CN111841589B - Nickel-cobalt-tungsten phosphide catalyst and preparation method and application thereof - Google Patents
Nickel-cobalt-tungsten phosphide catalyst and preparation method and application thereof Download PDFInfo
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- CN111841589B CN111841589B CN202010744108.7A CN202010744108A CN111841589B CN 111841589 B CN111841589 B CN 111841589B CN 202010744108 A CN202010744108 A CN 202010744108A CN 111841589 B CN111841589 B CN 111841589B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- YCOASTWZYJGKEK-UHFFFAOYSA-N [Co].[Ni].[W] Chemical compound [Co].[Ni].[W] YCOASTWZYJGKEK-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 claims abstract description 49
- 239000006260 foam Substances 0.000 claims abstract description 47
- MRSPBKIUPJRMPO-UHFFFAOYSA-N [W]=O.[Ni].[Co] Chemical compound [W]=O.[Ni].[Co] MRSPBKIUPJRMPO-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 230000004888 barrier function Effects 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000001257 hydrogen Substances 0.000 claims abstract description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 14
- 238000001035 drying Methods 0.000 claims abstract description 13
- -1 salt ions Chemical class 0.000 claims abstract description 11
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 6
- 208000028659 discharge Diseases 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 12
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 238000011065 in-situ storage Methods 0.000 claims description 8
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 6
- 229910052573 porcelain Inorganic materials 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- 238000005303 weighing Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000001681 protective effect Effects 0.000 claims description 4
- 238000007605 air drying Methods 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 239000011159 matrix material Substances 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 238000003892 spreading Methods 0.000 claims description 3
- 230000007480 spreading Effects 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000011144 upstream manufacturing Methods 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 abstract description 8
- 229910000531 Co alloy Inorganic materials 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 239000007772 electrode material Substances 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000000463 material Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 7
- 238000000034 method Methods 0.000 description 6
- 229910000510 noble metal Inorganic materials 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- 150000003624 transition metals Chemical class 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000010287 polarization Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- JPNWDVUTVSTKMV-UHFFFAOYSA-N cobalt tungsten Chemical compound [Co].[W] JPNWDVUTVSTKMV-UHFFFAOYSA-N 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910052698 phosphorus Inorganic materials 0.000 description 2
- 239000011574 phosphorus Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000006557 surface reaction Methods 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229910003271 Ni-Fe Inorganic materials 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/349—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of flames, plasmas or lasers
-
- 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
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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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- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
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- Thermal Sciences (AREA)
- Optics & Photonics (AREA)
- Health & Medical Sciences (AREA)
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- Toxicology (AREA)
- Inorganic Chemistry (AREA)
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- Metallurgy (AREA)
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Abstract
The invention discloses a nickel cobalt tungsten phosphide catalyst, a preparation method thereof and application thereof as a hydrogen evolution catalyst. The preparation method comprises the following steps: (1) Performing plasma surface pretreatment on nickel-cobalt alloy foam with a three-dimensional skeleton structure by adopting dielectric barrier discharge; (2) Adding the pretreated nickel-cobalt alloy foam into a sodium tungstate solution, performing hydrothermal reaction at 120-210 ℃, and cleaning and drying after the reaction is finished to obtain a nickel-cobalt-tungsten oxide catalyst; (3) And (3) placing the obtained nickel cobalt tungsten oxide catalyst into a tube furnace for phosphating, and cooling to obtain the octahedral nickel cobalt tungsten phosphide catalyst. The invention not only can effectively solve the problems of environmental pollution caused by residual metal salt ions in the traditional preparation process, poor electrochemical stability and the like, but also can reduce the cost and improve the stability of the electrode material, and has great industrial and practical application values.
Description
Technical Field
The invention relates to the technical field of catalysis, in particular to a nickel cobalt tungsten phosphide catalyst and a preparation method and application thereof.
Background
With the excessive consumption of traditional fossil fuels, the problem of environmental pollution is becoming more serious, and research and development of renewable new energy problems have become one of the hot spots of interest. Among the new energy production devices, the electrolysis of water to produce both hydrogen and oxygen is an effective way to obtain clean energy with considerable development prospects. Because of the slow kinetic conversion during electrolysis of water, a high overpotential needs to be applied to drive the reaction, researchers have been striving to develop efficient and feasible electrolysis water catalytic materials, and reduce the overpotential of the electrodes, thereby reducing the energy consumption. In the current research, noble metals such as Pt, ru and the like have higher catalytic activity on electrolyzed water, but the noble metals are difficult to put into large-scale application due to the scarcity of the noble metal elements, high use cost, poor electrochemical stability and other factors, so that the development of efficient, low-cost and large-scale non-noble metal-based electrolyzed water catalytic materials is imperative. For transition metal phosphide, the special electronic structure and reported high-efficiency electrocatalytic activity of the transition metal phosphide draw attention of a large number of researchers, but many researches show that the transition metal phosphide still has the defects of high manufacturing cost, complex preparation process, low catalytic efficiency, poor electrocatalytic stability, environmental pollution and the like.
Patent specification with publication number CN 108560017A discloses an amorphous cobalt-tungsten modified foam nickel catalytic electrode, a preparation method and application thereof. According to the preparation method, cobalt sulfate and sodium tungstate are respectively used as a cobalt source and a tungsten source, and an amorphous cobalt-tungsten deposition layer is deposited on the surface of the foam nickel in a constant current electrodeposition mode.
The patent specification with publication number of CN 107478699A discloses a preparation method of foam transition metal phosphide loaded noble metal, wherein foam transition metal is placed in a tubular annealing furnace, red phosphorus powder is placed in an upper tuyere, and phosphorus steam is contacted with a sample and reacts with the sample by air flow driving of protective gas, so that a three-dimensional porous transition metal phosphide carrier is generated.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of a nickel cobalt tungsten phosphide catalyst, which is characterized in that after nickel cobalt foam serving as a reaction metal source is subjected to plasma pretreatment by a dielectric barrier discharge device, the conductivity and the surface reaction area of the nickel cobalt foam can be obviously enhanced, so that the subsequent hydrothermal reaction by taking sodium tungstate as a tungsten source is facilitated, an octahedral nickel cobalt tungsten oxide with excellent stability is prepared on a metal foam substrate in situ, and finally, the octahedral nickel cobalt tungsten phosphide is formed by phosphating in a tubular furnace by adopting a chemical vapor deposition method. The preparation method disclosed by the invention is simple in process, not only improves the stability of the electrocatalyst, but also avoids the problems of high manufacturing cost and pollution of metal salt ions to the environment, and the obtained octahedral nickel cobalt tungsten phosphide has excellent electrocatalysis performance, strong stability and environmental friendliness.
A preparation method of a nickel cobalt tungsten phosphide catalyst comprises the following steps:
(1) Performing plasma surface pretreatment on nickel-cobalt alloy foam with a three-dimensional skeleton structure by adopting dielectric barrier discharge;
(2) Adding the pretreated nickel-cobalt alloy foam into a sodium tungstate solution, performing hydrothermal reaction at 120-210 ℃, and cleaning and drying after the reaction is finished to obtain a nickel-cobalt-tungsten oxide catalyst;
(3) And (3) placing the obtained nickel cobalt tungsten oxide catalyst into a tube furnace for phosphating, and cooling to obtain the octahedral nickel cobalt tungsten phosphide catalyst.
Preferably, in the step (1), the power of the dielectric barrier discharge is 50-100W, and the time for the plasma surface pretreatment is 5-20 min. Further preferably, in the step (1), the dielectric barrier discharge has a power of 50 to 60W.
Preferably, in the step (2), the molar concentration X of the sodium tungstate solution satisfies 0 < X.ltoreq.0.03 mol/L.
The pH of the sodium tungstate solution is about 9. Preferably, in the step (2), the pH of the sodium tungstate solution is adjusted to 4 to 7 with an acid before use. The acid is preferably hydrochloric acid.
Preferably, in the step (2), the volume of the sodium tungstate solution is 15 to 40mL.
Preferably, in the step (2), the hydrothermal reaction time is 3 to 12 hours.
Preferably, in the step (2), the drying temperature is 40-60 ℃ and the drying time is 2-12 h.
Preferably, in the step (3), the phosphorus source used in the phosphating process is red phosphorus, and the ratio of the mass of the red phosphorus to the volume of the nickel-cobalt alloy foam is 0.15cm 3 :0.1～0.5g。
Preferably, in the step (3), the temperature of the phosphating is 450-750 ℃ and the time is 1-4 h.
Preferably, in step (3), the phosphating process uses nitrogen and/or argon as a shielding gas.
Preferably, in the step (3), the air pressure in the tubular furnace in the phosphating process is 5-50 Pa.
According to the preparation method, the special octahedral nickel cobalt tungsten trimetallic phosphide catalyst is prepared in situ on the nickel cobalt foam substrate pretreated by the plasma, so that the catalytic performance, conductivity and stability of the electrocatalyst are improved, the problems of high manufacturing cost and pollution of metal salt ions to the environment are avoided, and the formed nickel cobalt tungsten phosphide further improves the electrocatalyst performance of the material greatly.
The invention also provides the octahedral nickel cobalt tungsten phosphide catalyst prepared by the preparation method.
The invention also provides application of the octahedral nickel cobalt tungsten phosphide catalyst as a hydrogen evolution catalyst.
Compared with the prior art, the invention has the main advantages that: according to the invention, dielectric barrier discharge plasma surface pretreatment is firstly carried out on the nickel-cobalt foam, so that the conductivity and the surface reaction area of the nickel-cobalt foam are obviously enhanced, on one hand, the electrocatalytic performance of the final catalyst is obviously improved, and on the other hand, the subsequent hydrothermal reaction can be in-situ grown to form the octahedral nickel-cobalt-tungsten oxide with excellent stability, so that the octahedral nickel-cobalt-tungsten phosphide is further phosphated to form. The invention not only can effectively solve the problems of environmental pollution caused by residual metal salt ions in the traditional preparation process, poor electrochemical stability and the like, but also can reduce the cost and improve the stability of the electrode material, and has great industrial and practical application values.
Drawings
FIG. 1 is a scanning electron micrograph of an octahedral nickel cobalt tungsten phosphide catalyst of example 1;
FIG. 2 is a graph of hydrogen evolution polarization of different materials;
FIG. 3 is a graph showing polarization of hydrogen evolution of nickel cobalt tungsten oxide/plasma pretreatment nickel cobalt foam of example 1 and nickel cobalt tungsten oxide/nickel cobalt foam of comparative example 1;
fig. 4 is a graph showing polarization of hydrogen evolution of nickel cobalt tungsten phosphide/plasma pretreatment foam nickel cobalt of example 1 and nickel cobalt tungsten phosphide/foam nickel cobalt of comparative example 1.
Detailed Description
The invention will be further elucidated with reference to the drawings and to specific embodiments. It is to be understood that these examples are illustrative of the present invention and are not intended to limit the scope of the present invention. The methods of operation, under which specific conditions are not noted in the examples below, are generally in accordance with conventional conditions, or in accordance with the conditions recommended by the manufacturer.
The preparation method of the nickel cobalt tungsten phosphide catalyst in the following embodiment comprises the following steps:
firstly, immersing nickel-cobalt foam into acetone for ultrasonic cleaning, respectively cleaning for a plurality of times by using ethanol and deionized water, and drying the cleaned nickel-cobalt foam in a vacuum drying oven;
step two, dielectric barrier discharge is opened for placement, power is adjusted for preheating treatment, and the appearance characteristic of glow discharge under normal pressure is light approaching blue, so that the discharge is uniform and stable; after the preheating treatment is finished, placing fully dried nickel-cobalt foam between two disc electrodes in a dielectric barrier discharge device, adjusting power, and treating the nickel-cobalt foam to obtain nickel-cobalt foam subjected to plasma pretreatment;
and thirdly, weighing sodium tungstate hexahydrate, dissolving in deionized water, stirring uniformly to a transparent solution at room temperature by using a magnetic stirrer, and adding hydrochloric acid to regulate the pH of the solution.
Transferring the nickel-cobalt foam pretreated by the plasma and the solution prepared in the step III into a polytetrafluoroethylene high-pressure reaction kettle, and placing the polytetrafluoroethylene high-pressure reaction kettle into a blast drying oven for hydrothermal reaction; and after cooling to room temperature, taking out the sample, cleaning the sample for a plurality of times by deionized water and absolute ethyl alcohol, and then drying the sample in a forced air drying oven to obtain the octahedral nickel cobalt tungsten oxide catalyst.
Weighing red phosphorus, spreading the red phosphorus in a porcelain boat, placing the porcelain boat in the upstream of a tube furnace, placing a sample nickel cobalt tungsten oxide catalyst in the downstream of the tube furnace, and vacuumizing the tube furnace; setting the temperature rising rate and the phosphating temperature of a temperature rising control program and the phosphating reaction time; introducing nitrogen as a protective gas in the reaction process, simultaneously ensuring continuous operation of a vacuum pump, and regulating the gas flow rate to 10-50 sccm and the pressure to 5-50 Pa; and after the reaction is completed, cooling the temperature to room temperature, and taking out a sample after the air pressure is restored to the standard atmospheric pressure, thereby obtaining the special octahedral nickel cobalt tungsten phosphide catalyst prepared on the nickel cobalt foam matrix in situ.
Example 1
Firstly, immersing nickel-cobalt foam with the thickness of 1cm multiplied by 1.5cm multiplied by 1mm into acetone for ultrasonic cleaning for about 15 minutes, respectively cleaning the nickel-cobalt foam with ethanol and deionized water for a plurality of times, and drying the cleaned nickel-cobalt foam in a vacuum drying oven;
step two, dielectric barrier discharge is opened for placement, the power is regulated, preheating treatment is carried out, the appearance characteristic of glow discharge under normal pressure is near blue light, and the discharge is uniform and stable; after the preheating treatment is finished, placing fully dried nickel-cobalt foam between two disc electrodes in a dielectric barrier discharge device, adjusting the power to be 52W, and performing discharge treatment on the nickel-cobalt foam for 10 minutes to obtain pretreated nickel-cobalt foam;
step three, weighing 0.168g of sodium tungstate dihydrate, dissolving in 30mL of deionized water, stirring uniformly to a transparent solution at room temperature by using a magnetic stirrer, and adding 5M hydrochloric acid to adjust the pH of the solution to about 5;
transferring the pretreated nickel-cobalt foam and the solution prepared in the step III into a polytetrafluoroethylene high-pressure reaction kettle, and placing the polytetrafluoroethylene high-pressure reaction kettle into a blast drying oven for hydrothermal reaction, wherein the reaction temperature is 180 ℃, and the reaction time is 6 hours; after cooling to room temperature, taking out a sample, washing the sample with deionized water and absolute ethyl alcohol for a plurality of times, and then drying the sample in a forced air drying oven to obtain the octahedral nickel cobalt tungsten oxide catalyst prepared in situ on the nickel cobalt foam substrate subjected to dielectric barrier discharge pretreatment;
weighing red phosphorus, spreading the red phosphorus in a porcelain boat, placing the porcelain boat in the upstream of a tube furnace, placing a sample nickel cobalt tungsten oxide catalyst in the downstream of the tube furnace, and vacuumizing the tube furnace; setting the temperature rise rate of a temperature rise control program, wherein the phosphating temperature is 550 ℃ and the phosphating reaction time is 2 hours; introducing nitrogen as a protective gas in the reaction process, and simultaneously ensuring continuous operation of a vacuum pump, wherein the gas flow rate is 20sccm, and the gas pressure is 25Pa; and after the reaction is completed, cooling the temperature to room temperature, and taking out a sample after the air pressure is restored to the standard atmospheric pressure, thereby obtaining the special octahedral nickel cobalt tungsten phosphide catalyst prepared on the nickel cobalt foam matrix in situ.
Fig. 1 is a scanning electron micrograph of a nickel cobalt tungsten oxide/plasma pretreated foamed nickel cobalt catalytic material and a nickel cobalt tungsten phosphide/plasma pretreated foamed nickel cobalt catalytic material prepared in this example, and it can be seen from the photograph that octahedral particles uniformly grow on the plasma pretreated foamed nickel cobalt catalytic material.
Comparative example 1
The difference from example 1 is only that no step two is provided, i.e. no dielectric barrier discharge plasma pretreatment is performed, and the other conditions are the same, so that a nickel cobalt tungsten oxide catalyst and a nickel cobalt tungsten phosphide catalyst are obtained, wherein the nickel cobalt substrate is not subjected to dielectric barrier discharge pretreatment.
The preparation method of the Pt/C/foamed nickel-cobalt composite catalyst (Pt/C or Pt/C catalyst for short) is similar to that of the Pt/C/NF electrolytes disclosed in Exceptional Performance of Hierarchical Ni-Fe oxyhydrate@NiFe Alloy Nanowire Array Electrocatalysts for Large Current Density Water Splitting (DOI: 10.1039/C9ee02388 g), and the difference is only that the foam carrier is different.
Fig. 2 shows hydrogen evolution polarization curves for different catalysts tested using a three electrode system in 1.0M potassium hydroxide solution, including nickel cobalt foam substrates, example 1 plasma pretreated substrates, example 1 nickel cobalt tungsten oxide/plasma pretreated foam nickel cobalt, example 1 nickel cobalt tungsten phosphide/plasma pretreated foam nickel cobalt, and Pt/C. As can be seen from the graph, the nickel-cobalt substrate subjected to the plasma pretreatment has the hydrogen evolution performance obviously superior to that of the untreated nickel-cobalt substrate, and the plasma pretreatment has obvious effect of improving the hydrogen evolution performance; it can also be seen from the figure that nickel cobalt tungsten oxide and nickel cobalt tungsten phosphide have hydrogen evolution performance superior to noble metal platinum carbon Pt/C at high current density, which indicates that nickel cobalt tungsten phosphide can be used as a highly efficient electrocatalytic hydrogen evolution catalyst.
Fig. 3 and fig. 4 show the effect of the plasma pretreatment on the hydrogen evolution performance of the nickel cobalt tungsten oxide and nickel cobalt tungsten phosphide, respectively, showing that the plasma pretreatment has an obvious improvement effect on the catalyst performance, and the improvement effect on the catalyst performance of the nickel cobalt tungsten phosphide is more obvious.
Further, it will be understood that various changes and modifications may be made by those skilled in the art after reading the foregoing description of the invention, and such equivalents are intended to fall within the scope of the claims appended hereto.
Claims (2)
1. An octahedral nickel cobalt tungsten phosphide catalyst capable of being used as a hydrogen evolution catalyst, which is characterized in that the preparation method of the octahedral nickel cobalt tungsten phosphide catalyst comprises the following steps:
firstly, immersing nickel-cobalt foam with the thickness of 1cm multiplied by 1.5cm multiplied by 1mm into acetone for ultrasonic cleaning for 15 minutes, then respectively cleaning the nickel-cobalt foam with ethanol and deionized water for a plurality of times, and putting the cleaned nickel-cobalt foam into a vacuum drying oven for drying;
step two, dielectric barrier discharge is opened for placement, the power is regulated, preheating treatment is carried out, the appearance characteristic of glow discharge under normal pressure is near blue light, and the discharge is uniform and stable; after the preheating treatment is finished, placing fully dried nickel-cobalt foam between two disc electrodes in a dielectric barrier discharge device, adjusting the power to be 52W, and performing discharge treatment on the nickel-cobalt foam for 10 minutes to obtain pretreated nickel-cobalt foam;
step three, weighing 0.168g of sodium tungstate dihydrate, dissolving in 30mL of deionized water, stirring uniformly to a transparent solution at room temperature by using a magnetic stirrer, and adding 5M hydrochloric acid to adjust the pH of the solution to 5;
transferring the pretreated nickel-cobalt foam and the solution prepared in the step III into a polytetrafluoroethylene high-pressure reaction kettle, and placing the polytetrafluoroethylene high-pressure reaction kettle into a blast drying oven for hydrothermal reaction, wherein the reaction temperature is 180 ℃, and the reaction time is 6 hours; after cooling to room temperature, taking out a sample, washing the sample with deionized water and absolute ethyl alcohol for a plurality of times, and then drying the sample in a forced air drying oven to obtain the octahedral nickel cobalt tungsten oxide catalyst prepared in situ on the nickel cobalt foam substrate pretreated by dielectric barrier discharge;
weighing red phosphorus, spreading the red phosphorus in a porcelain boat, placing the porcelain boat in the upstream of a tube furnace, placing a sample nickel cobalt tungsten oxide catalyst in the downstream of the tube furnace, and vacuumizing the tube furnace; setting the temperature rise rate of a temperature rise control program, wherein the phosphating temperature is 550 ℃ and the phosphating reaction time is 2 hours; introducing nitrogen as a protective gas in the reaction process, and simultaneously ensuring continuous operation of a vacuum pump, wherein the gas flow rate is 20sccm, and the gas pressure is 25Pa; and after the reaction is completed, cooling the temperature to room temperature, and taking out a sample after the air pressure is restored to the standard atmospheric pressure, thereby obtaining the special octahedral nickel cobalt tungsten phosphide catalyst prepared on the nickel cobalt foam matrix in situ.
2. Use of an octahedral nickel cobalt tungsten phosphide catalyst according to claim 1 as hydrogen evolution catalyst.
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