CN117051429A - Platinum-based amorphous alloy electrolyzed water bifunctional catalyst and preparation method thereof - Google Patents
Platinum-based amorphous alloy electrolyzed water bifunctional catalyst and preparation method thereof Download PDFInfo
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- CN117051429A CN117051429A CN202311097508.3A CN202311097508A CN117051429A CN 117051429 A CN117051429 A CN 117051429A CN 202311097508 A CN202311097508 A CN 202311097508A CN 117051429 A CN117051429 A CN 117051429A
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 207
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 160
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 101
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 86
- 229910001868 water Inorganic materials 0.000 title claims abstract description 78
- 239000003054 catalyst Substances 0.000 title claims abstract description 73
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 48
- 239000000843 powder Substances 0.000 claims abstract description 37
- 239000002245 particle Substances 0.000 claims abstract description 34
- 239000010949 copper Substances 0.000 claims abstract description 25
- 239000011780 sodium chloride Substances 0.000 claims abstract description 24
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052802 copper Inorganic materials 0.000 claims abstract description 20
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 19
- 229910001925 ruthenium oxide Inorganic materials 0.000 claims abstract description 18
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000007731 hot pressing Methods 0.000 claims abstract description 15
- 238000000227 grinding Methods 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000001816 cooling Methods 0.000 claims abstract description 8
- 238000002844 melting Methods 0.000 claims abstract description 8
- 230000008018 melting Effects 0.000 claims abstract description 8
- 239000008213 purified water Substances 0.000 claims abstract description 8
- 238000005507 spraying Methods 0.000 claims abstract description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000003723 Smelting Methods 0.000 claims abstract description 7
- 238000005266 casting Methods 0.000 claims abstract description 7
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 7
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 7
- 239000011574 phosphorus Substances 0.000 claims abstract description 7
- 238000005868 electrolysis reaction Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 16
- 239000012298 atmosphere Substances 0.000 claims description 9
- 238000010791 quenching Methods 0.000 claims description 7
- 230000000171 quenching effect Effects 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 6
- 229910000831 Steel Inorganic materials 0.000 claims description 5
- 239000010959 steel Substances 0.000 claims description 5
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 5
- 229910052721 tungsten Inorganic materials 0.000 claims description 5
- 239000010937 tungsten Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 27
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 239000001301 oxygen Substances 0.000 description 19
- 229910052760 oxygen Inorganic materials 0.000 description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 238000012360 testing method Methods 0.000 description 9
- 150000001485 argon Chemical class 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 8
- 238000004502 linear sweep voltammetry Methods 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 description 6
- 238000005086 pumping Methods 0.000 description 5
- VREFGVBLTWBCJP-UHFFFAOYSA-N alprazolam Chemical compound C12=CC(Cl)=CC=C2N2C(C)=NN=C2CN=C1C1=CC=CC=C1 VREFGVBLTWBCJP-UHFFFAOYSA-N 0.000 description 4
- 239000010411 electrocatalyst Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000009718 spray deposition Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 description 2
- 230000005674 electromagnetic induction Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011812 mixed powder Substances 0.000 description 2
- 238000003825 pressing Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- ROZSPJBPUVWBHW-UHFFFAOYSA-N [Ru]=O Chemical group [Ru]=O ROZSPJBPUVWBHW-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000010891 electric arc Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a platinum-based amorphous alloy electrolyzed water bifunctional catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: s1, mixing platinum, nickel, copper and phosphorus, smelting and suction casting to obtain an amorphous alloy master ingot; s2, melting and spraying the amorphous alloy master ingot onto a rotating copper roller, and cooling to form an amorphous alloy strip; s3, grinding the amorphous alloy strips into amorphous alloy powder after crushing; s4, mixing amorphous alloy powder, sodium chloride particles and ruthenium oxide powder, and hot-pressing to obtain a platinum-based amorphous alloy primary product; s5, immersing the platinum-based amorphous alloy primary product into purified water to dissolve and remove sodium chloride particles, thereby obtaining the self-supporting porous platinum-based amorphous alloy electrolyzed water dual-function catalyst. The preparation method has the advantages of simple technological requirements, short preparation time, strong repeatability and suitability for large-scale production; the self-supporting porous on the bifunctional catalyst can enlarge the surface area to realize more active sites to improve the reaction efficiency, and has stable catalytic performance.
Description
Technical Field
The invention relates to the technical field of catalysis for producing hydrogen and oxygen by water electrolysis, in particular to a platinum-based amorphous alloy water electrolysis bifunctional catalyst and a preparation method thereof.
Background
The hydrogen production by water electrolysis is a method for decomposing water into hydrogen and oxygen by utilizing electric energy, and is a clean and renewable hydrogen energy production technology. Along with the consumption of fossil energy and the aggravation of environmental pollution, the demands of people for new energy and clean energy are increasing increasingly, and hydrogen energy is used as an efficient, environment-friendly and storable energy source, so that the method has wide application prospect. In the hydrogen production by water electrolysis, direct current is utilized to pass through two metal electrodes, so that water molecules are reduced into hydrogen at a cathode and oxidized into oxygen at an anode. The development and utilization of the energy can realize an energy conversion system which takes water, hydrogen and oxygen as circulation, and realize zero emission in the true sense. The key to the large scale application of this technology is the development of efficient electrocatalysts, reducing the high overpotential of the two half reactions (hydrogen evolution reaction (HER) and Oxygen Evolution Reaction (OER), respectively) and speeding up the reaction rate.
The preparation of the double-function electrocatalyst for producing hydrogen by water electrolysis is beneficial to simplifying the design of an electrolytic tank, avoiding the cross effect of different electrocatalysts on two electrodes and greatly reducing the manufacturing and operation cost of devices. The conventional preparation method of the bifunctional electrocatalyst generally uses electrochemical deposition, hydrothermal/solvothermal, chemical water bath deposition and other chemical methods to carry out molecular modification on the catalyst, has complex process, generally requires multi-step treatment, and has high requirement on each step of process and is not easy to repeat.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method of a platinum-based amorphous alloy electrolyzed water dual-function catalyst with simple process requirements and strong repeatability for preparing hydrogen and oxygen by using electrolyzed water as a catalyst and the prepared platinum-based amorphous alloy electrolyzed water dual-function catalyst.
The technical scheme adopted for solving the technical problems is as follows: the preparation method of the platinum-based amorphous alloy electrolyzed water bifunctional catalyst comprises the following steps:
s1, mixing platinum, nickel, copper and phosphorus according to a mass ratio of 36:1:3:2, smelting and suction casting to obtain an amorphous alloy master ingot;
s2, melting the amorphous alloy master ingot, spraying the molten amorphous alloy master ingot onto a rotating copper roller, and cooling to form an amorphous alloy strip;
s3, grinding the amorphous alloy strips into amorphous alloy powder after crushing;
s4, mixing the amorphous alloy powder, sodium chloride particles and ruthenium oxide powder according to a mass ratio of 16:4:1, and hot-pressing to obtain a platinum-based amorphous alloy primary product;
s5, immersing the platinum-based amorphous alloy primary product into purified water to dissolve and remove sodium chloride particles in the platinum-based amorphous alloy primary product, thereby obtaining the self-supporting porous platinum-based amorphous alloy electrolyzed water dual-function catalyst.
Preferably, in step S2, the amorphous alloy master ingot is put into a vacuum rapid quenching and melt-spinning machine, and the amorphous alloy master ingot is melted by induced current in inert gas atmosphere; spraying the amorphous alloy master ingot in a molten state onto a copper roller with the rotating speed of 3000r/min by utilizing air pressure, and cooling to obtain an amorphous alloy strip;
the thickness of the amorphous alloy strip is 0.04mm, and the width is 2 mm-4 mm.
Preferably, in the step S3, the amorphous alloy strip is cut into small sections with the length of 1 mm-2 mm, and the small sections of amorphous alloy are put into a rotary grinding instrument to be ground into amorphous alloy powder;
the particle size of the amorphous alloy powder is less than 60 mu m.
Preferably, in step S4, the particle size of the sodium chloride particles is 3 μm to 45 μm; the particle size of the ruthenium oxide powder is 1-5 mu m.
Preferably, in the step S4, the hot pressing pressure is 15 kN-20 kN; the hot pressing temperature is 185-190 ℃; the hot-pressing atmosphere is an inert gas atmosphere.
Preferably, in the step S4, the platinum-based amorphous alloy primary product has a wafer structure with a diameter of 5mm and a thickness of 1mm to 1.5 mm.
Preferably, in step S4, the mixed amorphous alloy powder, sodium chloride particles and ruthenium oxide powder are placed into a tungsten steel mold, and hot-pressed to form a wafer structure; the inner diameter of the tungsten steel mold is 5mm.
Preferably, in step S5, the platinum-based amorphous alloy primary product is soaked in purified water for 60 to 120 minutes.
Preferably, the component of the platinum-based amorphous alloy electrolyzed water bifunctional catalyst is Pt 57.5 Cu 14.7 Ni 5.3 P 22.5 。
The invention also provides a platinum-based amorphous alloy electrolyzed water dual-function catalyst, which is prepared by the preparation method of any one of the above, and comprises a main structure and a porous structure formed on the main structure; the porous structure is self-supporting and porous formed by dissolving sodium chloride particles.
The invention has the beneficial effects that: taking platinum, nickel, copper and phosphorus as raw materials, smelting, crushing, grinding and the like to obtain amorphous alloy powder, hot-pressing and molding the amorphous alloy powder, sodium chloride particles and ruthenium oxide powder, and dissolving the sodium chloride particles in the amorphous alloy powder to form a porous structure, thereby obtaining the self-supporting porous platinum-based amorphous alloy water electrolysis bifunctional catalyst; the preparation method has simple technological requirements, short preparation time and strong repeatability, and is suitable for large-scale production. The self-supporting porous on the prepared platinum-based amorphous alloy electrolyzed water bifunctional catalyst can enlarge the surface area to realize more active sites so as to improve the reaction efficiency, and has stable catalytic performance; is suitable for hydrogen evolution reaction and oxygen evolution reaction.
The invention has excellent performance in water electrolysis hydrogen production and oxygen production, and can reach 10mA/cm under the voltage of 1.50V 2 Is used for the current density of the battery.
Drawings
The invention will be further described with reference to the accompanying drawings and examples, in which:
FIG. 1 is an SEM image of a platinum-based amorphous alloy electrolyzed water bifunctional catalyst of the present invention;
FIG. 2 is a TEM image of a platinum-based amorphous alloy electrolyzed water bifunctional catalyst of the present invention;
FIG. 3 is an X-ray diffraction diagram of a platinum-based amorphous alloy electrolyzed water bifunctional catalyst of the present invention;
FIG. 4 is a linear sweep voltammetry scan (hydrogen evolution reaction) of a dual-function catalyst for platinum-based amorphous alloy electrolyzed water of the present invention with a platinum-based amorphous alloy plate, a platinum-carbon catalyst in a 1M KOH solution in a saturated argon atmosphere;
FIG. 5 is a Tafil plot of the dual-function catalyst of the platinum-based amorphous alloy electrolyzed water of the present invention with a platinum-based amorphous alloy plate, a platinum carbon catalyst in a 1M KOH solution in a saturated argon atmosphere;
FIG. 6 is a linear sweep voltammetry scan (oxygen evolution reaction) of a dual-function catalyst for platinum-based amorphous alloy electrolyzed water of the present invention with a platinum-based amorphous alloy plate, ruthenium oxide in a 1M KOH solution in a saturated argon atmosphere;
FIG. 7 is a Tafil plot of the dual-function catalyst for platinum-based amorphous alloy electrolyzed water of the present invention with a flat plate of platinum-based amorphous alloy, ruthenium oxide in a 1M KOH solution in a saturated argon atmosphere;
FIG. 8 is a graph of capacitance current density versus scan rate for a platinum-based amorphous alloy electrolyzed water dual-function catalyst of the present invention with a platinum carbon catalyst, a platinum-based amorphous alloy plate, and ruthenium oxide in a 1M KOH solution in a saturated argon atmosphere.
Detailed Description
The preparation method of the platinum-based amorphous alloy electrolyzed water bifunctional catalyst can comprise the following steps:
s1, mixing platinum (Pt), nickel (Ni), copper (Cu) and phosphorus (P) according to a mass ratio of 36:1:3:2, and smelting and suction casting to obtain an amorphous alloy master ingot.
The structural shape of the amorphous alloy master ingot can be, but is not limited to, a block, a bar, and the like.
In an alternative embodiment, the specific operation of step S1 is as follows:
according to the principle that the melting point is higher and the melting point is lower, platinum, nickel and copper are stacked in a copper cavity of a vacuum arc furnace (such as a WK series vacuum arc furnace), a mechanical pump is used for vacuumizing the arc furnace, after the low vacuum of 5Pa or lower is achieved, a molecular pump of the arc furnace is started for vacuumizing, and the high vacuum is achieved to 3 multiplied by 10 -3 Pa. Argon shielding gas is introduced into a copper cavity of the vacuum arc furnace, an arc gun is moved, and 120A current is used for burning titanium ingot to inhale oxygen so as to ensure that no oxygen exists in the reaction furnace. And (3) aligning the current to the copper cavity, and adjusting the arc current to 70-120A to enable the platinum, nickel and copper to be uniformly fused together to form the master alloy.
The smelted master alloy and the weighed phosphorus are put into a test tube, the tube is sealed by a tube sealing machine, the test tube is placed on the tube sealing machine at an inclined angle of 15 degrees to rotate at 10 revolutions per minute, the test tube is pumped to vacuum of 5Pa by a mechanical pump, and then a test tube port is sealed by a water-fuel oxyhydrogen machine at a flow rate of 200L/H-300L/H.
The test tube is arranged on a vacuum rapid quenching spray casting machine, a mechanical pump is used for pumping low vacuum of 5Pa or below, and then the molecular pump of the spray casting machine is opened for pumping high vacuum to 3X 10 -3 Pa, then introducing argon shielding gas, opening electromagnetic induction smelting, and stepping on a pedal to regulate current 20A until the raw materials in the pipe are completely melted. Adding diboron trioxide for purification after finishing, loading the test tube on a vacuum rapid quenching spray casting machine, pumping low vacuum of 5Pa or below by a mechanical pump, and opening a molecular pump of the spray casting machine to high vacuum to 3×10 -3 Pa, then introducing argon shielding gas, opening electromagnetic induction smelting, and stepping on a pedal to regulate current 20A until the raw materials in the pipe are completely melted. Finally, stacking the master alloy into which the phosphorus is dissolved in a copper cavity of a vacuum arc furnace (such as a WK series vacuum arc furnace), pumping the arc furnace to a low vacuum of 5Pa or less by a mechanical pump, and then opening a molecular pump of the arc furnace to pump the high vacuum to 3X 10 -3 Pa, after thatArgon shielding gas is introduced, an arc gun is moved, and 120A current is used for burning titanium ingot to inhale oxygen so as to ensure that no oxygen exists in the reaction furnace. And (3) aligning the current with the copper cavity, adjusting the arc current to 70A-120A, uniformly fusing the raw materials together, pressing a suction casting button, and suction casting to obtain the amorphous alloy bar.
The diameter, length, etc. of the amorphous alloy bar obtained above may be determined corresponding to the forming die, for example, the diameter of 5mm, etc.
S2, melting the amorphous alloy master ingot, spraying the molten amorphous alloy master ingot onto a rotating copper roller, and cooling to form an amorphous alloy strip.
Placing the amorphous alloy master ingot into a vacuum rapid quenching belt-throwing machine, and melting the amorphous alloy master ingot through induced current under the atmosphere of inert gas; spraying the amorphous alloy master ingot in a molten state onto a copper roller with the rotating speed of 3000r/min by utilizing air pressure, and cooling to obtain the amorphous alloy strip.
Alternatively, the amorphous alloy strip has a thickness of 0.04mm and a width of 2mm to 4mm.
Specifically, the amorphous alloy master ingot obtained in the step S1 is combined to be an amorphous alloy bar, the amorphous alloy bar is taken out from an electric arc furnace and then is put into a vacuum rapid quenching belt-throwing machine, the vacuum pumping operation is carried out on the inner part of a cavity of the vacuum rapid quenching belt-throwing machine, and the vacuum degree of the inner part of the cavity reaches 3 multiplied by 10 -3 When Pa or below, high-purity argon is filled for gas washing operation, and the gas is pumped again until the vacuum degree in the cavity reaches 3×10 -3 And (3) high vacuum of Pa or below, and finally, filling high-purity argon again as a shielding gas. And (3) melting the amorphous alloy bar by induction current, and spraying the amorphous alloy in a molten state onto a cooling copper roller with the rotating speed of 3000r/min by utilizing air pressure to obtain an amorphous alloy strip.
S3, grinding the amorphous alloy strips into amorphous alloy powder after crushing.
In the step S3, the amorphous alloy strip is cut into small sections with the length of 1 mm-2 mm, and the small sections of amorphous alloy are put into a rotary grinding instrument to be ground into amorphous alloy powder. The particle size of the amorphous alloy powder is less than 60 mu m.
Wherein, the rotating speed of the rotary grinding instrument can be 7000r/min during grinding. And (3) sieving the amorphous alloy powder obtained by grinding, wherein the mesh number of the sieve is 250 meshes, and the amorphous alloy powder with the particle size of less than 60 microns is obtained.
S4, mixing amorphous alloy powder, sodium chloride (NaCl) particles and ruthenium oxide powder according to a mass ratio of 16:4:1, and hot-pressing to obtain a platinum-based amorphous alloy primary product.
The particle size of the sodium chloride particles is 3-45 mu m; the particle size of the ruthenium oxide powder is 1-5 μm. After mixing the amorphous alloy powder, sodium chloride particles and ruthenium oxide powder, further mixing can be performed by adopting a grinding method to form mixed powder.
And (3) placing the mixed amorphous alloy powder, sodium chloride particles and ruthenium oxide powder into a tungsten steel die, hot-pressing under the conditions that the pressure is 15-20 kN and the temperature is 185-190 ℃, and hot-pressing the mixed powder to form a wafer structure or other solid structures.
Alternatively, the inner diameter of the die is 5mm. Correspondingly, the amorphous alloy primary product formed by pressing in the mould has a wafer structure with the diameter of 5mm and the thickness of 1 mm-1.5 mm.
In order to avoid oxidation reactions due to the presence of oxygen, the hot-pressing atmosphere is an inert gas atmosphere, preferably argon.
Before hot pressing, the mold is vacuumized to form a low vacuum of 5 Pa-10 Pa, and argon is then filled.
S5, immersing the platinum-based amorphous alloy primary product into purified water to dissolve and remove sodium chloride particles in the platinum-based amorphous alloy primary product, thereby obtaining the self-supporting porous platinum-based amorphous alloy electrolyzed water dual-function catalyst. The self-supporting porous is formed, so that the reaction area of the platinum-based amorphous alloy water electrolysis bifunctional catalyst is increased, and the reaction active area of the catalyst is further increased.
In order to thoroughly dissolve sodium chloride particles in water, the platinum-based amorphous alloy primary product is soaked in purified water for 60 to 120 minutes. After the sodium chloride particles are dissolved, holes are formed at the original positions of the sodium chloride particles on the platinum-based amorphous alloy primary product, and the holes form self-supporting multiple holes of the platinum-based amorphous alloy electrolyzed water dual-function catalyst.
The general structure of the platinum-based amorphous alloy electrolyzed water bifunctional catalyst corresponds to the structure of the platinum-based amorphous alloy primary product. For example, in the case that the platinum-based amorphous alloy primary product has a wafer structure, the platinum-based amorphous alloy electrolyzed water bifunctional catalyst obtained after soaking in purified water has a wafer structure. Unlike the platinum-based amorphous alloy precursor, the platinum-based amorphous alloy electrolyzed water bifunctional catalyst has a porous structure (i.e., self-supporting porous) thereon.
Further, the platinum-based amorphous alloy electrolyzed water bifunctional catalyst prepared by the preparation method of the embodiment comprises Pt as the component 57.5 Cu 14.7 Ni 5.3 P 22.5 。
The platinum-based amorphous alloy water electrolysis bifunctional catalyst prepared by the preparation method has the double functions of water electrolysis hydrogen production and oxygen production, structurally comprises a main structure and a porous structure formed on the main structure; the porous structure is self-supporting and porous formed by dissolving sodium chloride particles. The main structure comprises Pt 57.5 Cu 14.7 Ni 5.3 P 22.5 。
Fig. 1 is an SEM image of a platinum-based amorphous alloy electrolyzed water bifunctional catalyst. From the figure, the platinum-based amorphous alloy water electrolysis bifunctional catalyst has a three-dimensional porous structure, and the active area of the reaction is improved.
Fig. 2 is a TEM (projection transmission electron microscope) image of a platinum-based amorphous alloy electrolyzed water bifunctional catalyst. It is clear from the figure that the atoms are disordered and present in an amorphous phase, and that the crystal phase also contains ruthenium oxide atoms. The X-ray diffraction diagram of the platinum-based amorphous alloy electrolyzed water bifunctional catalyst is shown in fig. 3.
The platinum-based amorphous alloy electrolyzed water dual-function catalyst prepared by the invention is suitable for hydrogen evolution reaction and oxygen evolution reaction.
The catalytic effect of the platinum-based amorphous alloy electrolyzed water bifunctional catalyst of the invention is detected below.
Catalytic effect on Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) in electrolyzed water reactions:
1. a standard three-electrode system is used, a silver-silver chloride electrode is used as a reference electrode, a platinum sheet electrode is used as a counter electrode, a circular ring electrode clamp with the diameter of 5mm is used for clamping a platinum-based amorphous alloy water electrolysis bifunctional catalyst block, and the platinum-based amorphous alloy water electrolysis bifunctional catalyst block is used as a working electrode, and electrolyte is 1M potassium hydroxide solution. The catalytic performance of Hydrogen Evolution Reaction (HER) in electrolyzed water reaction was tested by linear sweep voltammetry at a sweep rate of 0.5mv/s in linear sweep voltammetry test using a Chen Hua CHI660 electrochemical workstation under saturated argon atmosphere.
Linear sweep voltammetry scan pair As shown in FIG. 4, the platinum-based amorphous alloy electrolyzed water bifunctional catalyst of the present invention (platinum-based amorphous electrolyzed water bifunctional catalyst) achieved 10mA/cm in 1M potassium hydroxide solution as compared to commercial platinum carbon catalysts and platinum-based amorphous alloy plates (without any porous structure) 2 The overpotential required by the current density is low, which proves that the self-supporting porous platinum-based amorphous alloy electrolyzed water bifunctional catalyst has obvious catalytic effect on hydrogen evolution reaction.
As shown in FIG. 5, the Tafil slope of the platinum-based amorphous alloy electrolyzed water bifunctional catalyst (platinum-based amorphous electrolyzed water bifunctional catalyst) of the present invention reaches 20.01mV/dec, which is better than that of a platinum carbon catalyst and a platinum-based amorphous alloy flat plate.
2. The catalytic performance of the Oxygen Evolution Reaction (OER) in the electrolyzed water reaction was tested by linear sweep voltammetry under saturated argon atmosphere with the same test conditions, and the sweep rate in the linear sweep voltammetry test was 0.5mv/s. Linear sweep voltammetry scan pair As shown in FIG. 6, the platinum-based amorphous alloy electrolyzed water bifunctional catalyst of the present invention (platinum-based amorphous electrolyzed water bifunctional catalyst) achieved 10mA/cm in 1M potassium hydroxide solution as compared with a platinum-based amorphous alloy flat plate (without any porous structure) 2 The overpotential required by the current density is low and is similar to that of ruthenium oxide powder, and the bipolar catalyst of the platinum-based amorphous alloy electrolyzed water with self-supporting and porous has obvious catalytic effect on oxygen evolution reaction.
As shown in FIG. 7, the Tafil slope of the platinum-based amorphous alloy electrolyzed water bifunctional catalyst (platinum-based amorphous electrolyzed water bifunctional catalyst) of the invention reaches 66.53mV/dec, and is better than that of a platinum-based amorphous alloy flat plate, and is similar to that of ruthenium oxide particles.
The platinum-based amorphous alloy electrolyzed water bifunctional catalyst with self-supporting porosity of the invention is tested for electrochemical activity specific surface area (ECSA) in a 1MKOH solution and a saturated argon atmosphere. As shown in fig. 8, the electrochemical activity specific surface area of the platinum-based amorphous alloy electrolyzed water bifunctional catalyst of the present invention (platinum-based amorphous electrolyzed water bifunctional catalyst) was larger than that of the platinum-carbon catalyst, the platinum-based amorphous alloy flat plate, and the ruthenium oxide powder.
The foregoing description is only illustrative of the present invention and is not intended to limit the scope of the invention, and all equivalent structures or equivalent processes or direct or indirect application in other related technical fields are included in the scope of the present invention.
Claims (10)
1. The preparation method of the platinum-based amorphous alloy electrolyzed water bifunctional catalyst is characterized by comprising the following steps of:
s1, mixing platinum, nickel, copper and phosphorus according to a mass ratio of 36:1:3:2, smelting and suction casting to obtain an amorphous alloy master ingot;
s2, melting the amorphous alloy master ingot, spraying the molten amorphous alloy master ingot onto a rotating copper roller, and cooling to form an amorphous alloy strip;
s3, grinding the amorphous alloy strips into amorphous alloy powder after crushing;
s4, mixing the amorphous alloy powder, sodium chloride particles and ruthenium oxide powder according to a mass ratio of 16:4:1, and hot-pressing to obtain a platinum-based amorphous alloy primary product;
s5, immersing the platinum-based amorphous alloy primary product into purified water to dissolve and remove sodium chloride particles in the platinum-based amorphous alloy primary product, thereby obtaining the self-supporting porous platinum-based amorphous alloy electrolyzed water dual-function catalyst.
2. The method for preparing the platinum-based amorphous alloy electrolyzed water bifunctional catalyst according to claim 1, wherein in step S2, the amorphous alloy master ingot is put into a vacuum rapid quenching belt-casting machine, and is melted by induced current in inert gas atmosphere; spraying the amorphous alloy master ingot in a molten state onto a copper roller with the rotating speed of 3000r/min by utilizing air pressure, and cooling to obtain an amorphous alloy strip;
the thickness of the amorphous alloy strip is 0.04mm, and the width is 2 mm-4 mm.
3. The method for preparing the platinum-based amorphous alloy water electrolysis bifunctional catalyst according to claim 1, wherein in the step S3, the amorphous alloy strips are sheared into small sections with the length of 1 mm-2 mm, and the small sections of amorphous alloy are put into a rotary grinding instrument to be ground into amorphous alloy powder;
the particle size of the amorphous alloy powder is less than 60 mu m.
4. The method for preparing a platinum-based amorphous alloy electrolyzed water bifunctional catalyst according to claim 1, wherein in step S4, the particle size of the sodium chloride particles is 3 μm to 45 μm; the particle size of the ruthenium oxide powder is 1-5 mu m.
5. The method for preparing a platinum-based amorphous alloy electrolyzed water bifunctional catalyst according to claim 1, wherein in step S4, the hot pressing pressure is 15kN to 20kN; the hot pressing temperature is 185-190 ℃; the hot-pressing atmosphere is an inert gas atmosphere.
6. The method for preparing the platinum-based amorphous alloy water electrolysis bifunctional catalyst according to claim 1, wherein in the step S4, the platinum-based amorphous alloy primary product has a wafer structure with a diameter of 5mm and a thickness of 1 mm-1.5 mm.
7. The method for preparing a platinum-based amorphous alloy water electrolysis bifunctional catalyst according to claim 1, wherein in step S4, mixed amorphous alloy powder, sodium chloride particles and ruthenium oxide powder are put into a tungsten steel mold, and hot pressed to form a wafer structure; the inner diameter of the tungsten steel mold is 5mm.
8. The method for preparing a platinum-based amorphous alloy water electrolysis bifunctional catalyst according to claim 1, wherein in step S5, the platinum-based amorphous alloy primary product is soaked in purified water for 60 to 120 minutes.
9. The method for preparing a platinum-based amorphous alloy electrolyzed water bifunctional catalyst of any one of claims 1 to 8, wherein the composition of the platinum-based amorphous alloy electrolyzed water bifunctional catalyst is Pt 57.5 Cu 14.7 Ni 5.3 P 22.5 。
10. A platinum-based amorphous alloy electrolyzed water bifunctional catalyst prepared by the preparation method of any one of claims 1 to 9, comprising a main structure and a porous structure formed on the main structure; the porous structure is self-supporting and porous formed by dissolving sodium chloride particles.
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