiments of the present invention.
Fig. 5 is a polarization diagram of the second, sixth and seventh embodiments of the present invention.
Fig. 6 is a polarization diagram of the third, eighth and ninth embodiments of the present invention.
Fig. 7 is a stability test chart according to a first embodiment of the present invention.
Detailed Description
The foregoing aspects are further described in conjunction with specific embodiments, and the following detailed description of preferred embodiments of the present invention is provided:
embodiment one:
in this embodiment, a preparation method of a nickel-molybdenum-copper ternary metal phosphide includes the following steps:
(1) The foam nickel with the size of 20mm multiplied by 30mm is put into 20mL of acetone for ultrasonic cleaning for 10 minutes, and then is ultrasonically washed by 20mL of hydrochloric acid with the concentration of 3M for 10 minutes; then sequentially using ultrapure water and absolute ethyl alcohol to clean the surface, and putting the cleaned foam nickel into a baking oven at 60 ℃ until the foam nickel is dried;
(2) 8mmol of urea, 6mmol of NH 4 F，1mmol Ni(NO 3 ) 2 ·6H 2 O and 1mmol Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 30mL deionized water; obtaining a mixed solution; transferring the mixed solution and the foam nickel obtained in the step (1) into a 50mL reaction kettle, drying in a drying box, and keeping at 120 ℃ for 6 hours; then cleaning the dried material with deionized water and ethanol for three times respectively, and drying the obtained clean material in a vacuum oven at 60 ℃ for 12 hours;
(3) 8mmol of urea and 4mmol of NH 4 F,2mmol of Ni (NO) 3 ) 2 ·5H 2 O,2mmol NaMoO 4 Dissolving in 30mL deionized water; transferring the mixed solution and the clean material prepared in the step (2) into a 50mL polytetrafluoroethylene stainless steel autoclave, drying the sealed reactor in a drying oven, and maintaining the temperature at 150 ℃ for 7 hours; washing the prepared product with deionized water and ethanol for three times respectively; the product was then dried in a vacuum oven at 60 ℃ for 12 hours;
(4) The material prepared in said step (3) was placed in the center of a tube furnace and 1g of NaH was charged 2 PO 2 A ceramic boat of powder is placed on the upstream side of the material prepared in the step (3); heating the material at 350 ℃ in Ar atmosphere at a heating rate of 5 ℃/min for 2 hours; the product was then collected after cooling to room temperature under Ar shielding gas and rinsed with deionized water.
Example two
This embodiment is substantially the same as the first embodiment, and is characterized in that:
in this embodiment, a preparation method of a nickel-molybdenum-copper ternary metal phosphide includes the following steps:
(1) The foam nickel with the size of 20mm multiplied by 30mm is put into 20mL of acetone for ultrasonic cleaning for 10 minutes, and then is ultrasonically washed by 20mL of hydrochloric acid with the concentration of 3M for 10 minutes; then sequentially using ultrapure water and absolute ethyl alcohol to clean the surface, and putting the cleaned foam nickel into a baking oven at 60 ℃ until the foam nickel is dried;
(2) 8mmol of urea, 6mmol of NH 4 F，0.67mmol Ni(NO 3 ) 2 ·6H 2 O and 1.33mmol Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 30mL deionized water; obtaining a mixed solution; transferring the mixed solution and the foam nickel obtained in the step (1) into a 50mL reaction kettle, drying in a drying box, and keeping at 120 ℃ for 6 hours; then cleaning the dried material with deionized water and ethanol for three times respectively, and drying the obtained clean material in a vacuum oven at 60 ℃ for 12 hours;
(3) 8mmol of urea and 4mmol of NH 4 F,2mmol of Ni (NO) 3 ) 2 ·5H 2 O,2mmol NaMoO 4 Dissolving in 30mL deionized water; transferring the mixed solution and the clean material prepared in the step (2) into a 50mL polytetrafluoroethylene stainless steel autoclave, drying the sealed reactor in a drying oven, and maintaining the temperature at 150 ℃ for 7 hours; washing the prepared product with deionized water and ethanol for three times respectively; the product was then dried in a vacuum oven at 60 ℃ for 12 hours;
(4) The material prepared in said step (3) was placed in the center of a tube furnace and 1g of NaH was charged 2 PO 2 A ceramic boat of powder is placed on the upstream side of the material prepared in the step (3); heating the material at 350 ℃ in Ar atmosphere at a heating rate of 5 ℃/min for 2 hours; the product was then collected after cooling to room temperature under Ar shielding gas and rinsed with deionized water.
Example III
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a preparation method of a nickel-molybdenum-copper ternary metal phosphide includes the following steps:
(1) The foam nickel with the size of 20mm multiplied by 30mm is put into 20mL of acetone for ultrasonic cleaning for 10 minutes, and then is ultrasonically washed by 20mL of hydrochloric acid with the concentration of 3M for 10 minutes; then sequentially using ultrapure water and absolute ethyl alcohol to clean the surface, and putting the cleaned foam nickel into a baking oven at 60 ℃ until the foam nickel is dried;
(2) 8mmol of urea, 6mmol of NH 4 F，1.33mmol Ni(NO 3 ) 2 ·6H 2 O and 0.67mmol Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 30mL deionized water; obtaining a mixed solution; transferring the mixed solution and the foam nickel obtained in the step (1) into a 50mL reaction kettle, drying in a drying box, and keeping at 120 ℃ for 6 hours; then cleaning the dried material with deionized water and ethanol for three times respectively, and drying the obtained clean material in a vacuum oven at 60 ℃ for 12 hours;
(3) 8mmol of urea and 4mmol of NH 4 F,2mmol of Ni (NO) 3 ) 2 ·5H 2 O,2mmol NaMoO 4 Dissolving in 30mL deionized water; transferring the mixed solution and the clean material prepared in the step (2) into a 50mL polytetrafluoroethylene stainless steel autoclave, drying the sealed reactor in a drying oven, and maintaining the temperature at 150 ℃ for 7 hours; washing the prepared product with deionized water and ethanol for three times respectively; the product was then dried in a vacuum oven at 60 ℃ for 12 hours;
(4) The material prepared in said step (3) was placed in the center of a tube furnace and 1g of NaH was charged 2 PO 2 Of powdersA ceramic boat placed on an upstream side of the material prepared in the step (3); heating the material at 350 ℃ in Ar atmosphere at a heating rate of 5 ℃/min for 2 hours; the product was then collected after cooling to room temperature under Ar shielding gas and rinsed with deionized water.
Example IV
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a preparation method of a nickel-molybdenum-copper ternary metal phosphide includes the following steps:
(1) The foam nickel with the size of 20mm multiplied by 30mm is put into 20mL of acetone for ultrasonic cleaning for 10 minutes, and then is ultrasonically washed by 20mL of hydrochloric acid with the concentration of 3M for 10 minutes; then sequentially using ultrapure water and absolute ethyl alcohol to clean the surface, and putting the cleaned foam nickel into a baking oven at 60 ℃ until the foam nickel is dried;
(2) 8mmol of urea, 6mmol of NH 4 F，1mmol Ni(NO 3 ) 2 ·6H 2 O and 1mmol Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 30mL deionized water; obtaining a mixed solution; transferring the mixed solution and the foam nickel obtained in the step (1) into a 50mL reaction kettle, drying in a drying box, and keeping at 120 ℃ for 6 hours; then cleaning the dried material with deionized water and ethanol for three times respectively, and drying the obtained clean material in a vacuum oven at 60 ℃ for 12 hours;
(3) 8mmol of urea and 4mmol of NH 4 F,2mmol of Ni (NO) 3 ) 2 ·5H 2 O,2mmol NaMoO 4 Dissolving in 30mL deionized water; transferring the mixed solution and the clean material prepared in the step (2) into a 50mL polytetrafluoroethylene stainless steel autoclave, drying the sealed reactor in a drying oven, and maintaining the temperature at 150 ℃ for 7 hours; washing the prepared product with deionized water and ethanol for three times respectively; the product was then dried in a vacuum oven at 60 ℃ for 12 hours;
(4) The material prepared in said step (3) was placed in the center of a tube furnace and 1g of NaH was charged 2 PO 2 The ceramic boat of the powder is arranged inAn upstream side of the material prepared in step (3); heating the material at 350 ℃ in Ar atmosphere at a heating rate of 5 ℃/min for 1 hour; the product was then collected after cooling to room temperature under Ar shielding gas and rinsed with deionized water.
Example five
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a preparation method of a nickel-molybdenum-copper ternary metal phosphide includes the following steps:
(1) The foam nickel with the size of 20mm multiplied by 30mm is put into 20mL of acetone for ultrasonic cleaning for 10 minutes, and then is ultrasonically washed by 20mL of hydrochloric acid with the concentration of 3M for 10 minutes; then sequentially using ultrapure water and absolute ethyl alcohol to clean the surface, and putting the cleaned foam nickel into a baking oven at 60 ℃ until the foam nickel is dried;
(2) 8mmol of urea, 6mmol of NH 4 F，1mmol Ni(NO 3 ) 2 ·6H 2 O and 1mmol Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 30mL deionized water; obtaining a mixed solution; transferring the mixed solution and the foam nickel obtained in the step (1) into a 50mL reaction kettle, drying in a drying box, and keeping at 120 ℃ for 6 hours; then cleaning the dried material with deionized water and ethanol for three times respectively, and drying the obtained clean material in a vacuum oven at 60 ℃ for 12 hours;
(3) 8mmol of urea and 4mmol of NH 4 F,2mmol of Ni (NO) 3 ) 2 ·5H 2 O,2mmol NaMoO 4 Dissolving in 30mL deionized water; transferring the mixed solution and the clean material prepared in the step (2) into a 50mL polytetrafluoroethylene stainless steel autoclave, drying the sealed reactor in a drying oven, and maintaining the temperature at 150 ℃ for 7 hours; washing the prepared product with deionized water and ethanol for three times respectively; the product was then dried in a vacuum oven at 60 ℃ for 12 hours;
(4) The material prepared in said step (3) was placed in the center of a tube furnace and 1g of NaH was charged 2 PO 2 The ceramic boat of powder is placed in the step (3)An upstream side of the prepared material; heating the material at 350 ℃ in Ar atmosphere at a heating rate of 5 ℃/min for 3 hours; the product was then collected after cooling to room temperature under Ar shielding gas and rinsed with deionized water.
Example six
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a preparation method of a nickel-molybdenum-copper ternary metal phosphide includes the following steps:
(1) The foam nickel with the size of 20mm multiplied by 30mm is put into 20mL of acetone for ultrasonic cleaning for 10 minutes, and then is ultrasonically washed by 20mL of hydrochloric acid with the concentration of 3M for 10 minutes; then sequentially using ultrapure water and absolute ethyl alcohol to clean the surface, and putting the cleaned foam nickel into a baking oven at 60 ℃ until the foam nickel is dried;
(2) 8mmol of urea, 6mmol of NH 4 F，0.67mmol Ni(NO 3 ) 2 ·6H 2 O and 1.33mmol Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 30mL deionized water; obtaining a mixed solution; transferring the mixed solution and the foam nickel obtained in the step (1) into a 50mL reaction kettle, drying in a drying box, and keeping at 120 ℃ for 6 hours; then cleaning the dried material with deionized water and ethanol for three times respectively, and drying the obtained clean material in a vacuum oven at 60 ℃ for 12 hours;
(3) 8mmol of urea and 4mmol of NH 4 F,2mmol of Ni (NO) 3 ) 2 ·5H 2 O,2mmol NaMoO 4 Dissolving in 30mL deionized water; transferring the mixed solution and the clean material prepared in the step (2) into a 50mL polytetrafluoroethylene stainless steel autoclave, drying the sealed reactor in a drying oven, and maintaining the temperature at 150 ℃ for 7 hours; washing the prepared product with deionized water and ethanol for three times respectively; the product was then dried in a vacuum oven at 60 ℃ for 12 hours;
(4) The material prepared in said step (3) was placed in the center of a tube furnace and 1g of NaH was charged 2 PO 2 A ceramic boat of powder is placed on the material prepared in the step (3)An upstream side; heating the material at 350 ℃ in Ar atmosphere at a heating rate of 5 ℃/min for 1 hour; the product was then collected after cooling to room temperature under Ar shielding gas and rinsed with deionized water.
Example seven
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a preparation method of a nickel-molybdenum-copper ternary metal phosphide includes the following steps:
(1) The foam nickel with the size of 20mm multiplied by 30mm is put into 20mL of acetone for ultrasonic cleaning for 10 minutes, and then is ultrasonically washed by 20mL of hydrochloric acid with the concentration of 3M for 10 minutes; then sequentially using ultrapure water and absolute ethyl alcohol to clean the surface, and putting the cleaned foam nickel into a baking oven at 60 ℃ until the foam nickel is dried;
(2) 8mmol of urea, 6mmol of NH 4 F，0.67mmol Ni(NO 3 ) 2 ·6H 2 O and 1.33mmol Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 30mL deionized water; obtaining a mixed solution; transferring the mixed solution and the foam nickel obtained in the step (1) into a 50mL reaction kettle, drying in a drying box, and keeping at 120 ℃ for 6 hours; then cleaning the dried material with deionized water and ethanol for three times respectively, and drying the obtained clean material in a vacuum oven at 60 ℃ for 12 hours;
(3) 8mmol of urea and 4mmol of NH 4 F,2mmol of Ni (NO) 3 ) 2 ·5H 2 O,2mmol NaMoO 4 Dissolving in 30mL deionized water; transferring the mixed solution and the clean material prepared in the step (2) into a 50mL polytetrafluoroethylene stainless steel autoclave, drying the sealed reactor in a drying oven, and maintaining the temperature at 150 ℃ for 7 hours; washing the prepared product with deionized water and ethanol for three times respectively; the product was then dried in a vacuum oven at 60 ℃ for 12 hours;
(4) The material prepared in said step (3) was placed in the center of a tube furnace and 1g of NaH was charged 2 PO 2 A ceramic boat of powder is placed on the upstream side of the material prepared in the step (3); addingHeating the material at 350 ℃ in Ar atmosphere at a heating rate of 5 ℃/min for 3 hours; the product was then collected after cooling to room temperature under Ar shielding gas and rinsed with deionized water.
Example eight
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a preparation method of a nickel-molybdenum-copper ternary metal phosphide includes the following steps:
(1) The foam nickel with the size of 20mm multiplied by 30mm is put into 20mL of acetone for ultrasonic cleaning for 10 minutes, and then is ultrasonically washed by 20mL of hydrochloric acid with the concentration of 3M for 10 minutes; then sequentially using ultrapure water and absolute ethyl alcohol to clean the surface, and putting the cleaned foam nickel into a baking oven at 60 ℃ until the foam nickel is dried;
(2) 8mmol of urea, 6mmol of NH 4 F，1.33mmol Ni(NO 3 ) 2 ·6H 2 O and 0.67mmol Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 30mL deionized water; obtaining a mixed solution; transferring the mixed solution and the foam nickel obtained in the step (1) into a 50mL reaction kettle, drying in a drying box, and keeping at 120 ℃ for 6 hours; then cleaning the dried material with deionized water and ethanol for three times respectively, and drying the obtained clean material in a vacuum oven at 60 ℃ for 12 hours;
(3) 8mmol of urea and 4mmol of NH 4 F,2mmol of Ni (NO) 3 ) 2 ·5H 2 O,2mmol NaMoO 4 Dissolving in 30mL deionized water; transferring the mixed solution and the clean material prepared in the step (2) into a 50mL polytetrafluoroethylene stainless steel autoclave, drying the sealed reactor in a drying oven, and maintaining the temperature at 150 ℃ for 7 hours; washing the prepared product with deionized water and ethanol for three times respectively; the product was then dried in a vacuum oven at 60 ℃ for 12 hours;
(4) The material prepared in said step (3) was placed in the center of a tube furnace and 1g of NaH was charged 2 PO 2 A ceramic boat of powder is placed on the upstream side of the material prepared in the step (3); heating rate of temperature riseHeating the material at 350 ℃ in Ar atmosphere at 5 ℃/min for 1 hour; the product was then collected after cooling to room temperature under Ar shielding gas and rinsed with deionized water.
Example nine
This embodiment is substantially the same as the above embodiment, and is characterized in that:
in this embodiment, a preparation method of a nickel-molybdenum-copper ternary metal phosphide includes the following steps:
(1) The foam nickel with the size of 20mm multiplied by 30mm is put into 20mL of acetone for ultrasonic cleaning for 10 minutes, and then is ultrasonically washed by 20mL of hydrochloric acid with the concentration of 3M for 10 minutes; then sequentially using ultrapure water and absolute ethyl alcohol to clean the surface, and putting the cleaned foam nickel into a baking oven at 60 ℃ until the foam nickel is dried;
(2) 8mmol of urea, 6mmol of NH 4 F，1.33mmol Ni(NO 3 ) 2 ·6H 2 O and 0.67mmol Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 30mL deionized water; obtaining a mixed solution; transferring the mixed solution and the foam nickel obtained in the step (1) into a 50mL reaction kettle, drying in a drying box, and keeping at 120 ℃ for 6 hours; then cleaning the dried material with deionized water and ethanol for three times respectively, and drying the obtained clean material in a vacuum oven at 60 ℃ for 12 hours;
(3) 8mmol of urea and 4mmol of NH 4 F,2mmol of Ni (NO) 3 ) 2 ·5H 2 O,2mmol NaMoO 4 Dissolving in 30mL deionized water; transferring the mixed solution and the clean material prepared in the step (2) into a 50mL polytetrafluoroethylene stainless steel autoclave, drying the sealed reactor in a drying oven, and maintaining the temperature at 150 ℃ for 7 hours; washing the prepared product with deionized water and ethanol for three times respectively; the product was then dried in a vacuum oven at 60 ℃ for 12 hours;
(4) The material prepared in said step (3) was placed in the center of a tube furnace and 1g of NaH was charged 2 PO 2 A ceramic boat of powder is placed on the upstream side of the material prepared in the step (3); the heating rate is 5 ℃/min,heating the material in Ar atmosphere at 350 ℃ for 3 hours respectively; the product was then collected after cooling to room temperature under Ar shielding gas and rinsed with deionized water.
Experimental characterization and performance testing:
(1) The surface morphology of example one was subjected to scanning electron microscopy characterization and the results are shown in figure 1. From the figure it can be seen that the surface of the material grows in a number of spherical particles with a larger surface area.
(2) For a clearer study of the phase composition of the catalyst, XRD analysis was performed for example one, as shown in fig. 2, and three strong peaks at 44.507, 51.846 ° and 76.370 ° were clearly observed, which were found to match the (111) crystal plane, (200) crystal plane, (220) crystal plane of nickel (PDF # 04-0850), which could be attributed to the diffraction peaks of the base foam nickel. Diffraction peaks at 14.686 °,36.843 °,45.091 °,46.158 °,47.29 °, and 54.879 ° correspond to the (100), (112), (300), (113), (212), and (310) crystal planes of Cu3P (pdf#71-2261), respectively. Peaks at 36.005 ℃and 47.219 ℃correspond to the (002) and (112) crystal planes of MoP (PDF#76-2363). Whereas at 31.771 °,40.714 °,47.362 °,54.998 ° and 88.824 ° correspond to the (101), (111), (210), (211) and (321) planes of NiP (pdf#74-1385). From the peak intensities, the diffraction peak intensities of the (111) planes of NiP are highest except for the peak of NF substrate, indicating that the catalyst is mainly of NiP (111) planes.
(3) The electrode materials prepared in the first, second and third examples were subjected to a hydrogen evolution catalytic performance test, and the results are shown in fig. 3. When the potential density is 10mA/cm 2 The overpotential was 119mV, 121mV and 167mV, respectively. The catalytic performance of example one is best.
(4) The electrode materials prepared in the first, fourth and fifth examples were subjected to a hydrogen evolution catalytic performance test, and the results are shown in fig. 4. When the potential density is 10mA/cm 2 The overpotential was 119mV, 159mV and 122mV, respectively. The catalytic performance of example one is best.
(5) Electrode materials prepared in examples two, six and sevenThe hydrogen evolution catalytic performance test was performed and the results are shown in fig. 5. When the potential density is 10mA/cm 2 The overpotential was 121mV, 125mV and 165mV, respectively.
(6) The electrode materials prepared in the third, eighth and ninth examples were subjected to hydrogen evolution catalytic performance test, and the results are shown in fig. 6. When the potential density is 10mA/cm 2 The overpotential was 167mV, 239mV and 211mV, respectively.
(7) Performance stability testing was performed on example one, as shown in figure 7. The material is subjected to 2000 circles of cyclic voltammetry scanning, then hydrogen evolution performance test is carried out, and the performance change of the material is observed. As can be seen from fig. 7, the catalyst performance of example one was unchanged after 2000 cyclic voltammetry scans, showing excellent stability.
The results show that the material prepared by the invention has excellent performance in electrocatalytic hydrogen evolution reaction. The catalytic performance of the material is regulated and controlled by changing the proportion of nickel and copper elements and the phosphating time, and the result shows that the catalytic performance of the first embodiment is the best. The nickel-molybdenum-copper ternary metal phosphide material provided by the embodiment of the invention is applied to the technical field of water electrolysis hydrogen production. The ternary composite metal material is prepared by adopting metal Ni as a base and selecting Cu element and Mo element with good hydrogen evolution performance, and the catalytic performance of the ternary composite metal material is further improved by phosphating. The foam nickel is used as a substrate, and the catalyst is grown on the foam nickel substrate in situ by a hydrothermal method, so that the catalyst has excellent conductivity. The prepared catalyst has excellent hydrogen evolution catalytic activity and stability. The raw materials used in the embodiment are abundant in reserves and low in cost. Meanwhile, the synthesis method used by the invention is simple to operate and easy to control, and can realize large-scale production.
The embodiments of the present invention have been described above with reference to the accompanying drawings, but the present invention is not limited to the embodiments described above, and various changes, modifications, substitutions, combinations or simplifications made under the spirit and principles of the technical solution of the present invention can be made according to the purpose of the present invention, and all the changes, modifications, substitutions, combinations or simplifications should be equivalent to the substitution, so long as the purpose of the present invention is met, and all the changes are within the scope of the present invention without departing from the technical principles and the inventive concept of the present invention.
Claims (7)
1. The preparation method of the nickel-molybdenum-copper ternary metal phosphide is characterized by comprising the following steps of:
(1) Placing the foam nickel into acetone for ultrasonic cleaning for at least 10 minutes, and then ultrasonic cleaning with hydrochloric acid with the concentration not lower than 3moL/L for at least 10 minutes; then sequentially using ultrapure water and absolute ethyl alcohol to clean the surface, and putting the cleaned foam nickel into an oven at the temperature of not lower than 60 ℃ until the foam nickel is dried;
(2) 8mmoL urea, 6mmoLNH 4 F，Ni(NO 3 ) 2 ·6H 2 O and Cu (NO) 3 ) 2 ·3H 2 O is dissolved in at least 30mL of deionized water, and the molar ratio of Ni to Cu is (0.67-1.33): (1.33-0.67); obtaining a mixed solution; transferring the mixed solution and the foam nickel obtained in the step (1) into a reaction kettle, and drying in a drying box; then washing the dried material with deionized water and ethanol for at least three times respectively, and drying the obtained clean material in a vacuum oven at a temperature of not lower than 60 ℃ for at least 12 hours;
(3) 8mmoL of urea, 4mmoL of NH 4 F,2mmoL of Ni (NO) 3 ) 2 ·5H 2 NaMoO of O,2mmoL 4 Dissolving in at least 30mL deionized water; transferring the mixed solution and the clean material prepared in the step (2) into a polytetrafluoroethylene stainless steel autoclave, and drying the sealed reactor in a drying oven; washing the prepared product with deionized water and ethanol for at least three times respectively; drying the product in a vacuum oven at a temperature of not less than 60 ℃ for at least 12 hours;
(4) Placing the material prepared in said step (3) in the center of a tube furnace to be charged with NaH 2 PO 2 A ceramic boat of powder is placed on the upstream side of the material prepared in the step (3); heating the material in Ar atmosphere at the temperature rising speed of not lower than 5 ℃/min and at the temperature of not lower than 350 ℃; the product was then collected after cooling to room temperature under Ar shielding gas and rinsed with deionized water.
2. The method for preparing the nickel-molybdenum-copper ternary metal phosphide according to claim 1, wherein the method comprises the following steps: in the step (1), the amount of acetone is not less than 20mL, and the amount of hydrochloric acid is at least 20mL.
3. The method for preparing the nickel-molybdenum-copper ternary metal phosphide according to claim 1, wherein the method comprises the following steps: in the step (2), the total metal ion concentration of Ni and Cu is not less than 2mmoL.
4. The method for preparing the nickel-molybdenum-copper ternary metal phosphide according to claim 1, wherein the method comprises the following steps: in the step (2), the molar ratio of Ni to Cu is 0.67:1.33, 1:1 or 1.33:0.67.
5. The method for preparing the nickel-molybdenum-copper ternary metal phosphide according to claim 1, wherein the method comprises the following steps: in the step (4), naH 2 PO 2 The powder consumption is at least 1g, and the heating time of the tube furnace is 1-3 hours.
6. A nickel molybdenum copper ternary metal phosphide, characterized in that: the nickel-molybdenum-copper ternary metal phosphide is prepared by the preparation method of the nickel-molybdenum-copper ternary metal phosphide.
7. The application of the nickel-molybdenum-copper ternary metal phosphide is characterized in that: the nickel-molybdenum-copper ternary metal phosphide prepared by the preparation method of the nickel-molybdenum-copper ternary metal phosphide as defined in claim 1 is used for producing hydrogen in water electrolysis.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108568304A (en) * | 2017-10-12 | 2018-09-25 | 湖南大学 | A kind of electro-catalysis dehalogenation catalyst |
| US20180327918A1 (en) * | 2015-11-20 | 2018-11-15 | INL - International lberian Nanotechnology Laboratory | Electrode material |
| CN109055976A (en) * | 2018-08-03 | 2018-12-21 | 北京化工大学 | A kind of multilevel structure transition metal nitride electrode material and preparation method thereof |
| CN109811360A (en) * | 2019-03-12 | 2019-05-28 | 华中农业大学 | A kind of NiFeMo ternary electrolysis water electrode and preparation method thereof |
| CN110227531A (en) * | 2019-05-23 | 2019-09-13 | 太原理工大学 | A kind of preparation method of molybdenum doping cobalt iron oxide nanometer sheet bifunctional electrocatalyst |
| CN110711596A (en) * | 2019-10-24 | 2020-01-21 | 江西理工大学 | Efficient full-hydrolysis water catalyst IPBAP/Ni2P@MoOx/NF and preparation method thereof |
| CN112877727A (en) * | 2021-01-17 | 2021-06-01 | 大连理工大学 | Preparation method and application of efficient seawater full-electrolysis hydrogen production phosphide catalyst |
-
2021
- 2021-06-11 CN CN202110655721.6A patent/CN113428847B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180327918A1 (en) * | 2015-11-20 | 2018-11-15 | INL - International lberian Nanotechnology Laboratory | Electrode material |
| CN108568304A (en) * | 2017-10-12 | 2018-09-25 | 湖南大学 | A kind of electro-catalysis dehalogenation catalyst |
| CN109055976A (en) * | 2018-08-03 | 2018-12-21 | 北京化工大学 | A kind of multilevel structure transition metal nitride electrode material and preparation method thereof |
| CN109811360A (en) * | 2019-03-12 | 2019-05-28 | 华中农业大学 | A kind of NiFeMo ternary electrolysis water electrode and preparation method thereof |
| CN110227531A (en) * | 2019-05-23 | 2019-09-13 | 太原理工大学 | A kind of preparation method of molybdenum doping cobalt iron oxide nanometer sheet bifunctional electrocatalyst |
| CN110711596A (en) * | 2019-10-24 | 2020-01-21 | 江西理工大学 | Efficient full-hydrolysis water catalyst IPBAP/Ni2P@MoOx/NF and preparation method thereof |
| CN112877727A (en) * | 2021-01-17 | 2021-06-01 | 大连理工大学 | Preparation method and application of efficient seawater full-electrolysis hydrogen production phosphide catalyst |
Non-Patent Citations (1)
| Title |
|---|
| Crystalline Copper Phosphide Nanosheets as an Efficient Janus Catalyst for Overall Water Splitting;Ali Han et al.;《ACS APPLIED MATERLALS&INTERFACES》;第9卷;摘要、实验部分 * |
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