CN115156546A - Preparation method of monodisperse PtM alloy nanoparticles or nanoclusters - Google Patents
Preparation method of monodisperse PtM alloy nanoparticles or nanoclusters Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 71
- 239000000243 solution Substances 0.000 claims abstract description 61
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 52
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- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 claims description 6
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 claims description 6
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- 239000000203 mixture Substances 0.000 claims description 5
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
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- 235000015393 sodium molybdate Nutrition 0.000 claims description 5
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 5
- -1 yttrium tetrachloride hydrate Chemical compound 0.000 claims description 5
- 230000001476 alcoholic effect Effects 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 239000003599 detergent Substances 0.000 claims description 3
- SONJTKJMTWTJCT-UHFFFAOYSA-K rhodium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Rh+3] SONJTKJMTWTJCT-UHFFFAOYSA-K 0.000 claims description 3
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 3
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 2
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 150000001875 compounds Chemical class 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- YCKOAAUKSGOOJH-UHFFFAOYSA-N copper silver Chemical compound [Cu].[Ag].[Ag] YCKOAAUKSGOOJH-UHFFFAOYSA-N 0.000 description 1
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- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
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- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
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- 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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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a preparation method of monodisperse PtM alloy nanoparticles or nanoclusters, which comprises the following steps: dissolving a metal platinum precursor solution in a surfactant solution to obtain a feed liquid A; dissolving a metal M precursor solution in a surfactant solution to obtain a feed liquid B; dissolving a reducing agent in a mixed solution of water and alcohol to obtain a feed liquid C; opening the hypergravity reactor; introducing the feed liquid A, the feed liquid B and the feed liquid C into a supergravity reactor through a peristaltic pump, and reacting to obtain a PtM nano alloy dispersion solution; and centrifuging and washing the PtM nano alloy dispersion solution, and dispersing in water to obtain the monodisperse PtM alloy nanoparticles or nanoclusters. The PtM alloy nano-particles obtained by the method have controllable morphology, good dispersion, narrow particle size distribution and particle size less than or equal to 10nm; the grain diameter of the obtained monodisperse PtM alloy particle cluster is 20-300 nm.
Description
Technical Field
The invention relates to the technical field of nano-catalysts; and more particularly, to a method for preparing monodisperse PtM alloy nanoparticles or nanoclusters.
Background
The noble metal Pt-based catalyst is widely applied to electrocatalysis, photocatalysis, biosensing and other directions. However, due to its low abundance and high cost, the practical application of platinum is severely hampered. In addition, pt-based catalysts are also susceptible to deactivation by CO poisoning, sintering, and limited in catalyst activity, selectivity, and durability. Therefore, in order to improve the catalytic activity of the Pt-based catalyst, many researchers compound various metals to prepare a nano alloy material, and the nano alloy shows excellent performance that more single metals do not have under the action of various acting forces such as an intermetallic synergistic effect and an electronic effect. On one hand, the use amount of noble metal in the alloy can be reduced, and the cost is reduced; on the other hand, the unique advantages of the alloy material can be exerted, and the overall activity, selectivity and durability of the catalyst are improved. The preparation of platinum-based alloy materials with controlled morphology, composition and geometry to achieve the best catalytic performance and the best precious metal utilization is the focus of research at this stage.
The catalytic performance of the nano Pt-based alloy catalyst mainly depends on the particle size, the dispersion degree, the number of surface active sites and the like. When the composition of the Pt-based alloy is changed, various properties thereof may be greatly changed. In recent years, there have been various methods for preparing monodisperse and uniformly distributed particle size nano-alloys, such as a template method, a hydrothermal method, a chemical liquid phase reduction method, a thermal decomposition method, a gas phase reduction method, a coprecipitation method, a microwave method, and the like. Among the many methods of preparation, one of the most common methods is a chemical liquid phase reduction method, which has advantages of simple reaction, efficiency, and low cost compared to other methods. For example, in Chinese patent publication No. CN108568518A, named "a method of preparing alloy nanoparticlesParticle method in the patent, a method for preparing a core-shell structure bimetallic structure with controllable particle size is disclosed, which utilizes SiO 2 The nano layer maintains the original shape of the alloy, and different metal atoms migrate in the core-shell structure to form the polymetallic alloy nano particles with unchanged shapes. However, there are disadvantages in that the reaction step is complicated, the reaction time is 20 to 40 hours, the particle size is large, and the number of active sites is small compared to small particles.
In the patent of Chinese patent publication No. CN111916775A, entitled "platinum-based alloy catalyst for fuel cell and preparation method thereof", a high temperature atmosphere reduction method is used to prepare platinum-based alloy, the atomic utilization rate of Pt is high, but the reaction temperature is too high, 400-1000 ℃, and the reaction conditions are harsh. In a patent with Chinese patent publication No. CN112237914A and the name of "platinum rare earth alloy @ platinum core-shell catalyst, a preparation method and application thereof", a proton exchange membrane fuel cell which adopts a glycol/oleylamine high-temperature reduction method, can controllably prepare the load of the platinum rare earth alloy on a carbon substrate by adjusting factors such as reaction ratio, temperature, time and the like, and is subsequently applied to an electrocatalyst is disclosed. The method has the defects that oleylamine/glycol insulation requires high-temperature carbonization treatment at 600-900 ℃, the process is complicated, and electrochemical reaction is not facilitated.
In addition, the prior art also discloses a preparation method for preparing nano-bimetal by using a supergravity reactor. For example, chinese patent publication No. CN101007344a, entitled "a method for preparing nano-copper-silver bimetallic composite powder". The method firstly utilizes chemical reduction copper ions to generate nano copper seed crystals, and then leads copper and silver to grow on the seed crystals to prepare the copper-silver bimetallic powder, and has the defects that the nano powder has poor dispersity in water, the average grain diameter is 30nm, the grain diameter is larger, the agglomeration is serious, and the catalytic performance is influenced.
Aiming at the existing defects, the preparation method of the monodisperse nano PtM alloy which has the advantages of simple preparation process, short reaction time, low energy consumption, good dispersibility, small particle size and narrow particle size distribution is needed to be provided.
Disclosure of Invention
The first technical problem to be solved by the invention is to provide a preparation method of monodisperse PtM alloy nanoparticles or nanoclusters. The method adopts a chemical liquid phase original method to prepare a PtM alloy aqueous phase dispersoid, and then the product is washed and dispersed to prepare monodisperse nano PtM alloy nano particles or nano cluster bodies; the obtained PtM alloy nanoparticles have controllable morphology, good dispersion, narrow particle size distribution and particle size less than or equal to 10nm; the grain diameter of the obtained monodisperse PtM alloy particle cluster is between 20 and 300 nm; the structure, size and metal proportion in the alloy can be regulated and controlled by regulating and controlling the charging sequence, reaction temperature and reaction time. Compared with other preparation methods, the method does not need high-temperature hydrothermal, has simple preparation process, short reaction time and is green, clean and environment-friendly; the method well solves the problems of harsh reaction conditions, long reaction time, easy agglomeration of products, large particle size of particles, wide distribution, few active sites and the like, and is easy for large-scale production.
In order to solve the technical problems, the invention adopts the following technical scheme:
a preparation method of monodisperse PtM alloy nanoparticles or nanoclusters comprises the following steps:
s1, dissolving a metal platinum precursor solution in a surfactant solution to obtain a feed liquid A;
s2, dissolving the metal M precursor solution into a surfactant solution to obtain a feed liquid B;
s3, dissolving a reducing agent in a water and alcohol mixed solution to obtain a feed liquid C;
s4, starting the supergravity reactor;
s5, introducing the feed liquid A, the feed liquid B and the feed liquid C into a supergravity reactor through a peristaltic pump, and reacting to obtain a PtM nano alloy dispersion solution;
and S6, centrifuging and washing the PtM nano alloy dispersion solution, and dispersing in water to obtain the monodisperse PtM alloy nanoparticles or nanoclusters.
As a further improvement of the technical solution, in step S1, the metal platinum precursor is selected from one or more of the following substances: chloroplatinic acid, potassium tetrachloroplatinate, potassium hexachloroplatinate, platinum nitrate solution; preferably, the metal platinum precursor is selected from one or more of the following: chloroplatinic acid, potassium hexachloroplatinate.
Preferably, in the step S1, the concentration of the metal platinum precursor in the feed liquid a is 0.125-2.5mmol/L; preferably, the concentration of the metal platinum precursor in the feed liquid A is 0.3125-1.25mmol/L.
As a further improvement of the technical solution, in step S2, the metal M precursor is selected from one or more of the following substances: sodium molybdate, silver nitrate, copper nitrate, palladium chloride, potassium chloropalladate, chloroauric acid, ruthenium trichloride, rhodium chloride, iridium chloride and yttrium tetrachloride hydrate.
Preferably, in the step S2, the concentration of the metal M precursor solution is 0.125-2.5mmol/L; more preferably, the concentration of the metal M precursor solution is 0.3125-1.25mmol/L.
As a further improvement of the technical scheme, in the step S3, the alcohol solvent is selected from one or more of the following substances: methanol, ethanol, ethylene glycol, glycerol, n-butanol, 2-butanol, n-decanol, nonanol, n-hexanol, and polyethylene glycol; more preferably, in step S1, the alcoholic solvent is selected from one or more of the following: methanol, ethanol, ethylene glycol, glycerol and polyethylene glycol.
Preferably, in steps S1, S2, the surfactant is selected from one or more of the following: polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride and polyethylene glycol; more preferably, the surfactant is selected from one or more of the following: polyvinylpyrrolidone, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride.
Preferably, in the steps S1 and S2, the modification temperature of the surface modifier is 10-90 ℃; more preferably, the surface modifier modification temperature is 50 to 90 ℃.
Preferably, in the steps S1 and S2, the surfactant accounts for 10 to 40 mass percent of the modified nano PtM alloy.
As a further improvement of the technical solution, in step S3, the reducing agent is selected from one of the following substances: sodium borohydride, hydrazine hydrate.
As a further improvement of the technical scheme, in the step S4, the reaction temperature in the hypergravity reactor is 10-90 ℃; preferably, in the step S4, the reaction temperature in the hypergravity reactor is 50-90 ℃; most preferably, in step S4, the reaction temperature in the hypergravity reactor is 50 to 70 ℃.
Preferably, in step S4, the hypergravity reactor is selected from a hypergravity rotating packed bed reactor, a baffled hypergravity rotating bed reactor, a spiral channel hypergravity rotating bed reactor, a stator-rotor hypergravity rotating bed reactor or a rotating disc hypergravity rotating bed reactor; the rotating speed of a rotor of the hypergravity reactor is 500-2500rpm; preferably, the rotational speed of the rotor of the hypergravity reactor is 500-1500rpm.
As a further improvement of the technical solution, in step S5, the feeding sequence of the feed liquid a, the feed liquid B, and the feed liquid C is selected from one of the following: simultaneously introducing the feed liquid A and the feed liquid C, and continuously feeding the feed liquid B after the feed liquid A is completely fed; mixing the feed liquid A and the feed liquid B, and introducing the mixture and the feed liquid C at the same time; and simultaneously introducing the feed liquid B and the feed liquid C, and continuously feeding the feed liquid A after the feed liquid B is completely fed.
Preferably, in step S5, the feed flow rate of the feed liquid a is 90 to 180ml/min, the feed flow rate of the feed liquid B is 90 to 180ml/min, the feed flow rate of the feed liquid C is 90 to 180ml/min, and the ratio of the feed flow rates of the feed liquid a and the feed liquid B is 1;
as a further improvement of the technical scheme, in the step S6, the rotating speed of the centrifugal machine for centrifugation is 8000-12000rpm; more preferably, the centrifuge rotation speed is 10000-12000rpm; centrifuging for 2-20min;
preferably, in step S6, the detergent used in the washing process is selected from one or more of the following substances: methanol, ethanol, isopropanol, glycerol, butanol, acetone and butanone.
Preferably, in step S6, the dispersing method is mechanical stirring or ultrasonic dispersing;
preferably, in step S6, the ratio of the metal Pt to the metal M in the PtM alloy nanoparticles or nanoclusters is 1:3-3:1.
Any range recited herein is intended to include any and all subranges between the endpoints and any subrange between the endpoints or any subrange between the endpoints.
The starting materials of the present invention can be obtained commercially, unless otherwise specified, and the equipment used in the present invention can be carried out by conventional equipment in the art or by referring to the prior art in the art.
Compared with the prior art, the invention has the following beneficial effects:
1) The method provided by the invention can be used for obtaining the monodisperse PtM nano particles with controllable morphology, uniform arrangement, narrow particle size distribution and particle size of less than or equal to 10nm and the monodisperse PtM alloy nanoclusters with particle size of 20-300 nm.
2) The preparation process of the invention does not need high-temperature hydrothermal, and has the advantages of simple preparation process, short reaction time, mild reaction process conditions, greenness, cleanness and environmental protection;
3) The invention can greatly strengthen the mass transfer and micro mixing process of the reaction by utilizing the supergravity technology, and prepares the monodisperse nano PtM alloy aqueous phase dispersoid with high stability and more uniform particle size distribution by combining the supergravity technology and a chemical reduction method.
4) The invention adopts continuous operation, the retention time of reactants in the reactor is less than 1s, and the reaction products immediately leave the reactor after being formed.
5) The used process flow is simple, the required reactor has small volume, and the process is easy to operate; the product has high purity and good quality; the experiment has strong repeatability and is easy to amplify.
Drawings
The following detailed description of embodiments of the invention is provided in connection with the accompanying drawings
FIG. 1 shows a schematic diagram of a hypergravity reactor used in the solution of the invention;
FIG. 2 shows a transmission electron micrograph of a dispersion of nano PtAg alloy particles of a product obtained in example 1 of the present invention;
FIG. 3 is a pictorial representation of a dispersion of nano-PtAg alloy particles of a product obtained in example 1 of the present invention;
fig. 4 shows a transmission electron micrograph of a dispersion of nano-PtAg alloy clusters obtained in example 2 of the present invention;
FIG. 5 shows a transmission electron micrograph of a dispersion of nano-PtMo alloy particles of a product obtained in example 3 of the present invention;
FIG. 6 shows a physical representation of a dispersion of nano-PtMo alloy particles of a product obtained in example 3 of the invention;
figure 7 shows the XRD diffraction pattern of the product nano PtMo alloy particle dispersion obtained in example 3 of the present invention;
fig. 8 shows a transmission electron micrograph of a dispersion of nano PtMo alloy clusters of the product obtained in example 4 of the present invention;
FIG. 9 shows a transmission electron micrograph of a dispersion of nano-PtPd alloy particles of a product obtained in example 5 of the present invention;
fig. 10 shows a transmission electron micrograph of a dispersion of nano-PtPd alloy clusters of a product obtained in example 6 of the present invention;
the numbers referred to in the figures are numbered as follows:
1-feed liquid A feed inlet, 2-feed liquid B feed inlet, 3-filler, 4-motor, 5-liquid phase discharge outlet.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
As one aspect of the present invention, a method for producing monodisperse PtM alloy nanoparticles or nanoclusters of the present invention includes the steps of:
s1, dissolving a metal platinum precursor solution in a surfactant solution to obtain a feed liquid A;
s2, dissolving the metal M precursor solution into a surfactant solution to obtain a feed liquid B;
s3, dissolving a reducing agent in a water and alcohol mixed solution to obtain a feed liquid C;
s4, starting the hypergravity reactor;
s5, introducing the feed liquid A, the feed liquid B and the feed liquid C into a supergravity reactor through a peristaltic pump, and reacting to obtain a PtM nano alloy dispersion solution;
and S6, centrifuging and washing the PtM nano alloy dispersion solution, and dispersing in water to obtain the monodisperse PtM alloy nanoparticles or nanoclusters.
In certain embodiments of the present invention, in step S1, the metal platinum precursor is selected from one or more of the following: chloroplatinic acid, potassium tetrachloroplatinate, potassium hexachloroplatinate, platinum nitrate solution; preferably, the metal platinum precursor is selected from one or more of the following: chloroplatinic acid, potassium tetrachloroplatinate, potassium hexachloroplatinate.
In some embodiments of the present invention, in step S1, the concentration of the metal platinum precursor in the feed liquid a is 0.125-2.5mmol/L; preferably, the concentration of the metal platinum precursor in the feed liquid A is 0.3125-1.25mmol/L.
In certain embodiments of the present invention, in step S2, the metal M precursor is selected from one or more of the following: sodium molybdate, silver nitrate, copper nitrate, palladium chloride, potassium chloropalladate, chloroauric acid, ruthenium trichloride, rhodium chloride, iridium chloride and yttrium tetrachloride hydrate.
In certain embodiments of the present invention, in step S2, the concentration of the metal M precursor solution is 0.125-2.5mmol/L; more preferably, the concentration of the metal M precursor solution is 0.3125-1.25mmol/L.
In certain embodiments of the invention, in step S3, the alcoholic solvent is selected from one or more of the following: methanol, ethanol, ethylene glycol, isopropanol, glycerol, n-butanol, 2-butanol, n-decanol, nonanol, n-hexanol, polyethylene glycol; more preferably, in step S1, the alcoholic solvent is selected from one or more of the following: methanol, ethanol, ethylene glycol, glycerol and polyethylene glycol.
In certain embodiments of the invention, in steps S1, S2, the surfactant is selected from one or more of the following: polyvinylpyrrolidone, cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride and polyethylene glycol; more preferably, the surfactant is selected from one or more of the following: polyvinylpyrrolidone, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride.
In certain embodiments of the present invention, the surface modifier modification temperature in steps S1, S2 is 10 to 90 ℃; more preferably, the surface modifier modification temperature is 50 to 90 ℃.
In some embodiments of the invention, in steps S1 and S2, the surfactant accounts for 10 to 40% by mass of the modified nano PtM alloy.
In certain embodiments of the present invention, in step S3, the reducing agent is selected from one of the following: sodium borohydride, hydrazine hydrate. It should be noted that, in the present invention, when the reducing agent used is sodium borohydride, the prepared product is monodisperse PtM alloy nanoparticles; when the reducing agent is hydrazine hydrate, the prepared product is a monodisperse PtM alloy nanocluster.
In certain embodiments of the invention, in step S4, the reaction temperature in the hypergravity reactor is 10 to 90 ℃; preferably, in the step S4, the reaction temperature in the hypergravity reactor is 50-90 ℃; most preferably, in step S4, the reaction temperature in the hypergravity reactor is 50 to 70 ℃.
In certain embodiments of the present invention, in step S4, the hypergravity reactor is selected from a hypergravity rotating packed bed reactor, a baffled hypergravity rotating bed reactor, a spiral channel hypergravity rotating bed reactor, a stator-rotor hypergravity rotating bed reactor, or a rotating disk hypergravity rotating bed reactor; the rotating speed of a rotor of the hypergravity reactor is 500-2500rpm; preferably, the rotational speed of the rotor of the hypergravity reactor is 500-1500rpm.
In certain embodiments of the present invention, in step S5, the feed sequence of the feed liquid a, the feed liquid B, and the feed liquid C is selected from one of the following: simultaneously introducing the feed liquid A and the feed liquid C, and continuously feeding the feed liquid B after the feed liquid A is completely fed; mixing the feed liquid A and the feed liquid B, and introducing the mixture and the feed liquid C at the same time; and simultaneously introducing the feed liquid B and the feed liquid C, and continuously feeding the feed liquid A after the feed liquid B is completely fed.
In certain embodiments of the present invention, in step S5, the feed flow rate of the feed liquid a is 90 to 180ml/min, the feed flow rate of the feed liquid B is 90 to 180ml/min, the feed flow rate of the feed liquid C is 90 to 180ml/min, and the ratio of the feed flow rate of the feed liquid a to the feed flow rate of the feed liquid B is 1;
in certain embodiments of the present invention, in step S6, the centrifuge rotation speed for centrifugation is 8000 to 12000rpm; more preferably, the centrifuge rotation speed is 10000-12000rpm; the centrifugation time is 2-20min.
In certain embodiments of the present invention, in step S6, the detergent used in the washing process is selected from one or more of the following: methanol, ethanol, isopropanol, glycerol, butanol, acetone and butanone.
In certain embodiments of the present invention, in step S6, the method of dispersing is ultrasonic dispersing.
In certain embodiments of the invention, in step S6, the ratio of metal Pt to metal M in the PtM alloy nanoparticles or nanoclusters is 1:3-3:1.
The supergravity reactor used in the present invention is a conventional one, such as the published patent (publication number: CN2221437a, title of invention "rotating bed supergravity field device for enhanced transfer reaction"; FIG. 1 is a schematic diagram of a hypergravity reactor used in the present invention, which is specifically implemented by opening a hypergravity reactor device, adjusting the rotation speed to make the rotation speed of a rotor in the hypergravity reactor device reach a preset value, driving a material liquid A into a material liquid A feed port 1 in the hypergravity reactor after being measured by a pump and a flow meter, driving a material liquid B into a material liquid B feed port 2 in the hypergravity reactor after being measured by a pump and a flow meter, driving a rotor filler 3 in the hypergravity reactor to rotate at a high speed by a motor 4 to obtain a hypergravity environment, spraying the material liquid A and the material liquid B to the inner edge of the rotor filler of the hypergravity reactor through a liquid distributor on a feed pipe, colliding with the filler and entering the filler, cutting, crushing and tearing the material liquid A and the material B through a wire mesh filler to generate a large amount of fast renewed liquid surface, greatly enhancing the intermolecular process, shortening the crystal nucleus growth time after the reactant reaction precipitation crystallization, further effectively controlling the particle size and morphology of the nucleation particles, collecting a homogeneous liquid phase solution after the reaction in the hypergravity reactor from a hypergravity reactor, and collecting a black phase solution through a black phase solution outlet after the ultrasonic washing and a black phase dispersion, and collecting a black phase dispersion after the ultrasonic washing process.
Example 1
A preparation method of a nano PtAg alloy particle dispersion comprises the following steps:
1) Preparing a feed liquid A: mixing 12.15mg of potassium chloroplatinate, 25mg of polyvinylpyrrolidone and 10ml of water, and magnetically stirring for 30min; preparing a feed liquid B: mixing 4.25mg of silver nitrate, 25mg of polyvinylpyrrolidone and 10ml of water, and magnetically stirring for 30min; preparing a feed liquid C: mixing 18.91mg sodium borohydride and 20ml water;
2) By adopting the device shown in FIG. 1, firstly, the circulating water device is started, the water temperature is set to be 50 ℃, and the supergravity reactor is heated;
3) Setting the rotation speed of a rotor to be 1500rpm, starting the supergravity reactor, mixing A, B solution, respectively introducing feed liquid A, B and C into the supergravity reactor through a peristaltic pump, wherein the flow rate of the mixed feed liquid A, B is 120ml/min, and the flow rate of the feed liquid C is 120ml/min, so as to obtain PtAg nano dispersion solution;
4) The PtAg nano dispersion solution is centrifugally washed for 3-5 times by absolute ethyl alcohol, and the weight ratio of water: ethanol =1: and 5, dispersing the washed PtAg precipitate into water at the rotation speed of 12000rpm for 15min each time to obtain a monodisperse nano PtAg particle dispersion.
Fig. 2 is a transmission electron microscope photograph of the monodisperse nano PtAg particle dispersion obtained in this example 1, and it can be seen from fig. 1 that the obtained product has an elliptical particle shape with a particle morphology of not less than 80%, an average size of 4-5nm, and a high particle specific surface area.
Fig. 3 is a physical diagram of the monodisperse nano PtAg particle dispersion obtained in example 1, and it can be seen that the dispersion is transparent and stable, and does not precipitate after being placed for more than 6 months.
Example 2
A preparation method of a nano PtAg alloy cluster dispersion comprises the following steps:
1) Preparing a feed liquid A: mixing 12.15mg potassium chloroplatinate, 25mg polyvinylpyrrolidone, 5ml water and 5ml ethanol, and magnetically stirring for 30min; preparing a feed liquid B: mixing 4.25mg of silver nitrate, 25mg of polyvinylpyrrolidone and 5ml of water and 5ml of ethanol, and magnetically stirring for 30min; preparing a feed liquid C: mixing 1ml of hydrazine hydrate and 20ml of ethanol;
2) The device shown in FIG. 1 is adopted, firstly, the water circulating device is started, the water temperature is set to be 50 ℃, and the supergravity reactor is heated;
3) Setting the rotation speed of a rotor to be 1500rpm, starting the supergravity reactor, mixing A, B solution, respectively introducing feed liquid A, B and C into the supergravity reactor through a peristaltic pump, wherein the flow rate of the mixed feed liquid A, B is 120ml/min, and the flow rate of the feed liquid C is 120ml/min, so as to obtain PtAg nano dispersion solution;
4) And (3) centrifugally washing the PtAg nano dispersion solution for 3-5 times by using absolute ethyl alcohol, wherein the absolute ethyl alcohol is =1:1, the rotation speed is 10000rpm, and the PtAg precipitate after washing is dispersed into water every time for 10min, so that the monodisperse nano PtAg cluster dispersion is obtained.
Fig. 4 is a transmission electron micrograph of the monodisperse nano PtAg cluster dispersion obtained in this example 2, and it can be seen from fig. 4 that the obtained product has a uniform flower-like particle morphology, an average size of 200nm, and no precipitation after cluster dispersion for more than 1 month.
Example 3
A preparation method of a nano PtMo alloy particle dispersion comprises the following steps:
1) Preparing a feed liquid A: mixing 12.15mg potassium chloroplatinate, 25mg polyvinylpyrrolidone and 10ml water, and magnetically stirring for 30min; preparing a feed liquid B: mixing 12.05mg of sodium molybdate, 25mg of polyvinylpyrrolidone and 10ml of water, and magnetically stirring for 30min; preparing a feed liquid C: mixing 18.91mg sodium borohydride and 20ml water;
2) The device shown in FIG. 1 is adopted, firstly, the water circulating device is started, the water temperature is set to be 70 ℃, and the supergravity reactor is heated;
3) Setting the rotation speed of a rotor to be 1500rpm, starting the supergravity reactor, mixing A, B solution, respectively introducing feed liquid A, B and C into the supergravity reactor through a peristaltic pump, wherein the flow rate of the mixed feed liquid A, B is 120ml/min, and the flow rate of the feed liquid C is 120ml/min, so as to obtain PtMo nano dispersion solution;
4) And (3) centrifugally washing the PtMo nano dispersion solution for 3-5 times by using absolute ethyl alcohol, wherein the absolute ethyl alcohol is =1:5, the rotating speed is 12000rpm, and the PtMo precipitate after washing is dispersed into water every time for 15min, so that the monodisperse nano PtMo particle dispersion is obtained.
Fig. 5 is a transmission electron microscope photograph of the monodisperse nano PtMo particle dispersion of the product obtained in this example 3, and it can be seen from fig. 5 that the obtained product has an elliptical particle shape with a morphology of not less than 90%, an average size of 2 to 3nm, and a high specific surface area.
Fig. 6 is a real image of the monodisperse nano PtMo particle dispersion of the product obtained in this example 3, which is transparent and stable, and does not precipitate after being placed for more than 6 months.
FIG. 7 is an XRD diffraction pattern of the product obtained in example 3. From fig. 7, it can be seen that the obtained product is a PtMo alloy, a face-centered cubic structure of Pt is only formed on the surface in the diffraction pattern, the whole diffraction peak is symmetrical, and the diffraction peak is shifted to the left by doping Mo, indicating that a uniform PtMo alloy structure is generated.
Example 4
A preparation method of a nano PtMo alloy cluster dispersion comprises the following steps:
1) Preparing a feed liquid A: mixing 12.15mg potassium chloroplatinate, 25mg polyvinylpyrrolidone, 5ml water and 5ml ethanol, and magnetically stirring for 30min; preparing a feed liquid B: mixing 12.05mg of sodium molybdate, 25mg of polyvinylpyrrolidone and 5ml of water and 5ml of ethanol, and magnetically stirring for 30min; preparing a feed liquid C: mixing 1ml of hydrazine hydrate and 20ml of ethanol;
2) By adopting the device shown in FIG. 1, firstly, the circulating water device is started, the water temperature is set to be 70 ℃, and the supergravity reactor is heated;
3) Setting the rotation speed of a rotor to be 1500rpm, starting the supergravity reactor, mixing A, B solution, respectively introducing feed liquid A, B and C into the supergravity reactor through a peristaltic pump, wherein the flow rate of the mixed feed liquid A, B is 120ml/min, and the flow rate of the feed liquid C is 120ml/min, so as to obtain PtMo nano dispersion solution;
4) And (3) centrifugally washing the PtMo nano dispersion solution for 3-5 times by using absolute ethyl alcohol, wherein the absolute ethyl alcohol is =1:1, the rotation speed is 10000rpm, and the PtMo precipitate after washing is dispersed into water every time for 10min, so that the monodisperse nano PtMo cluster dispersion is obtained.
Fig. 8 is a transmission electron micrograph of the monodisperse nano PtMo cluster dispersion obtained in this example 4, and it can be seen from fig. 8 that the obtained product has a spherical particle morphology, an average size of 200nm, and no precipitation after cluster dispersion for more than 1 month.
Example 5
A preparation method of a nano PtPd alloy particle dispersion comprises the following steps:
1) Preparing a feed liquid A: mixing 12.15mg of potassium chloroplatinate, 25mg of polyvinylpyrrolidone and 10ml of water, and magnetically stirring for 30min; preparing a feed liquid B: mixing 4.43mg of palladium chloride, 25mg of polyvinylpyrrolidone and 10ml of water, and magnetically stirring for 30min; preparing a feed liquid C: mixing 18.91mg sodium borohydride and 20ml water;
2) The device shown in FIG. 1 is adopted, firstly, the water circulating device is started, the water temperature is set to be 90 ℃, and the supergravity reactor is heated;
3) Setting the rotation speed of a rotor to be 1500rpm, starting the supergravity reactor, mixing A, B solution, respectively introducing feed liquid A, B and C into the supergravity reactor through a peristaltic pump, wherein the flow rate of the mixed feed liquid A, B is 120ml/min, and the flow rate of the feed liquid C is 120ml/min, so as to obtain PtPd nano dispersion solution;
4) And (3) centrifugally washing the PtPd nano dispersion solution by using absolute ethyl alcohol for 3-5 times, wherein the absolute ethyl alcohol is =1:5, the rotating speed is 12000rpm, and each time is 15min, and dispersing the washed PtPd precipitate into water to obtain a monodisperse nano PtPd particle dispersion.
Fig. 9 is a transmission electron micrograph of the monodisperse nano PtPd particle dispersion obtained in this example 5, and it can be seen from fig. 5 that the obtained product has an elliptical particle morphology of not less than 90%, an average size of 5-10nm, a high specific surface area of the particle, and the dispersion does not precipitate after being left for more than 6 months.
Example 6
A preparation method of a nano PtPd alloy cluster dispersion comprises the following steps:
1) Preparing a feed liquid A: mixing 12.15mg of potassium chloroplatinate, 25mg of polyvinylpyrrolidone, 5ml of water and 5ml of ethanol, and magnetically stirring for 30min; preparing a feed liquid B: mixing 4.43mg of palladium chloride, 25mg of polyvinylpyrrolidone, 5ml of water and 5ml of ethanol, and magnetically stirring for 30min; preparing a feed liquid C: mixing 1ml of hydrazine hydrate and 20ml of ethanol;
2) The device shown in FIG. 1 is adopted, firstly, the water circulating device is started, the water temperature is set to be 90 ℃, and the supergravity reactor is heated;
3) Setting the rotation speed of a rotor to be 1500rpm, starting the super-gravity reactor, mixing A, B solution, respectively introducing feed liquid A, B and C into the super-gravity reactor through a peristaltic pump, wherein the flow rate of the mixed feed liquid A, B is 120ml/min, and the flow rate of the feed liquid C is 120ml/min, so as to obtain PtPd nano dispersion solution;
4) And centrifuging and washing the PtPd nano dispersion solution by using absolute ethyl alcohol for 3-5 times, wherein the ethanol =1:1, the rotation speed is 10000rpm, and the PtPd precipitate after washing is dispersed into water every time for 10min, so that the monodisperse nano PtPd cluster dispersion is obtained.
Fig. 10 is a transmission electron micrograph of the monodisperse nano PtPd cluster dispersion obtained in this example 6, and it can be seen from fig. 8 that the obtained product has a spherical particle morphology, an average size of 80-100nm, and no precipitation after cluster dispersion for more than 1 month.
Example 7
Example 1 was repeated with the difference that: step 1) is to; the effect of changing potassium hexachloroplatinate to chloroplatinic acid was similar to that of example 1.
Example 8
Example 1 was repeated with the difference that: the dosage of the polyvinylpyrrolidone in the step 1) is 70mg or 100mg; the effect is similar to that of example 1.
Example 9
Example 1 was repeated with the difference that: changing the solvent water added in the step 1) into one or more of mixed solution of water, methanol, ethanol and glycol; the effect is similar to that of example 1.
Example 10
Example 1 was repeated with the difference that: the concentration of the precursor solution in the step 1) is 0.025mmol-0.1mmol; the effect is similar to that of example 1.
Example 11
Example 1 was repeated with the difference that: the reaction temperature in the step 2) is 30 ℃; the effect is as follows: the average particle size of the obtained product was 3.9nm.
Example 12
Example 1 was repeated with the difference that: the reaction temperature in the step 2) is 70 ℃; the effect is as follows: the average particle size of the obtained product was 5.8nm.
Example 13
Example 1 was repeated with the difference that: in the step 3), the feed liquid A and the feed liquid C are simultaneously introduced into the hypergravity reactor, the feed liquid B is added after the A is consumed, so that the feed liquid B and the feed liquid C are simultaneously introduced into the hypergravity reactor, and the effect is as follows: the obtained product is in a core-shell type alloy structure with Pt as a core and PtM alloy as a shell.
Example 14
Example 1 was repeated with the difference that: in the step 3), the feed liquid B and the feed liquid C are simultaneously introduced into the hypergravity reactor, the feed liquid A is added after the B is consumed, so that the feed liquid A and the feed liquid C are simultaneously introduced into the hypergravity reactor, and the effect is as follows: the obtained product is in a core-shell type alloy structure with M as a core and PtM alloy as a shell.
Examples15
Example 2 was repeated with the difference that: in the step 1), the ethanol in the feed liquid A is changed into methanol; the effect is as follows: the average particle size of the obtained product was 200nm.
Example 16
Example 2 was repeated with the difference that: changing ethanol in the feed liquid A in the step 1) into glycol; the effect is as follows: the average particle size of the resulting product was 127nm.
Example 17
Example 2 was repeated with the difference that: in the step 1), ethanol in the feed liquid A is changed into glycerol; the effect is as follows: the average particle size of the obtained product was 135nm.
Example 18
Example 2 was repeated with the difference that: changing ethanol in the feed liquid A in the step 1) into polyethylene glycol; the effect is as follows: the average particle size of the resulting product was 173nm.
Example 19
Example 2 was repeated with the difference that: changing the solvent of 5ml of water and 35ml of ethanol and 10ml of water and 30ml of ethanol in the step 1) into one of 40ml of water, 20ml of water and 20ml of ethanol, 30ml of water and 10ml of ethanol and 35ml of water and 5ml of ethanol; the effect is similar to that of example 1.
Comparative example 1
A dispersion of nano PtAg alloy particles was made using the procedure as described in example 1, except that: in the step 1), one or more of glucose and sodium citrate which are not in the reducing agent range of the step 1) are selected, and the result is as follows: nano PtAg alloy particle dispersions cannot be prepared by this method.
Comparative example 2
A dispersion of nano PtAg alloy particles was made using the procedure as described in example 1, except that: in the step 1), the modifier polyvinylpyrrolidone is changed into one or more of KH570 silane coupling agent and KH550 silane coupling agent, and the result is as follows: the nano PtAg alloy particle dispersoid cannot be prepared by the method and cannot be stably dispersed in water, so that the method needs to reasonably select the type of the modifier, and other aqueous modifiers cannot effectively modify the surface of the alloy.
Comparative example 3
A dispersion of nano PtAg alloy particles was made using the procedure as described in example 1, except that: the dosage of the polyvinylpyrrolidone in the step 1) is 0-50mg or 100-200 mg, and the result is as follows: the modifier dosage is too low to prepare stable nanometer PtAg alloy particle dispersoid by the method, and partial precipitates exist. Too high modifier dosage and too large alloy surface coating amount affect subsequent catalytic performance. Therefore, the modifier needs to be controlled in the preferable range, the modifier cannot be effectively modified when the amount of the modifier is too small, and the catalytic effect of the product prepared by exceeding the range is poor.
Comparative example 4
A dispersion of nano PtAg alloy particles was made using the procedure as described in example 1, except that: the dosage of the potassium chloroplatinate in the step 1) is a certain dosage out of the range of 0.3125-1.25mmol/L, and the result is as follows: alloy particles of uniform size cannot be obtained.
Comparative example 5
A dispersion of nano PtAg alloy particles was made using the procedure as described in example 1, except that: the dosage of the silver nitrate in the step 1) is a certain dosage out of the range of 0.3125-1.25mmol/L, and the result is as follows: alloy particles of uniform size cannot be obtained.
Comparative example 6
A dispersion of nano PtAg alloy particles was made using the procedure as described in example 1, except that: in the step 1), the reaction temperature is selected from a certain temperature range of 70-90 ℃, and the result is as follows: the high temperature leads to too fast reaction, partial precursor can not be completely consumed, and the method can not be used for preparing the nano PtAg alloy particle dispersoid with uniform size.
Comparative example 7
A dispersion of nano PtAg alloy particles was made using the procedure as described in example 1, except that: the rotating speed of the hypergravity reactor in the step 3) is selected from a certain rotating speed of 450 rpm or 3000rpm, and the result is as follows: nanometer PtAg alloy particle dispersoids with uniform size cannot be prepared by the method.
Comparative example 8
A dispersion of nano PtAg alloy clusters was prepared using the procedure as described in example 1, except that: the rotating speed of the centrifuge in the step 4) is 7000rpm, and the result is as follows: the rotational speed is too low. The alloy particles cannot be completely separated.
Comparative example 9
A dispersion of nano PtAg alloy particles was made using the procedure as described in example 1, except that: in the step 1), the precursor of platinum in the feed liquid A is platinum nitrate solution, and the result is as follows: the nano PtAg alloy cluster dispersion cannot be prepared by the method.
Comparative example 10
A dispersion of nano PtAg alloy clusters was made using the procedure as described in example 2, except that: the solvent used in step 1) was 40ml ethanol, and the results were as follows: too high polarity of the solvent can lead to the product being undispersed, and the nano PtAg alloy cluster dispersoids cannot be prepared by the method.
In conclusion, the technical scheme of the invention is an organic whole, and the required product of the invention can be obtained only by matching and coordinating the technical characteristics.
It should be understood that the above-described embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. Not all embodiments are exhaustive. All obvious changes and modifications which are obvious to the technical scheme of the invention are covered by the protection scope of the invention.
Claims (10)
1. A preparation method of monodisperse PtM alloy nanoparticles or nanoclusters is characterized by comprising the following steps:
s1, dissolving a metal platinum precursor solution in a surfactant solution to obtain a feed liquid A;
s2, dissolving the metal M precursor solution into a surfactant solution to obtain a feed liquid B;
s3, dissolving a reducing agent in a mixed solution of water and alcohol to obtain a feed liquid C;
s4, starting the supergravity reactor;
s5, introducing the feed liquid A, the feed liquid B and the feed liquid C into a supergravity reactor through a peristaltic pump, and reacting to obtain a PtM nano alloy dispersion solution;
and S6, centrifuging and washing the PtM nano alloy dispersion solution, and dispersing in water to obtain the monodisperse PtM alloy nanoparticles or nanoclusters.
2. The method according to claim 1, wherein the method comprises: in step S1, the metal platinum precursor is selected from one or more of the following substances: chloroplatinic acid, potassium tetrachloroplatinate, potassium hexachloroplatinate, platinum nitrate solution; preferably, the metal platinum precursor is selected from one or more of the following: chloroplatinic acid, potassium hexachloroplatinate.
3. The method according to claim 1, wherein the method comprises: in the step S1, the concentration of the metal platinum precursor in the feed liquid A is 0.125-2.5mmol/L; preferably, the concentration of the metal platinum precursor in the feed liquid A is 0.3125-1.25mmol/L.
4. The method according to claim 1, wherein the method comprises: in step S2, the metal M precursor is selected from one or more of the following substances: sodium molybdate, silver nitrate, copper nitrate, palladium chloride, potassium chloropalladate, chloroauric acid, ruthenium trichloride, rhodium chloride, iridium chloride and yttrium tetrachloride hydrate.
5. The method according to claim 1, wherein the method comprises: in the step S2, the concentration of the metal M precursor solution is 0.125-2.5mmol/L; more preferably, the concentration of the metal M precursor solution is 0.3125-1.25mmol/L.
6. The method according to claim 1, wherein the method comprises: in step S3, the alcohol solvent is selected from one or more of the following substances: methanol, ethanol, ethylene glycol, isopropanol, glycerol, propanol, n-butanol, 2-butanol, n-decanol, nonanol, n-hexanol, polyethylene glycol; more preferably, in step S1, the alcoholic solvent is selected from one or more of the following: methanol, ethanol, ethylene glycol, glycerol and polyethylene glycol.
7. The method according to claim 1, wherein the method comprises: in the steps S1 and S2, the surfactant is selected from one or more of the following substances: polyvinylpyrrolidone, hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium chloride and polyethylene glycol; more preferably, the surfactant is selected from one or more of the following: polyvinylpyrrolidone, cetyltrimethylammonium bromide, cetyltrimethylammonium chloride;
preferably, in the steps S1 and S2, the modification temperature of the surface modifier is 10-90 ℃; more preferably, the surface modifier modification temperature is 50-90 ℃;
preferably, in the steps S1 and S2, the surfactant accounts for 10 to 40 mass percent of the modified nano PtM alloy.
8. The method according to claim 1, wherein the method comprises: in step S3, the reducing agent is selected from one of the following substances: sodium borohydride, hydrazine hydrate.
9. The method according to claim 1, wherein the method comprises: in the step S4, the reaction temperature in the hypergravity reactor is 10-90 ℃; preferably, in the step S4, the reaction temperature in the hypergravity reactor is 50-90 ℃; most preferably, in the step S4, the reaction temperature in the hypergravity reactor is 50-70 ℃;
preferably, in step S4, the hypergravity reactor is selected from a hypergravity rotating packed bed reactor, a baffled hypergravity rotating bed reactor, a spiral channel hypergravity rotating bed reactor, a stator-rotor hypergravity rotating bed reactor or a rotating disc hypergravity rotating bed reactor; the rotating speed of a rotor of the hypergravity reactor is 500-2500rpm; preferably, the rotational speed of the rotor of the hypergravity reactor is 500-1500rpm.
10. The method according to claim 1, wherein the method comprises: in step S5, the feeding sequence of the feed liquid a, the feed liquid B, and the feed liquid C is selected from one of the following: simultaneously introducing the feed liquid A and the feed liquid C, and continuously feeding the feed liquid B after the feed liquid A is completely fed; mixing the feed liquid A and the feed liquid B, and introducing the mixture and the feed liquid C at the same time; introducing the feed liquid B and the feed liquid C at the same time, and replacing the feed liquid A for continuous feeding after the feed liquid B is completely fed;
preferably, in step S5, the feed flow rate of the feed liquid a is 90 to 180ml/min, the feed flow rate of the feed liquid B is 90 to 180ml/min, the feed flow rate of the feed liquid C is 90 to 180ml/min, and the ratio of the feed flow rates of the feed liquid a and the feed liquid B is 1;
as a further improvement of the technical scheme, in the step S6, the rotating speed of the centrifugal machine for centrifugation is 8000-12000rpm; more preferably, the centrifuge rotation speed is 8000-10000rpm; centrifuging for 2-20min;
preferably, in step S6, the detergent used in the washing process is selected from one or more of the following substances: methanol, ethanol, isopropanol, glycerol, butanol, acetone, butanone;
preferably, in step S6, the dispersing method is mechanical stirring or ultrasonic dispersing;
preferably, in step S6, the ratio of the metal Pt to the metal M in the PtM alloy nanoparticles or nanoclusters is 1:3-3:1.
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