CN113437318A - Carbon-loaded noble metal alloy nanoparticle and preparation method and application thereof - Google Patents
Carbon-loaded noble metal alloy nanoparticle and preparation method and application thereof Download PDFInfo
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- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 88
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 52
- 239000000956 alloy Substances 0.000 title claims abstract description 52
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 41
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 47
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 47
- 239000002994 raw material Substances 0.000 claims abstract description 38
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims abstract description 27
- 150000001342 alkaline earth metals Chemical class 0.000 claims abstract description 27
- 239000000203 mixture Substances 0.000 claims abstract description 27
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000002245 particle Substances 0.000 claims abstract description 20
- 229910001514 alkali metal chloride Inorganic materials 0.000 claims abstract description 16
- 229910000941 alkaline earth metal alloy Inorganic materials 0.000 claims abstract description 10
- 238000000498 ball milling Methods 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000011068 loading method Methods 0.000 claims abstract description 6
- 239000001301 oxygen Substances 0.000 claims abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 15
- 229910052786 argon Inorganic materials 0.000 claims description 14
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- 239000012300 argon atmosphere Substances 0.000 claims description 10
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 claims description 10
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229910020437 K2PtCl6 Inorganic materials 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 5
- 229910002093 potassium tetrachloropalladate(II) Inorganic materials 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000002923 metal particle Substances 0.000 claims description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 8
- 238000006722 reduction reaction Methods 0.000 abstract description 6
- 239000000758 substrate Substances 0.000 abstract description 2
- 238000009827 uniform distribution Methods 0.000 abstract 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 11
- 239000003054 catalyst Substances 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002243 precursor Substances 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 229910000923 precious metal alloy Inorganic materials 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910000946 Y alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000013341 scale-up Methods 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9041—Metals or alloys
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M2004/8678—Inert electrodes with catalytic activity, e.g. for fuel cells characterised by the polarity
- H01M2004/8689—Positive electrodes
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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
- Y02E60/50—Fuel cells
Abstract
The invention discloses a carbon-loaded noble metal alloy nanoparticle and a preparation method and application thereof. The carbon-loaded noble metal alloy nanoparticles are carbon-loaded noble metal and rare earth metal or alkaline earth metal alloy nanoparticles, the average particle size is between 5nm and 100nm, and the loading amount of the noble metal and the rare earth metal or the alkaline earth metal alloy on the carbon carrier is between 1 percent and 50 percent; is prepared by the following steps: (1) mixing noble metal chloride, alkali metal chloride, rare earth metal raw materials or alkaline earth metal raw materials and carbon, and carrying out ball milling to obtain a milled mixture, and (2) heating and reacting the milled mixture at the temperature of 600-800 ℃ for 1-20 h. The carbon-loaded noble metal alloy nanoparticles have pure phases, small particle sizes, uniform distribution on a porous carbon substrate, high catalytic activity on oxygen reduction reaction and excellent electrocatalytic performance.
Description
Technical Field
The invention belongs to the field of transition metal alloy preparation methods and electrocatalysis, and particularly relates to carbon-supported noble metal alloy nanoparticles as well as a preparation method and application thereof.
Background
At present, noble metal alloys are important catalytic materials, compared with pure noble metals, noble metal alloys generally have higher catalytic performance, and meanwhile, the content of noble metals is also lower, so that the noble metal alloys are an important development direction of noble metal catalysts. The common noble metal alloy is an alloy composed of noble metals such as Pt, Pd, Rh, etc. and late transition metals of the fourth period such as Fe, Co, Ni, etc., and the alloy composed of noble metals, rare earth metals, and alkaline earth metals is less, and the properties thereof are not much known. However, in certain catalytic applications, alloys of noble metals with rare earth metals or alkaline earth metals exhibit very good properties, for example, in the Oxygen Reduction Reaction (ORR) of fuel cell anodes, both theory and experiment show that alloys of Pt with rare earth metals have better performance than pure Pt.
In practical catalytic applications, noble metals and their alloys are usually prepared as nanoparticles, supported on supports of high specific surface area, such as porous carbon, porous oxides, etc. The preparation of nanoparticles of noble metal simple substances and noble metal and late transition metal alloys such as Fe, Co, Ni and the like and the loading method thereof on porous carriers are very mature, but the preparation of nanoparticles of noble metal and rare earth metal and alkaline earth metal alloys and the loading thereof on porous carriers are very difficult.
Currently, precious metals and rare earth and alkaline earth metal alloys are mainly prepared by physical methods including: (1) smelting metal simple substances, and crushing by ball milling and other methods, wherein the obtained particles have micron-sized sizes and are non-uniform in size distribution; (2) magnetron sputtering, but this method can only obtain thin film materials with low yield. Few reports have been made on chemical synthesis, including: reduction of rare earth and noble metal chloride salts or C by hydrogen at elevated temperature3N4ComplexesSynthesizing alloy nanoparticles by using a precursor and the like; and (3) reducing the rare earth and noble metal salt precursors by using the triethyl borohydrite as a reducing agent. However, these methods either require the preparation of complex precursors, or require the liquid-solid reaction or continuous introduction of a reducing atmosphere, which is not suitable for large-scale preparation
In view of the above, the present invention is particularly proposed.
Disclosure of Invention
The invention aims to provide carbon-loaded noble metal alloy nanoparticles, a preparation method and application thereof, and solves the problem of difficulty in preparation of the nanoparticles of noble metals, rare earth metals and alkaline earth metal alloys.
In order to achieve the purpose, the carbon-supported noble metal alloy nanoparticles are carbon-supported noble metal and rare earth metal or alkaline earth metal alloy nanoparticles, the average particle size is between 5nm and 100nm, and the loading amount of the noble metal and the rare earth metal or the alkaline earth metal alloy on the carbon support is between 1% and 50%.
Further, carbon-supported noble metal alloy nanoparticles, prepared by the steps of: (1) mixing and ball-milling noble metal chloride, alkali metal chloride, rare earth metal raw material or alkaline earth metal raw material and carbon to obtain a ground mixture; (2) heating the ground mixture at 600-800 ℃ for reaction for 1-20 h.
Preferably, the molar ratio of the noble metal chloride to the rare earth metal raw material or the alkaline earth metal raw material in step (1) is 0.5 to 2.5; the mass ratio of the noble metal chloride to the carbon is 1/10-1/3, and the mass ratio of the noble metal chloride to the alkali metal chloride is 0.1-1.
Preferably, the ground mixture in step (2) is heated under argon atmosphere, the argon content is 100%, the total pressure of argon is 0.1MPa, and the flow rate of argon gas is 10-5000 mL/min;
the noble metal chloride is K2PtCl6、K2PdCl4Or PdCl2(ii) a The alkali metal chloride is one or a mixture of more of KCl, NaCl, LiCl and CsCl; the diluentThe earth metal raw material is rare earth metal particles or rare earth metal hydride, and the particle size of the rare earth metal raw material is 1 mu m-1 mm; the alkaline earth metal raw material is Ca or CaH2The particle size of the alkaline earth metal raw material is 1 mu m-1 mm.
Preferably, the ground mixture in step (2) is heated under a vacuum atmosphere;
the noble metal chloride is K2PtCl6、K2PdCl4Or PdCl2(ii) a The alkali metal chloride is one or a mixture of more of KCl, NaCl, LiCl and CsCl; the rare earth metal raw material is rare earth metal particles, and the particle size of the rare earth metal raw material is 1 mu m-1 mm; the alkaline earth metal raw material is Ca, and the particle size of the alkaline earth metal raw material is 1 mu m-1 mm.
The invention also provides a preparation method of the carbon-supported noble metal alloy nanoparticle, which comprises the following steps:
(1) mixing and ball-milling noble metal chloride, alkali metal chloride, rare earth metal raw material or alkaline earth metal raw material and carbon to obtain a ground mixture;
(2) heating and reacting the ground mixture at the temperature of 600-800 ℃ for 1-20h to obtain a primary noble metal alloy product;
(3) and washing the noble metal alloy primary product with acid, and drying the solid obtained by filtering to obtain the carbon-loaded noble metal alloy nano-particles.
Preferably, the molar ratio of the noble metal chloride to the rare earth metal raw material or the alkaline earth metal raw material in step (1) is 0.5 to 2.5; the mass ratio of the noble metal chloride to the carbon is 1/10-1/3, and the mass ratio of the noble metal chloride to the alkali metal chloride is 0.1-1.
Preferably, the ground mixture in step (2) is heated under vacuum or argon atmosphere, and when the ground mixture is heated under argon atmosphere, the argon content is 100%, the total pressure of argon is 0.1MPa, and the flow rate of argon gas is 10-5000 mL/min.
Preferably, in the step (3), the acid is sulfuric acid, hydrochloric acid or acetic acid, the concentration of the acid is 0.01-0.5mol/L, when the noble metal alloy primary product is washed by the acid, the volume of the acid for single washing is 2-100mL per gram of solid, and the washing times are 2-5 times.
The invention also provides application of the carbon-supported noble metal alloy nanoparticle, which is characterized by electrocatalysis of the carbon-supported noble metal alloy nanoparticle to oxygen reduction reaction.
The carbon-loaded noble metal alloy nanoparticle and the preparation method and application thereof provided by the invention have the following beneficial effects:
all reactants are solid, the mixture is in a molten state in the reaction process, stirring is not needed in the reaction process, the synthesis method is simple, and if rare earth metal or alkaline earth metal is used as a raw material, no volatile substance or gas is generated, so that the scale-up production is easy. Meanwhile, the phase purity of the obtained carbon-loaded noble metal alloy nanoparticles can be controlled, the size of the alloy nanoparticles is small, the particles are uniformly distributed on a porous carbon substrate, and the carbon-loaded noble metal alloy nanoparticles have high catalytic activity on oxygen reduction reaction and excellent electrocatalysis performance.
Drawings
FIG. 1 shows Pt as a product of example 13X-ray diffraction spectrum of Y/C.
FIG. 2 shows Pt as a product of example 13Transmission electron micrograph of Y/C.
FIG. 3 shows Pt as a product of example 13Linear scan profile of Y/C in redox reaction.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments in order to make the technical field better understand the scheme of the present invention.
As shown in figure 1, the carbon-supported noble metal alloy nanoparticles have an average particle size of 5-100 nm, are uniformly supported on a carbon carrier, have a noble metal and rare earth metal or alkaline earth metal alloy loading of 1-50% on the carbon carrier, and have excellent catalytic oxygen reduction reaction performance in an acid solution. The carbon-loaded noble metal alloy nano-particles are synthesized by a full solid phase chemical method, and the preparation method of the carbon-loaded noble metal alloy nano-particles comprises the following steps:
(1) mixing noble metal chloride, alkali metal chloride, rare earth metal or alkaline earth metal and carbon according to a certain proportion to obtain a raw material mixture, wherein the rare earth metal or alkaline earth metal can be selected from particles or powder, and the molar ratio of the noble metal chloride to the rare earth metal or alkaline earth metal is 0.5-2.5; the mass ratio of the noble metal chloride to the carbon is 1/10-1/3, and the mass ratio of the noble metal chloride to the alkali metal chloride is 0.1-1. The noble metal chloride includes K2PtCl6、K2PdCl4、PdCl2Etc.; the alkali metal chloride is one or a mixture of more of KCl, NaCl, LiCl and CsCl and mainly serves as a melting reaction medium; the rare earth metal comprises 17 rare earth metals of scandium, yttrium and lanthanide series, the particle size is 1 μm-1mm, and corresponding rare earth metal hydride powder can be used for replacement; the alkaline earth metal is mainly Ca, the particle size is 1 μm-1mm, CaH can also be used2Powder was used instead.
(2) Adding the raw material mixture obtained in the step (1) into a ball milling tank for milling, and carrying out ball milling and mixing for a period of time under an argon atmosphere to obtain a milled mixture, wherein a planetary ball mill can be adopted, and the ball-material ratio is 10: 1-100: 1, the rotating speed is 100 and 500rpm, and the ball milling time is 1-20 h.
(3) And (3) heating the ground mixture obtained in the step (2) at a certain temperature for a period of time in a vacuum or argon atmosphere to obtain a primary noble metal alloy product, wherein the heating reaction temperature is 600-800 ℃, and the heating time is 1-20 hours.
If argon atmosphere is used, the content of argon is 100%, the total pressure is 0.1MPa, and the gas flow rate is 10-5000 mL/min. The argon atmosphere is suitable for the case where a rare earth metal or an alkaline earth metal is used as a raw material, and also for the case where a rare earth metal hydride or an alkaline earth metal hydride is used as a raw material.
If a vacuum atmosphere is used, a quartz tube sealing method can be adopted, and the method is only suitable for the case of using rare earth metal or alkaline earth metal as a raw material.
(4) And (4) washing the precious metal alloy primary product obtained in the step (3) by using diluted acid with a certain concentration, washing away unreacted solids, and drying filtered solids to obtain the carbon-supported precious metal alloy nanoparticles. The diluted acid for washing comprises sulfuric acid, hydrochloric acid or acetic acid, the concentration of the diluted acid is 0.01-0.5mol/L, the volume of the diluted acid for one washing is 2-100mL per gram of solid, and the washing times are 2-5 times.
Example 1
Taking 100mg potassium chloroplatinate K2PtCl6132mg of metallic yttrium particles, 1g of potassium chloride and 350mg of conductive carbon black (EC300J) were charged into a ball mill pot, 80g of tungsten steel balls were added, and ball milling was carried out at a rotational speed of 250rpm for 5 hours. Then reacting for 2h at 700 ℃ under the protection of argon to obtain the product, namely the carbon-supported noble metal alloy nano-particle Pt3Y/C。
For the obtained product Pt3The X-ray diffraction characterization is carried out on the Y/C, and the result of the X-ray diffraction spectrum is shown in figure 1, which shows that the method synthesizes pure-phase Pt3And Y alloy. For product Pt3The transmission electron micrograph of Y/C is shown in FIG. 2, and shows that the alloy particle size of the product Pt3Y/C is between 5 and 100nm and is uniformly distributed on the carbon carrier. The ORR catalytic performance for the product Pt3Y/C catalyst is shown in FIG. 3, indicating that the product Pt3Y/C catalyst has comparable properties to the commercial Pt-C catalyst.
The inventive concept is explained in detail herein using specific examples, which are given only to aid in understanding the core concepts of the invention. It should be understood that any obvious modifications, equivalents and other improvements made by those skilled in the art without departing from the spirit of the present invention are included in the scope of the present invention.
Claims (10)
1. The carbon-supported noble metal alloy nanoparticle is characterized in that the carbon-supported noble metal and rare earth metal or alkaline earth metal alloy nanoparticle has an average particle size of 5-100 nm, and the loading amount of the noble metal and the rare earth metal or the alkaline earth metal alloy on the carbon support is 1-50%.
2. The carbon-supported noble metal alloy nanoparticle of claim 1, prepared by: (1) mixing and ball-milling noble metal chloride, alkali metal chloride, rare earth metal raw material or alkaline earth metal raw material and carbon to obtain a ground mixture; (2) heating the ground mixture at 600-800 ℃ for reaction for 1-20 h.
3. The carbon-supported noble metal alloy nanoparticle of claim 2, wherein the molar ratio of the noble metal chloride and the rare earth metal feedstock or the alkaline earth metal feedstock in step (1) is 0.5-2.5; the mass ratio of the noble metal chloride to the carbon is 1/10-1/3, and the mass ratio of the noble metal chloride to the alkali metal chloride is 0.1-1.
4. The carbon-supported noble metal alloy nanoparticle of claim 2, wherein the milled mixture of step (2) is heated under an argon atmosphere, with 100% argon, an argon total pressure of 0.1MPa, and an argon gas flow rate of 10-5000 mL/min;
the noble metal chloride is K2PtCl6、K2PdCl4Or PdCl2(ii) a The alkali metal chloride is one or a mixture of more of KCl, NaCl, LiCl and CsCl; the rare earth metal raw material is rare earth metal particles or rare earth metal hydride, and the particle size of the rare earth metal raw material is 1 mu m-1 mm; the alkaline earth metal raw material is Ca or CaH2The particle size of the alkaline earth metal raw material is 1 mu m-1 mm.
5. The carbon-supported noble metal alloy nanoparticle of claim 2, wherein the milled mixture of step (2) is heated under a vacuum atmosphere;
the noble metal chloride is K2PtCl6、K2PdCl4Or PdCl2(ii) a The alkali metal chloride is KCl, NaCl, LiCl,One or a mixture of more of CsCl; the rare earth metal raw material is rare earth metal particles, and the particle size of the rare earth metal raw material is 1 mu m-1 mm; the alkaline earth metal raw material is Ca, and the particle size of the alkaline earth metal raw material is 1 mu m-1 mm.
6. A method of making the carbon-supported noble metal alloy nanoparticles of any one of claims 1-5, comprising the steps of:
(1) mixing and ball-milling noble metal chloride, alkali metal chloride, rare earth metal raw material or alkaline earth metal raw material and carbon to obtain a ground mixture;
(2) heating and reacting the ground mixture at the temperature of 600-800 ℃ for 1-20h to obtain a primary noble metal alloy product;
(3) and washing the noble metal alloy primary product with acid, and drying the solid obtained by filtering to obtain the carbon-loaded noble metal alloy nano-particles.
7. The method of preparing carbon-supported noble metal alloy nanoparticles of claim 6, wherein the molar ratio of the noble metal chloride and the rare earth metal raw material or the alkaline earth metal raw material in step (1) is 0.5 to 2.5; the mass ratio of the noble metal chloride to the carbon is 1/10-1/3, and the mass ratio of the noble metal chloride to the alkali metal chloride is 0.1-1.
8. The method of preparing carbon-supported noble metal alloy nanoparticles of claim 6, wherein the milled mixture in step (2) is heated under vacuum or an argon atmosphere, and when heated under an argon atmosphere, the argon content is 100%, the total pressure of argon is 0.1MPa, and the flow rate of argon gas is 10-5000 mL/min.
9. The method for preparing carbon-supported noble metal alloy nanoparticles of claim 6, wherein the acid in step (3) is sulfuric acid, hydrochloric acid or acetic acid, the concentration of the acid is 0.01-0.5mol/L, and when the noble metal alloy primary product is washed with the acid, the volume of the acid for one washing is 2-100 mL/g of solid, and the washing times are 2-5 times.
10. Use of carbon-supported noble metal alloy nanoparticles according to any one of claims 1 to 5 for electrocatalytic reduction of oxygen.
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