CN114523120A - Preparation method of metal alloy nano-cluster particles - Google Patents

Preparation method of metal alloy nano-cluster particles Download PDF

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CN114523120A
CN114523120A CN202111673623.1A CN202111673623A CN114523120A CN 114523120 A CN114523120 A CN 114523120A CN 202111673623 A CN202111673623 A CN 202111673623A CN 114523120 A CN114523120 A CN 114523120A
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aqueous solution
precursor
metal precursor
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姜海波
李春忠
毕瓅元
余盛伟
张文会
陆吉源
孙雪
张丽丽
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East China University of Science and Technology
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Abstract

The invention discloses a preparation method of metal alloy nano-cluster particles. The preparation method comprises the following steps: mixing and reacting a mixed aqueous solution containing a reducing precursor, a metal precursor and a carrier; the reducing precursors include citrates and ferrous salts; the molar ratio of the citrate to the ferrous salt is 12: 30-8: 1; the temperature of the mixing reaction is at least 80 ℃. The preparation method disclosed by the invention is simple to operate, green and environment-friendly, low in preparation cost and low in energy consumption, and is very suitable for industrial large-scale production. The metal alloy cluster prepared by the invention has small particle size, uniform size, high dispersion and relatively clean components.

Description

Preparation method of metal alloy nano-cluster particles
Technical Field
The invention relates to a preparation method of metal alloy nano-cluster particles.
Background
Metal nano materials are very important multifunctional materials, and are receiving close attention due to wide application in the fields of photo/electro-catalysis, chemical energy storage, information sensing, biomedical diagnosis, treatment and the like. Among them, the metal alloy nanoclusters are of great interest due to small particles, large specific surface activity and wide application range.
The currently reported metal alloy nano material and oil phase synthesis preparation method are mature processes for preparing high-dispersion catalyst particles, Chao Wang et al (Multimetallic Au/FePt3 nanoparticles as high-purity durable electrochemical catalyst. Nano Lett 2011,11(3),919-26.) use oleylamine as a solvent, borane tert-butylamine reduces gold nanoparticles, an alloy nano film is deposited on the basis, platinum bimetallic alloy particles are obtained through organic solvent thermal reduction, the preparation process lasts 3-4 days, organic solvents and other materials used in the reaction process are complicated, and the time of pickling treatment is more than one day due to the need of removing surfactants and organic solvents; the CoFe @ Pt core/shell nano-particles are synthesized in organic solvent oleylamine by Ngo T.Dung et al (High mapping, monodisperse and water-discrete CoFe @ Pt core/shell nanoparticles. nanoscale 2017,9(26),8952-8961.) to obtain well-dispersed metal alloy nano-particles; junrui Li et al (Hard-Magnet L10-CoPt Nanoparticles Advance Fuel Cell catalysis, Joule 2019,3(1),124-135.) synthesized CoPt metal alloy Nanoparticles with oleylamine as solvent and reducing agent to obtain the cashew-shaped alloy catalyst, the size of the Nanoparticles is about 10nm, the dispersibility is good, and the residual organic solvent after cleaning is removed through high-temperature annealing post-treatment.
In summary, the current organic solvent thermal synthesis method (wet synthesis) mainly based on oleylamine is difficult to produce in large scale due to complex and long-time post-treatment processes such as centrifugal cleaning, acid washing, high-temperature annealing and the like. In addition, organic surfactants are used to control particle morphology, contaminate the surface, and require careful cleaning to expose the active surface. The complicated contaminant removal steps and the complexity of the synthesis procedure increase the production cost of the organosolv synthesis method and the environmental pollution is also serious.
The templating method is also considered to be an effective strategy for synthesizing nanoparticle structures. The mesoporous silicon attracts people's attention as an ideal hard template for preparing porous nano-structures. Utilizing a chemical dealloying method to etch Au-Ag nano-sphere particles coated with a silicon dioxide layer on the surface to finally obtain ultrathin silicon dioxide coated porous Au-Ag alloy nano-particles; liu et al (Residual silver re-marked anodic activity and dual of metallic nanosponent [ J ]. Nano Letters,2016,16(11): 7248-; liu et al (Nanoporous Pt-Co alloy nanowines: contamination, chromatography, and electrolytic properties [ J ]. Nano Letters,2009,9(12): 4352-. However, the synthesis method has difficulty in efficiently synthesizing metal alloy nanocluster particles due to the complexity of template removal through multiple steps.
The key to preparing the metal alloy nanocluster particles is to ensure high dispersion, small size and uniform growth of the nanoparticles. In addition, water is used as a reaction solvent, which is green and environment-friendly, but related synthesis methods are reported less at present. Ji et al (Size Control of Gold Nanocrystals in Gold Reduction The Third Role of ditate [ J ]. Jacs particles, 2007,10(19):13939-13948) prepared Gold nanoparticles with a particle Size of 20-40nm by controlling The concentrations of chloroauric acid and sodium Citrate, however, The particle Size, The degree of dispersion and The uniformity of The Gold nanoparticles still need to be improved.
Therefore, it is highly desirable to provide a method for preparing metal nanocluster particles with small particle size, high dispersion and uniform growth, which is simple to operate and environmentally friendly.
Disclosure of Invention
The invention aims to overcome the defects of large size, uneven dispersion and uneven size of metal alloy nano-cluster particles in the prior art, and provides a preparation method of the metal alloy nano-cluster particles. The method has the advantages of low cost, simple operation, no pollution and large-scale production. The prepared metal alloy nano-cluster particles have the diameter range of 3-7 nm, uniform size, uniform dispersion and relatively clean components, and almost contain no impurities.
The present invention provides the following technical solutions to solve the above technical problems.
The invention provides a preparation method of metal alloy nano-cluster particles, which comprises the following steps:
mixing and reacting a mixed aqueous solution containing a reducing precursor, a metal precursor and a carrier; the reducing precursor comprises citrate and ferrous salts; the molar ratio of the citrate to the ferrous salt is 12: 30-8: 1;
the temperature of the mixing reaction is at least 80 ℃.
In the present invention, the molar ratio of the reducing precursor, the metal precursor, and the support may be 4 to 60: 0.5-3: 1 to 6, preferably 10 to 50: 0.7-2.8: 2 to 5.5, preferably 11 to 48: 0.7-2.8: 2 to 5.5, for example, 11: 1: 5.3, 14: 1.1: 4.2, 36: 2: 3.8 or 48: 2.7: 2.2.
in the present invention, the citrate may be one or more of sodium citrate, ammonium citrate and potassium citrate, preferably sodium citrate.
In the present invention, the ferrous salt may be one or more of ferrous sulfate, ferrous phosphate and ferrocene, and is preferably ferrous sulfate.
In the present invention, the molar ratio of the citrate to the ferrous salt is preferably 12:25 to 8:3, more preferably 12:24 to 8:3, for example 8:6, 8:10, 8:13, 18:30 or 8: 15.
In the present invention, the concentration of the reducing precursor in the mixed aqueous solution may be 4 to 60mM, preferably 10 to 50mM, more preferably 11 to 48mM, such as 14mM or 36 mM.
In the present invention, the concentration of the metal precursor in the mixed aqueous solution may be 0.5 to 3mM, preferably 0.7 to 2.8mM, such as 1mM, 1.1mM, 2mM or 2.7 mM.
In the present invention, the metal precursor may be a noble metal precursor and/or a transition metal precursor.
The noble metal precursor is generally a noble metal-containing salt, for example, a noble metal-containing halide. The halide salt containing a noble metal may be a chlorate salt containing a noble metal, preferably chloroplatinic acid and/or chloroauric acid.
The transition metal precursor is typically a transition metal-containing salt, such as a transition metal-containing halide salt. The halide salt containing a transition metal may be a chloride salt containing a transition metal, preferably one or more of nickel chloride, cobalt chloride and copper chloride, such as nickel chloride, cobalt chloride or copper chloride.
In the present invention, when the metal precursor is a mixture of the noble metal precursor and the transition metal precursor, the molar ratio of the noble metal precursor to the transition metal precursor may be 0.5:1 to 3:1, preferably 0.5:0.5 to 2:1, for example 0.7:0.4, 1.2:0.8 or 1.6: 1.1.
In the present invention, the concentration of the noble metal precursor in the mixed aqueous solution may be 0.1 to 2mM, preferably 0.2 to 1.2mM, such as 0.4mM, 0.6mM, 1.2mM, 1.6mM, or 0.7 mM.
When the noble metal precursor comprises chloroplatinic acid, the concentration of the chloroplatinic acid in the mixed aqueous solution may be 0.1 to 2mM, preferably 0.2 to 1.2mM, such as 0.6mM, 1.2mM, or 1.6 mM.
When the noble metal precursor includes chloroauric acid, the concentration of the chloroauric acid in the mixed aqueous solution may be 0.1 to 2mM, preferably 0.2 to 1.2mM, such as 0.4mM or 0.7 mM.
When the noble metal precursor is a mixture of the chloroauric acid and the chloroplatinic acid, the molar ratio of the chloroauric acid to the chloroplatinic acid may be 0.1:0.4 to 0.5:0.25, preferably 0.4: 0.6.
In the present invention, the concentration of the transition metal precursor in the mixed aqueous solution may be 0.1 to 2mM, preferably 0.2 to 1.2mM, such as 0.4mM, 0.8mM, or 1.1 mM.
When the transition metal precursor is nickel chloride, the concentration of the nickel chloride in the mixed aqueous solution may be 0.1 to 2mM, preferably 0.2 to 1.2mM, for example, 0.4 mM.
When the transition metal precursor is cobalt chloride, the concentration of the cobalt chloride in the mixed aqueous solution may be 0.1-2 mM, preferably 0.2-1.2 mM, for example 0.8 mM.
When the transition metal precursor is copper chloride, the concentration of the copper chloride in the mixed aqueous solution may be 0.1-2 mM, preferably 0.2-1.2 mM, for example 1.1 mM.
In the present invention, the support is generally a carbon support, preferably carbon black. In a preferred embodiment of the present invention, Vulcan XC-72 carbon black is used.
In the present invention, the concentration of the carrier in the mixed aqueous solution may be 1 to 6mM, preferably 2 to 5.5mM, such as 2.2mM, 3.8mM, 4.2mM or 5.3 mM.
In the present invention, the water in the mixed aqueous solution is generally deionized water.
In the present invention, the method for preparing the mixed aqueous solution preferably comprises the steps of: and sequentially adding the solution containing the reducing precursor and the solution containing the metal precursor into the solution containing the carrier, and uniformly mixing.
The preparation method of the carrier solution can be conventional in the art, and the carrier and water are generally mixed uniformly. In the solution containing the carrier, the concentration of the carrier may be conventional in the art, and generally the carrier can be dispersed uniformly, for example, 0.13mg/mL, 0.23mg/mL, 0.25mg/mL or 0.32 mg/mL. The water in the solution containing the carrier is typically deionized water.
The preparation method of the solution of the reducing precursor may be conventional in the art, and the reducing precursor and water are generally mixed uniformly. The concentration of the reducing precursor in the solution containing the reducing precursor may be conventional in the art, e.g. 8 wt% or 0.8 mM. The water in the solution containing the reducing precursor is typically deionized water.
The preparation method of the metal precursor solution can be conventional in the art, and the metal precursor and water are generally mixed uniformly. The concentration of the metal precursor in the solution containing the metal precursor may be conventional in the art, for example, 10 mg/mL. The water in the solution containing the metal precursor is typically deionized water.
In the invention, the amount of water in the mixed aqueous solution can be controlled according to a reaction instrument, and generally does not exceed 80 percent of the total volume of the reaction instrument. The water is typically deionized water.
In the present invention, the temperature of the mixing reaction is preferably 80 to 100 ℃, for example, 90 ℃.
In the present invention, the mixing reaction time may be 20 to 200min, preferably 30 to 120min, such as 60min or 90 min.
In the present invention, the mixing reaction preferably further comprises a drying step.
Wherein, the drying treatment step can be freeze-drying, centrifugal drying or rotary evaporation drying. The manner of the drying treatment step may be generally selected depending on the volume of the solution after the mixing reaction. For example, the volume of the solution after mixing the reaction is less than 50mL, and optionally lyophilized. After mixing and reacting, the volume of the solution is less than 100mL, and centrifugal drying can be selected. After mixing and reacting, the volume of the solution is more than 100mL, and rotary evaporation drying can be selected.
In the present invention, preferably, an organic solvent is not used in the method for preparing the metal alloy nanocluster particles. The organic solvent generally refers to a dispersion solvent conventionally used in the art for preparing nanoparticles, such as oleylamine, oleic acid, N-Dimethylformamide (DMF), toluene, or chloroform.
In the present invention, the diameter of the metal alloy nanocluster particles may be 3 to 7nm, preferably 3.5 to 5nm, such as 3.52nm, 3.69nm, 4.16nm or 4.76 nm.
In the invention, the metal alloy nano-cluster particles can be used as a catalyst to be applied to catalytic reaction of a fuel cell. The fuel cell catalytic reaction is typically an ORR reaction, MOR reaction or OER reaction.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and starting materials used in the present invention are commercially available.
The positive progress effects of the invention are as follows:
(1) the metal alloy cluster prepared by the invention has small particle size (the particle diameter range can reach 3-7 nm), uniform size, uniform dispersion and relatively clean components.
(2) The preparation method disclosed by the invention is simple to operate, can adopt the aqueous solution as a reaction solvent, is green and environment-friendly, has low preparation cost and low energy consumption, and is very suitable for industrial large-scale production.
Drawings
FIG. 1 is a transmission electron micrograph of AuPt/C prepared in example 1.
FIG. 2 is a particle diameter distribution histogram of AuPt/C prepared in example 1.
FIG. 3 is a TEM image of NiPt/C prepared in example 2.
FIG. 4 is a histogram of particle diameter distribution of NiPt/C prepared in example 2.
FIG. 5 is a TEM image of CoPt/C prepared in example 3.
FIG. 6 is a histogram of particle diameter distribution of CoPt/C prepared in example 3.
FIG. 7 is a TEM image of CuPt/C prepared in example 4.
FIG. 8 is a histogram of particle diameter distribution of CuPt/C prepared in example 4.
FIG. 9 is a TEM image of CoPt/C prepared in example 5.
FIG. 10 is a histogram of particle diameter distribution of CoPt/C prepared in example 5.
FIG. 11 is a TEM image of CoPt/C prepared in example 6.
FIG. 12 is a histogram of particle diameter distribution of CoPt/C prepared in example 6.
FIG. 13 is a transmission electron micrograph of AuPt/C prepared in comparative example 1.
FIG. 14 is a particle diameter distribution histogram of AuPt/C prepared in comparative example 1.
FIG. 15 is a TEM image of AuPt/C prepared in comparative example 2.
FIG. 16 is a particle diameter distribution histogram of AuPt/C prepared in comparative example 2.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The experimental reagents used in the following examples and comparative examples are commercially available.
Example 1 preparation of AuPt/C Metal alloy nanocluster particles
The first step is as follows: dispersing 16mg of a carrier (Vulcan XC-72 carbon black) in 50mL of deionized water to obtain a suspended aqueous solution of carbon black (wherein the carrier concentration is 0.32mg/mL) and placing the suspended aqueous solution in a three-neck flask with the volume of 100 mL;
the second step is that: preparing sodium citrate aqueous solution and FeSO4·7H2Aqueous O solution, HAuCl4Aqueous solution and H2PtCl6An aqueous solution;
the third step: heating the carbon black suspension aqueous solution prepared in the first step in a three-neck flask to 100 ℃ in a magnetic stirring heating sleeve, and then sequentially adding the carbon black suspension aqueous solution to the three-neck flaskAdding the aqueous solution of sodium citrate (2mL, concentration 2 wt%) prepared in the second step and FeSO into the suspension aqueous solution4·7H2O aqueous solution (2mL, concentration 0.1mM), HAuCl4Aqueous solution (350. mu.L, 10mg/mL) and H2PtCl6Aqueous solution (420. mu.L, concentration 10mg/mL) to give a mixed aqueous solution (wherein the molar concentration of the sodium citrate solution is 8mM, FeSO)4·7H2The molar concentration of O is 3mM and HAuCl4The molarity of the solution is 0.4mM, H2PtCl6Is 0.6mM, and the molar concentration of Vulcan XC-72 carbon black is 5.3mM, i.e., the molar ratio of the reducing precursor, the metal precursor, and the support is 11: 1: 5.3), preserving the temperature of the mixed aqueous solution at 100 ℃, mixing and reacting for 30min to obtain a suspension;
the fourth step: and freeze-drying the obtained suspension to obtain the required AuPt/C metal alloy nano-cluster particles.
EXAMPLE 2 preparation of NiPt/C Metal alloy nanocluster particles
The first step is as follows: dispersing 20mg of a carrier (Vulcan XC-72 carbon black) in 80mL of deionized water to obtain a suspended aqueous solution of the carbon black (wherein the concentration of the carrier is 0.25mg/mL) and placing the suspended aqueous solution in a three-neck flask with the volume of 150 mL;
the second step is that: preparing sodium citrate aqueous solution and FeSO4·7H2Aqueous O solution, HAuCl4An aqueous solution;
the third step: heating the carbon black suspension water solution in the three-neck flask in the first step to 80 ℃ in a magnetic stirring heating sleeve, and sequentially adding the sodium citrate water solution (4mL, the concentration of 4 wt%) and FeSO prepared in the second step into the suspension water solution4·7H2O aqueous solution (4mL, concentration 0.4mM), HAuCl4Aqueous solution (1.9mL, 10mg/mL concentration) and NiCl2·H2O (3.2mg) to obtain a mixed aqueous solution (wherein, the molar concentration of the sodium citrate solution is 8mM, FeSO)4·7H2The molar concentration of O is 6mM and HAuCl4The molar concentration is 0.7mM and NiCl2·H2The molar concentration of O was 0.4mM and that of Vulcan XC-72 carbon black was 4.2mM, i.e., the moles of the reducing precursor, the metal precursor and the supportThe molar ratio is 14: 1.1: 4.2) preserving the temperature of the mixed aqueous solution at 80 ℃, mixing and reacting for 60min to obtain suspension;
the fourth step: and freeze-drying the obtained suspension to obtain the NiPt/C metal alloy nano-cluster particles.
Example 3 preparation of CoPt/C Metal alloy nanocluster particles
The first step is as follows: 28mg of a carrier (Vulcan XC-72 carbon black) was dispersed in 120mL of deionized water to obtain a suspended aqueous solution of carbon black (wherein, the carrier concentration was 0.23mg/mL) and placed in a three-necked flask having a volume of 200 mL;
the second step is that: preparing sodium citrate aqueous solution and FeSO4·7H2O aqueous solution, H2PtCl6An aqueous solution;
the third step: heating the carbon black suspension aqueous solution in the three-neck flask prepared in the first step to 90 ℃ in a magnetic stirring heating sleeve, and sequentially adding the sodium citrate aqueous solution (6mL, the concentration of 8 wt%) prepared in the second step and FeSO into the suspension aqueous solution4·7H2O aqueous solution (6mL, concentration 0.8mM), H2PtCl6Aqueous solution (4.89mL, concentration 10mg/mL) and CoCl2·6H2O (9.8mg) to give a mixed aqueous solution (sodium citrate solution of 12mM in molar concentration, FeSO)4·7H2The molar concentration of O is 24mM, H2PtCl6The molar concentration is 1.2mM, CoCl2·6H2The molar concentration of O was 0.8mM, the molar concentration of Vulcan XC-72 carbon black was 3.8mM, i.e., the molar ratio of reducing precursor, metal precursor and support was 36: 2: 3.8) preserving the temperature of the mixed aqueous solution at 90 ℃, mixing and reacting for 90min to obtain a suspension;
the fourth step: and freeze-drying the obtained suspension to obtain the required CoPt/C metal alloy nano-cluster particles.
Example 4 preparation of CuPt/C Metal alloy nanocluster particles
The first step is as follows: 40mg of a carrier (Vulcan XC-72 carbon black) was dispersed in 300mL of deionized water to obtain a suspended aqueous solution of carbon black (wherein, the carrier concentration was 0.13mg/mL) and placed in a three-necked flask having a volume of 500 mL;
the second step is that: preparing sodium citrate water solution and FeSO4·7H2O aqueous solution, H2PtCl6An aqueous solution;
the third step: heating the carbon black suspension water solution in the three-neck flask in the first step to 90 ℃ in a magnetic stirring heating jacket, and sequentially adding the sodium citrate water solution (12mL, with the concentration of 10 wt%) and FeSO prepared in the second step into the suspension water solution4·7H2O aqueous solution (12mL, concentration 1mM), H2PtCl6Aqueous solution (16.3mL, 10mg/mL concentration) and CuCl2(24.5mg) to obtain a mixed aqueous solution (wherein, the molar concentration of the sodium citrate solution is 18mM, FeSO)4·7H2The molar concentration of O is 30mM, H2PtCl6The molar concentration is 1.6mM and CuCl21.1mM, and a molar concentration of Vulcan XC-72 carbon black of 2.2mM, i.e., the molar ratio of reducing precursor, metal precursor and support is 48: 2.7: 2.2) preserving the temperature of the mixed aqueous solution at 90 ℃, mixing and reacting for 90min to obtain a suspension;
the fourth step: and (4) freeze-drying the obtained suspension to obtain the required CuPt/C metal alloy nano-cluster particles.
EXAMPLE 5 preparation of CoPt/C Metal alloy nanocluster particles (ferrocene substituted for ferrous sulfate)
The first step is as follows: 28mg of a carrier (Vulcan XC-72 carbon black) was dispersed in 120mL of deionized water to obtain a suspended aqueous solution of carbon black (wherein, the carrier concentration was 0.23mg/mL) and placed in a three-necked flask having a volume of 200 mL;
the second step is that: preparing sodium citrate aqueous solution, ferrocene aqueous solution and H2PtCl6An aqueous solution;
the third step: heating the carbon black suspension aqueous solution in the three-neck flask prepared in the first step to 90 ℃ in a magnetic stirring heating sleeve, and then sequentially adding the sodium citrate aqueous solution (6mL, the concentration of 8 wt%), the ferrocene aqueous solution (6mL, the concentration of 0.8mM) and the H prepared in the second step into the suspension aqueous solution2PtCl6Aqueous solution (4.89mL, 10mg/mL concentration) and CoCl2·6H2O(98mg) to obtain a mixed aqueous solution (wherein, the molar concentration of the sodium citrate solution is 12mM, FeSO)4·7H2The molar concentration of O is 24mM, H2PtCl6The molar concentration is 1.2mM, CoCl2·6H2The molar concentration of O was 0.8mM, the molar concentration of Vulcan XC-72 carbon black was 3.8mM, i.e., the molar ratio of reducing precursor, metal precursor and support was 36: 2: 3.8), preserving the temperature of the mixed aqueous solution at 90 ℃, mixing and reacting for 90min to obtain a suspension;
the fourth step: and freeze-drying the obtained suspension to obtain the required CoPt/C metal alloy nano-cluster particles.
Example 6 preparation of CoPt/C Metal alloy nanocluster particles (ferrous phosphate instead of ferrous sulfate)
The first step is as follows: 28mg of a carrier (Vulcan XC-72 carbon black) was dispersed in 120mL of deionized water to obtain a suspended aqueous solution of carbon black (wherein, the carrier concentration was 0.23mg/mL) and placed in a three-necked flask having a volume of 200 mL;
the second step is that: preparing sodium citrate aqueous solution, ferrous phosphate aqueous solution and H2PtCl6An aqueous solution;
the third step: heating the carbon black suspension aqueous solution in the three-neck flask prepared in the first step to 90 ℃ in a magnetic stirring heating sleeve, and sequentially adding the sodium citrate aqueous solution (6mL, the concentration of 8 wt%), the ferrous phosphate aqueous solution (6mL, the concentration of 0.8mM) and H prepared in the second step into the suspension aqueous solution2PtCl6Aqueous solution (4.89mL, 10mg/mL concentration) and CoCl2·6H2O (9.8mg) to give a mixed aqueous solution (sodium citrate solution of 12mM in molar concentration, FeSO)4·7H2The molar concentration of O is 24mM, H2PtCl6The molar concentration is 1.2mM, CoCl2·6H2The molar concentration of O was 0.8mM, the molar concentration of Vulcan XC-72 carbon black was 3.8mM, i.e., the molar ratio of reducing precursor, metal precursor and support was 36: 2: 3.8), preserving the temperature of the mixed aqueous solution at 90 ℃, mixing and reacting for 90min to obtain a suspension;
the fourth step: and freeze-drying the obtained suspension to obtain the required CoPt/C metal alloy nano-cluster particles.
COMPARATIVE EXAMPLE 1 preparation of AuPt/C Metal alloy nanocluster particles (ferrous sulfate is not added during preparation)
The first step is as follows: dispersing 16mg of a carrier (Vulcan XC-72 carbon black) in 50mL of deionized water to obtain a suspended aqueous solution of carbon black (wherein the carrier concentration is 0.32mg/mL) and placing the suspended aqueous solution in a three-neck flask with the volume of 100 mL;
the second step is that: preparing sodium citrate aqueous solution and HAuCl4Aqueous solution and H2PtCl6An aqueous solution;
the third step: heating the carbon black suspension water solution in the three-neck flask in the first step to 100 ℃ in a magnetic stirring heating sleeve, and sequentially adding the sodium citrate water solution (2mL, the concentration of 2 wt%) and HAuCl in the second step into the suspension water solution4Aqueous solution (350. mu.L, concentration 10mg/mL) and H2PtCl6Aqueous solution (420. mu.L, concentration 10mg/mL) to give a mixed aqueous solution (wherein, the molar concentration of the sodium citrate solution is 8mM, HAuCl4The molarity of the solution is 0.4mM, H2PtCl6Is 0.6mM, and the molar concentration of Vulcan XC-72 carbon black is 5.3mM, i.e., the molar ratio of the reducing precursor, the metal precursor, and the support is 8: 1: 5.3), preserving the temperature of the mixed aqueous solution at 100 ℃, mixing and reacting for 30min to obtain a suspension;
the fourth step: and freeze-drying the obtained suspension to obtain the required AuPt/C metal alloy nano-cluster particles.
COMPARATIVE EXAMPLE 2 preparation of AuPt/C Metal alloy nanocluster particles (sodium citrate is not added during preparation)
The first step is as follows: dispersing 16mg of a carrier (Vulcan XC-72 carbon black) in 50mL of deionized water to obtain a suspension aqueous solution of the carbon black (wherein the carrier concentration is 0.32mg/mL) and placing the suspension aqueous solution in a three-necked flask with a volume of 100 mL;
the second step is that: FeSO4·7H2Aqueous O solution, HAuCl4Aqueous solution and H2PtCl6An aqueous solution;
the third step: placing the carbon black suspension water solution prepared in the first step in a three-neck flask in a magnetic forceHeating to 100 deg.C with stirring heating jacket, and sequentially adding FeSO prepared in the second step into the above suspension water solution4·7H2O aqueous solution (2mL, concentration 0.1mM), HAuCl4Aqueous solution (350. mu.L, 10mg/mL) and H2PtCl6Aqueous solution (420. mu.L, concentration 10mg/mL) to obtain mixed aqueous solution (wherein, FeSO4·7H2The molar concentration of O is 3mM and HAuCl4The molarity of the solution is 0.4mM, H2PtCl6Is 0.6mM, and the molar concentration of Vulcan XC-72 carbon black is 5.3mM, i.e., the molar ratio of the reducing precursor, the metal precursor, and the support is 3: 1: 5.3), preserving the temperature of the mixed aqueous solution at 100 ℃, mixing and reacting for 30min to obtain a suspension;
the fourth step: and freeze-drying the obtained suspension to obtain the required AuPt/C metal alloy nano-cluster particles.
Comparative example 3
The reaction conditions were the same as in example 1 except that the magnetic stirring heating mantle was heated to 60 ℃ in the third step.
In comparative example 3, it can be observed that the color of the mixed reaction solution in comparative example 3 is colorless and transparent from the viewpoint of no change in the solution color, while the color of the mixed reaction solution in examples 1 to 6 changes to gray black within 10s to 2min after the start of the reaction, and thus it can be seen that the transition metal precursor cannot be reduced and the AuPt/C metal alloy nanocluster particles cannot be prepared in the reaction system at a reaction temperature of 60 ℃.
Effect example 1
Test samples: the metal alloy nanocluster particles prepared in examples 1 to 6 and comparative examples 1 to 2.
Test equipment and conditions:
transmission electron microscope: model JEOL-2100, test voltage 200 kV.
The determination of the particle diameter distribution histogram is a routine determination in the art.
And (3) testing results:
fig. 1, 3, 5, 7,9 and 11 are transmission electron micrographs of the metal alloy nanocluster particles prepared in examples 1 to 6, respectively, and fig. 13 and 15 are transmission electron micrographs of the metal alloy nanocluster particles prepared in comparative examples 1 to 2, respectively. Fig. 2, 4, 6,8, 10 and 12 are distribution histograms of particle diameters of the metal alloy nanocluster particles prepared in examples 1 to 6, respectively, and fig. 14 and 16 are distribution histograms of particle diameters of the metal alloy nanocluster particles prepared in comparative examples 1 to 2, respectively. The sizes of the metal alloy nanocluster particles prepared in examples 1 to 6 and comparative examples 1 to 2 are shown in table 1 below.
As can be seen from fig. 1 to 12 and table 1, the metal alloy nanocluster particles prepared in examples 1 to 6 of the present invention are small in size and uniformly dispersed; as can be seen from fig. 13 to 16 and table 1, the metal alloy nanoclusters prepared in comparative examples 1 to 2 have large particle size and are not uniformly dispersed.
TABLE 1
Figure BDA0003453708350000131
Effect example 2
Test samples: the metal alloy nanocluster particles prepared in examples 1 to 6 and comparative examples 1 to 2.
Test equipment and conditions:
transmission electron microscopy: inductively coupled plasma atomic emission spectrometry (ICP-OES)
And (3) testing results:
analyzing elements (such as Cl and Na) possibly remaining in the preparation process of the alloy nano-cluster particles by adopting inductively coupled plasma atomic emission spectrometry (ICP-OES), wherein the relative contents of other elements except the alloy are basically not detected and are all lower than 0.001%, and the metal alloy nano-cluster particles prepared by the method are pure and free of impurities.

Claims (10)

1. A method for preparing metal alloy nanocluster particles is characterized by comprising the following steps:
mixing and reacting a mixed aqueous solution containing a reducing precursor, a metal precursor and a carrier;
the reducing precursor comprises citrate and ferrous salts;
the molar ratio of the citrate to the ferrous salt is 12: 30-8: 1;
the temperature of the mixing reaction is at least 80 ℃.
2. The method of preparing metal alloy nanocluster particles of claim 1,
the molar ratio of the reducing precursor to the metal precursor to the support is 4-60: 0.5-3: 1 to 6, preferably 10 to 50: 0.7-2.8: 2 to 5.5, preferably 11 to 48: 0.7-2.8: 2 to 5.5, for example, 11: 1: 5.3, 14: 1.1: 4.2, 36: 2: 3.8 or 48: 2.7: 2.2.
3. the method of preparing metal alloy nanocluster particles as claimed in claim 1, wherein said citrate is one or more of sodium citrate, ammonium citrate and potassium citrate, preferably sodium citrate;
and/or the ferrous salt is one or more of ferrous sulfate, ferrous phosphate and ferrocene, and is preferably ferrous sulfate.
4. The method of claim 1, wherein the molar ratio of the citrate salt to the ferrous salt is 12:25 to 8:3, preferably 12:24 to 8:3, such as 8:6, 8:10, 8:13, 18:30, or 8: 15.
5. The method of claim 1, wherein the concentration of the reducing precursor in the mixed aqueous solution is 4-60 mM, preferably 10-50 mM, more preferably 11-48 mM, such as 14mM or 36 mM;
and/or, the concentration of the metal precursor in the mixed aqueous solution is 0.5-3 mM, preferably 0.7-2.8 mM, such as 1mM, 1.1mM, 2mM or 2.7 mM.
6. The method of preparing metal alloy nanocluster particles of claim 1, wherein the metal precursor is a noble metal precursor and/or a transition metal precursor.
7. The method for preparing metal alloy nanocluster particles as claimed in claim 6, wherein the noble metal precursor is a noble metal-containing salt, such as a noble metal-containing halate;
the halide salt containing a noble metal is preferably a chlorate salt containing a noble metal, more preferably chloroplatinic acid and/or chloroauric acid;
and/or, the transition metal precursor is a transition metal-containing salt, such as a transition metal-containing halide salt;
the halide salt containing a transition metal is preferably a chloride salt containing a transition metal, more preferably one or more of nickel chloride, cobalt chloride and copper chloride, such as nickel chloride, cobalt chloride or copper chloride;
when the metal precursor is a mixture of the noble metal precursor and the transition metal precursor, the molar ratio of the noble metal precursor to the transition metal precursor is 0.5: 1-3: 1, preferably 0.5: 0.5-2: 1, such as 0.7:0.4, 1.2:0.8 or 1.6: 1.1.
8. The method for preparing metal alloy nanocluster particles of claim 6, wherein the concentration of the noble metal precursor in the mixed aqueous solution is 0.1 to 2mM, preferably 0.2 to 1.2mM, such as 0.4mM, 0.6mM, 1.2mM, 1.6mM or 0.7 mM;
when the noble metal precursor comprises chloroplatinic acid, the concentration of the chloroplatinic acid in the mixed aqueous solution is 0.1-2 mM, preferably 0.2-1.2 mM, such as 0.6mM, 1.2mM or 1.6 mM;
when the noble metal precursor comprises chloroauric acid, the concentration of the chloroauric acid in the mixed aqueous solution is 0.1-2 mM, preferably 0.2-1.2 mM, such as 0.4mM or 0.7 mM;
when the noble metal precursor is a mixture of the chloroauric acid and the chloroplatinic acid, the molar ratio of the chloroauric acid to the chloroplatinic acid is 0.1: 0.4-0.5: 0.25, preferably 0.4: 0.6.
9. The method of preparing metal alloy nanocluster particles of claim 6,
the concentration of the transition metal precursor in the mixed aqueous solution is 0.1-2 mM, preferably 0.2-1.2 mM, such as 0.4mM, 0.8mM or 1.1 mM;
when the transition metal precursor is nickel chloride, the concentration of the nickel chloride in the mixed aqueous solution is 0.1-2 mM, preferably 0.2-1.2 mM, such as 0.4 mM;
when the transition metal precursor is cobalt chloride, the concentration of the cobalt chloride in the mixed aqueous solution is 0.1-2 mM, preferably 0.2-1.2 mM, such as 0.8 mM;
when the transition metal precursor is copper chloride, the concentration of the copper chloride in the mixed aqueous solution is 0.1-2 mM, preferably 0.2-1.2 mM, such as 1.1 mM.
10. The method of preparing metal alloy nanocluster particles as claimed in claim 1, wherein said carrier is a carbon carrier, preferably carbon black;
and/or, in the mixed aqueous solution, the concentration of the carrier is 1 to 6mM, preferably 2 to 5.5mM, such as 2.2mM, 3.8mM, 4.2mM or 5.3 mM;
and/or, the method for preparing the mixed aqueous solution preferably comprises the steps of: sequentially adding a solution containing the reducing precursor and a solution containing the metal precursor into the solution containing the carrier, and uniformly mixing;
and/or, in the preparation method of the metal alloy nano-cluster particles, no organic solvent is adopted,
wherein the organic solvent is oleylamine, oleic acid, N-dimethylformamide, toluene or chloroform;
and/or the temperature of the mixing reaction is 80-100 ℃, such as 90 ℃;
and/or the mixing reaction time is 20-200 min, preferably 30-120 min, such as 60min or 90 min;
and/or, a drying treatment step is also included after the mixing reaction;
wherein the drying treatment step is freeze-drying, centrifugal drying or rotary evaporation drying.
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