CN113560594B - Synthesis method for synthesizing intermetallic palladium copper nanocrystalline in one step and application thereof - Google Patents
Synthesis method for synthesizing intermetallic palladium copper nanocrystalline in one step and application thereof Download PDFInfo
- Publication number
- CN113560594B CN113560594B CN202110840957.7A CN202110840957A CN113560594B CN 113560594 B CN113560594 B CN 113560594B CN 202110840957 A CN202110840957 A CN 202110840957A CN 113560594 B CN113560594 B CN 113560594B
- Authority
- CN
- China
- Prior art keywords
- palladium
- copper
- reaction
- mixed solution
- oleylamine
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- 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
-
- 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
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8926—Copper and noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Composite Materials (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a synthesis method and application of one-step synthesis intermetallic palladium copper nanocrystalline, which comprises the steps of weighing a palladium precursor, copper acetylacetonate and potassium bromide according to a proportion; dispersing a palladium precursor, copper acetylacetonate and potassium bromide in a first mixed solution according to a certain proportion to obtain a second mixed solution with a certain concentration; heating and stirring the second mixed solution, and obtaining a reaction product after the reaction is completed; centrifuging and washing the reaction product to obtain intermetallic palladium copper nanocrystalline with an ordered structure; the method can obtain the corresponding product by mixing all the raw materials in one step for reaction, has the advantages of simple steps, short period, high yield, good repeatability, reduced energy consumption and production cost, is very suitable for industrialized mass production and application, and meanwhile, the average particle size of the palladium-copper nanocrystalline product is only 6.8 nanometers, the particles are smaller, and the atomic utilization rate and the catalytic activity can be effectively increased.
Description
Technical Field
The invention belongs to the technical field of nano science, and relates to a synthesis method and application of one-step synthesis of intermetallic palladium copper nanocrystalline.
Background
In recent years, platinum-based nanocatalysts have been widely used in the field of electrocatalysis due to their excellent catalytic activity and stability. However, the expensive price and scarce reserves of platinum severely limit its further mass production and practical use. Thus, reducing the amount of platinum used or finding other non-platinum materials can effectively solve this problem.
Since palladium and platinum have similar electronic structures and palladium is cheaper than platinum, the structural regulation and development of palladium-based nanocatalysts is becoming a focus of attention of scientists. However, in electrocatalytic reactions, palladium-based catalysts generally exhibit lower catalytic activity, mainly because the d-band center energy of palladium is higher, resulting in too strong adsorption of small molecule functional groups, which makes it difficult to desorb the small molecule functional groups. However, by regulating the crystal structure and composition of the palladium-based catalyst, the electronic structure of palladium atoms can be optimized, and the catalytic activity and stability of the palladium-based catalyst in electrocatalysis can be effectively improved.
For bimetallic palladium-based nanoalloys, there are typically two crystalline structures. One is a free disordered face centered cubic alloy structure. The other is an ordered intermetallic body-centered cubic alloy structure. Ordered intermetallic palladium-based alloys generally exhibit stronger electron interactions, larger bond lengths and changes in electron configuration than disordered face-centered cubic palladium-based alloys, which can all significantly increase their catalytic activity on small organic molecules. For example, in 2014, the kotarososaki and radosleavr.adzic problem group promoted the ordered transformation of palladium cobalt alloys by Au atoms. Such ordered intermetallic PdCo alloys exhibit catalytic activity and stability similar to platinum in electrocatalytic reactions. In 2016, the Huang Xiaoqing and Guo Shaojun subject groups synthesized ordered intermetallic palladium-based alloy nanocatalysts by a novel colloid chemistry. The ordered transformation of the crystal structure effectively enhances the electrocatalytic activity and stability. Ordered intermetallic palladium-based alloy nanocatalysts exhibit 1.3 times and 3.3 times enhanced mass activity in oxygen reduction reactions as compared to conventional commercial platinum-carbon and palladium-carbon catalysts. While exhibiting 12.9-fold and 17.5-fold enhancement of mass activity in Ethanol Oxidation (EOR). In 2018, takaoGunj and FutoshiMatsumoto subject groups prepared intermetallic PdCu of ordered structure by co-reduction method 3 Alloy nano catalyst. Showing a significant enhancement of electrocatalytic activity compared to the disordered palladium-copper alloy. The above researches all show that the catalyst activity and stability are greatly improved when the palladium-based alloy is converted from disordered free alloy to ordered intermetallic alloy structureThe improvement opens up a new direction for improving the electrocatalytic performance of the palladium-based alloy through structural optimization.
However, in these studies in the past, the ordering transition of palladium-based alloys is almost always dependent on the subsequent heat treatment process. However, in the high-temperature heat treatment process (the common treatment temperature is 250 ℃ to 800 ℃), the problems of Ostwald ripening and particle agglomeration growth of the nano-catalyst occur, so that the dispersibility and the original surface structure of the synthesized nano-catalyst are seriously damaged, and the due catalytic activity and stability of the catalyst are finally reduced.
Disclosure of Invention
The invention aims to provide a synthesis method and application of intermetallic palladium-copper nanocrystalline, which omits a high-temperature heat treatment process required by preparing intermetallic alloy, improves the catalytic activity of a product, and has the advantages of simple steps, short period, high yield and good repeatability.
The invention adopts the following technical scheme: a method for synthesizing intermetallic palladium-copper nanocrystalline by one step comprises the following steps:
weighing palladium precursor, copper acetylacetonate and potassium bromide according to a proportion;
dispersing a palladium precursor, copper acetylacetonate and potassium bromide in the first mixed solution to obtain a second mixed solution; wherein the first mixed solution is a mixed solution of ethylene glycol and oleylamine;
heating and stirring the second mixed solution until the reaction is completed to obtain a reaction product;
centrifuging and washing the reaction product to obtain palladium-copper nanocrystalline; wherein, palladium copper nanocrystalline is ordered intermetallic alloy structure.
Further, the volume ratio of ethylene glycol to oleylamine in the first mixed solution is 1: (5-10).
Further, the palladium precursor is sodium chloropalladate or palladium chloride.
Further, the ratio of the amounts of the substances among the palladium precursor, copper acetylacetonate and potassium bromide is (1 to 3): (1-3): (1-5);
the concentration of the palladium precursor in the second solution is 1.67-5.00 mg/mL, the concentration of the copper acetylacetonate is 1.67-5.00 mg/mL, and the concentration of the potassium bromide is 1.67-8.33 mg/mL.
Further, the method comprises the following steps:
1) Dispersing 10mg of sodium chloropalladate, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine to obtain a reaction solution; wherein, the volume ratio of the ethylene glycol to the oleylamine is 1:5;
2) Heating the reaction solution to 140 ℃ while stirring, and reacting for 180 minutes at a heating rate of 6 ℃/min;
and after the reaction is finished, obtaining palladium-copper nanocrystalline through centrifugation and washing.
Further, the method comprises the following steps:
1) Dispersing 10mg of palladium chloride, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine to obtain a reaction solution; wherein, the volume ratio of the ethylene glycol to the oleylamine is 1:5;
2) Heating the reaction solution to 140 ℃ while stirring, and reacting for 180 minutes at a heating rate of 6 ℃/min;
and after the reaction is finished, obtaining palladium-copper nanocrystalline through centrifugation and washing.
Further, the method comprises the following steps:
1) Dispersing 10mg of sodium chloropalladate, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine to obtain a reaction solution; wherein, the volume ratio of the ethylene glycol to the oleylamine is 1:8;
2) Heating the reaction solution to 140 ℃ while stirring, and reacting for 180 minutes at a heating rate of 6 ℃/min;
and after the reaction is finished, obtaining palladium-copper nanocrystalline through centrifugation and washing.
Further, the method comprises the following steps:
1) Dispersing 10mg of sodium chloropalladate, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine to obtain a reaction solution; wherein, the volume ratio of the ethylene glycol to the oleylamine is 1:10;
2) Heating the reaction solution to 140 ℃ while stirring, and reacting for 180 minutes at a heating rate of 6 ℃/min;
and after the reaction is finished, obtaining palladium-copper nanocrystalline through centrifugation and washing.
Another technical scheme of the invention is as follows: the use of one-step synthesis of intermetallic palladium copper nanocrystals as catalysts in the oxidation electrocatalytic reaction of formic acid.
The beneficial effects of the invention are as follows: according to the method, the palladium precursor, the copper acetylacetonate and the potassium bromide are directly dispersed into the first mixed solution, and the dispersed mixed solution is stirred and heated, so that the intermetallic palladium copper nanocrystalline with an ordered structure can be directly obtained.
Drawings
FIG. 1 is a bright field image transmission electron microscope image of the product of example 1 of the present invention;
FIG. 2 is a transmission electron micrograph of the dark field image of the product of example 1 of the present invention;
FIG. 3 is a high resolution transmission electron micrograph of the product of example 1 of the present invention;
FIG. 4 is an X-ray diffraction pattern of the product of example 1 of the present invention;
FIG. 5 is a line scan of individual particles of the product of example 1 of the present invention;
FIG. 6 is a statistical plot of the lateral dimensions of the product of example 1 of the present invention;
FIG. 7 is a bright field image transmission electron microscope image of the product of example 2 of the present invention;
FIG. 8 is a bright field image transmission electron microscope image of the product of example 3 of the present invention;
FIG. 9 is a bright field image transmission electron microscope image of the product of example 4 of the present invention;
FIG. 10 is a cyclic voltammogram of palladium copper nanocrystals, disordered palladium copper nanocrystals, commercial palladium on carbon, and commercial palladium black having an ordered intermetallic structure in an application example of the present invention;
FIG. 11 is a graph of quality normalized formic acid oxidation curves for palladium copper nanocrystals, disordered palladium copper nanocrystals, commercial palladium on carbon, and commercial palladium black having an ordered intermetallic structure in an application example of the present invention;
FIG. 12 is a graph of normalized area formic acid oxidation for palladium copper nanocrystals, disordered palladium copper nanocrystals, commercial palladium on carbon, and commercial palladium black having an ordered intermetallic structure in an application example of the present invention;
FIG. 13 is a mass activity histogram of palladium copper nanocrystals, disordered palladium copper nanocrystals, commercial palladium carbon, and commercial palladium black having an ordered intermetallic structure in an application example of the present invention;
FIG. 14 is an area activity histogram of palladium copper nanocrystals, disordered palladium copper nanocrystals, commercial palladium carbon, and commercial palladium black having an ordered intermetallic structure in an application example of the present invention.
Detailed Description
The invention will be described in detail below with reference to the drawings and the detailed description.
The ordered transformation of palladium-based alloys is almost dependent on the subsequent heat treatment process, which undoubtedly increases energy consumption, production costs and operational difficulties. Thus, the high temperature heat treatment process severely hampers the practical production and use of such ordered intermetallic palladium-based alloys, both from a process step point of view and from an economic cost point of view.
Therefore, if the palladium-copper nano alloy catalyst with an ordered intermetallic structure can be obtained in one step in liquid phase reduction, the original structure and catalytic activity of the palladium-copper nano catalyst can be maintained to the greatest extent, experimental steps can be greatly simplified, and energy consumption and production cost are reduced. The method brings new prospect for controllable synthesis and practical application of the ordered intermetallic palladium-copper nano alloy catalyst.
Specifically, the invention discloses a method for synthesizing intermetallic palladium copper nanocrystalline in one step, which comprises the following steps:
weighing palladium precursor, copper acetylacetonate and potassium bromide according to a proportion; dispersing a palladium precursor, copper acetylacetonate and potassium bromide in the first mixed solution to obtain a second mixed solution; wherein the first mixed solution is a mixed solution of ethylene glycol and oleylamine; the second mixed solution is heated and stirred until the reaction is completed to obtain a reaction product. In the invention, the mixed solution is light green, and the product formed after the reaction is black, so that after the color of the second mixed solution is completely changed from light green to black, the completion of the reaction can be judged. Centrifuging and washing the reaction product to obtain palladium-copper nanocrystalline; wherein, palladium copper nanocrystalline is ordered intermetallic alloy structure.
The preparation of the ordered intermetallic palladium-copper nano alloy completely eliminates the conventional process of requiring a second step of high-temperature heat treatment (250-800 ℃), and the ordered intermetallic palladium-copper nano alloy structure is synthesized by one step of control through novel system parameters of regulating and controlling reaction solution, so that the synthesis method has development and creativity.
Specifically, the volume ratio of ethylene glycol to oleylamine in the first mixed solution is 1: (5-10). As a specific implementation form, the palladium precursor is sodium chloropalladate or palladium chloride. The ratio of the amounts of the palladium precursor, copper acetylacetonate and potassium bromide was (1 to 3): (1-3): (1-5), wherein the concentration of the palladium precursor is 1.67-5.00 mg/mL, the concentration of the copper acetylacetonate is 1.67-5.00 mg/mL, and the concentration of the potassium bromide is 1.67-8.33 mg/mL.
Example 1:
the method of this embodiment comprises the steps of:
1) Dispersing 10mg of sodium chloropalladate, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine (the volume ratio of the ethylene glycol to the oleylamine is 1:5) to obtain a reaction solution;
2) And heating the reaction solution to 140 ℃ while stirring, reacting for 180 minutes (the heating rate is 6 ℃ per minute), and centrifuging and washing after the reaction is finished to obtain the palladium-copper nano alloy with the intermetallic structure. In the above reaction, the reaction time does not include the temperature rise time.
As shown in FIG. 1, which is a bright field image transmission electron micrograph of the product of this example, it can be seen that the resulting product has a good morphology of particles. This example is the preferred embodiment of the present application, and the resulting product is characterized in detail as a catalyst as follows:
as shown in fig. 1 and fig. 2, the palladium-copper nanocrystalline with intermetallic structure is characterized by a transmission electron microscope of bright field image and dark field image, and the palladium-copper nanocrystalline can be clearly seen in both the figures to have good particle morphology. As shown in fig. 3, which is a high resolution transmission electron microscope image of the product, the interplanar spacing of the (100) crystal plane and the (110) crystal plane of the intermetallic palladium copper nanocrystalline is 0.29 nm and 0.21 nm, respectively, which proves that the structure of the palladium copper nanocrystalline is an ordered structure. As shown in FIG. 4, the X-ray diffraction pattern of the product further shows that the palladium-copper nanocrystalline has an ordered intermetallic structure, and the standard card number corresponding to the ordered intermetallic structure is ICDD,01-078-4406. As shown in fig. 5, a line scan of individual particles in the product is shown, through which both elements palladium and copper are uniformly distributed throughout the particles. As shown in fig. 6, which is a statistical plot of the lateral dimensions of the product of this example, it can be seen that obtaining a lateral average dimension of about 6.8 nanometers effectively increases atomic utilization compared to larger particle sizes.
Example 2:
the embodiment method comprises the following steps:
1) Dispersing 10mg of sodium chloropalladate, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine (volume ratio is 1:5) to obtain a reaction solution;
2) And heating the reaction solution to 120 ℃ while stirring, reacting for 360 minutes (the heating rate is 6 ℃ per minute), and centrifuging and washing after the reaction is finished to obtain the palladium-copper nano alloy with the intermetallic structure.
As shown in fig. 7, a bright field image transmission electron microscope image corresponding to the product of this example shows that the product has good particle morphology.
Example 3:
the embodiment method comprises the following steps:
1) Dispersing 10mg of sodium chloropalladate, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine (volume ratio is 1:5) to obtain a reaction solution;
2) And heating the reaction solution to 100 ℃ while stirring, reacting for 600 minutes (the heating rate is 6 ℃ per minute), and centrifuging and washing after the reaction is finished to obtain the palladium-copper nano alloy with the intermetallic structure.
As shown in fig. 8, a bright field image transmission electron microscope image corresponding to the product of this example shows that the product has good particle morphology.
Example 4:
the method comprises the following steps:
1) Dispersing 10mg of palladium chloride, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine (volume ratio is 1:5) to obtain a reaction solution;
2) And heating the reaction solution to 140 ℃ while stirring, reacting for 180 minutes (the heating rate is 6 ℃ per minute), and centrifuging and washing after the reaction is finished to obtain the palladium-copper nano alloy with the intermetallic structure.
As shown in fig. 9, a bright field image transmission electron microscope image corresponding to the product of this example shows that the product has good particle morphology.
Example 5:
the method of this embodiment comprises the steps of:
1) Dispersing 10mg of sodium chloropalladate, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine (the volume ratio of the ethylene glycol to the oleylamine is 1:8) to obtain a reaction solution;
2) And heating the reaction solution to 140 ℃ while stirring, reacting for 180 minutes (the heating rate is 6 ℃ per minute), and centrifuging and washing after the reaction is finished to obtain the palladium-copper nano alloy with the intermetallic structure.
Example 6:
the method of this embodiment comprises the steps of:
1) Dispersing 10mg of sodium chloropalladate, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine (the volume ratio of the ethylene glycol to the oleylamine is 1:10) to obtain a reaction solution;
2) And heating the reaction solution to 140 ℃ while stirring, reacting for 180 minutes (the heating rate is 6 ℃ per minute), and centrifuging and washing after the reaction is finished to obtain the palladium-copper nano alloy with the intermetallic structure.
Example 7:
the method of this embodiment comprises the steps of:
1) Dispersing 30mg of sodium chloropalladate, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine (the volume ratio of the ethylene glycol to the oleylamine is 1:5) to obtain a reaction solution;
2) And heating the reaction solution to 140 ℃ while stirring, reacting for 180 minutes (the heating rate is 6 ℃ per minute), and centrifuging and washing after the reaction is finished to obtain the palladium-copper nano alloy with the intermetallic structure.
Example 8:
the method of this embodiment comprises the steps of:
1) Dispersing 10mg of sodium chloropalladate, 30mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine (the volume ratio of the ethylene glycol to the oleylamine is 1:5) to obtain a reaction solution;
2) And heating the reaction solution to 140 ℃ while stirring, reacting for 180 minutes (the heating rate is 6 ℃ per minute), and centrifuging and washing after the reaction is finished to obtain the palladium-copper nano alloy with the intermetallic structure.
Example 9:
the method of this embodiment comprises the steps of:
1) Dispersing 30mg of sodium chloropalladate, 10mg of copper acetylacetonate and 10mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine (the volume ratio of the ethylene glycol to the oleylamine is 1:5) to obtain a reaction solution;
2) And heating the reaction solution to 140 ℃ while stirring, reacting for 180 minutes (the heating rate is 6 ℃ per minute), and centrifuging and washing after the reaction is finished to obtain the palladium-copper nano alloy with the intermetallic structure.
Example 10:
the method of this embodiment comprises the steps of:
1) 30mg of sodium chloropalladate, 10mg of copper acetylacetonate and 50mg of potassium bromide are dispersed in 6mL of mixed solution of ethylene glycol and oleylamine (the volume ratio of the ethylene glycol to the oleylamine is 1:5), so as to obtain a reaction solution;
2) And heating the reaction solution to 140 ℃ while stirring, reacting for 180 minutes (the heating rate is 6 ℃ per minute), and centrifuging and washing after the reaction is finished to obtain the palladium-copper nano alloy with the intermetallic structure.
In addition, the invention also discloses application of the intermetallic palladium-copper nanocrystalline, and the intermetallic palladium-copper nanocrystalline is used as a catalyst in formic acid oxidation electrocatalytic reaction. Specific examples are as follows:
dispersing a catalyst (1.2 mg) in 1mL of a mixed solution of water and isopropanol (water: isopropanol=1:1); then adding 20 mu L of Nafion solution into the mixed solution for ultrasonic treatment for 20 minutes; dropping 5. Mu.L of the solution after ultrasonic homogenization on a surface of 0.196cm 2 And (3) carrying out electrochemical test after the sample is dried.
The electrochemical test process is carried out at room temperature, the reference electrode is Ag/AgCl (3 MKCl) electrode, the auxiliary electrode is platinum mesh electrode (1×1 cm) 2 ). With a three-electrode system at 0.5MH 2 SO 4 In the medium, as shown in FIG. 10, the cyclic voltammogram is shown at N 2 The scan rate was 50mV/s and the scan range was 0.05V to 1.2V, tested under an atmosphere. As shown in fig. 11 and 12, the data is at 0.5MH 2 SO 4 And 0.5MHCOOH, at a sweeping rate of 50mV/s.
The test data were converted, as shown in fig. 13 and 14, to activities per unit mass of palladium (fig. 13) and unit area of palladium (fig. 14), respectively, and it was clearly observed that the catalytic activity of the intermetallic palladium copper nanocrystals prepared according to the present invention was superior to the activities of the disordered palladium copper alloy, commercial palladium carbon and palladium black catalysts.
Claims (7)
1. The synthesis method for synthesizing the intermetallic palladium-copper nanocrystalline in one step is characterized by comprising the following steps:
weighing palladium precursor, copper acetylacetonate and potassium bromide according to a proportion;
dispersing the palladium precursor, copper acetylacetonate and potassium bromide in a first mixed solution to obtain a second mixed solution; wherein the first mixed solution is a mixed solution of ethylene glycol and oleylamine;
heating and stirring the second mixed solution until the reaction is completed to obtain a reaction product;
centrifuging and washing the reaction product to obtain palladium-copper nanocrystalline PdCu; wherein the palladium-copper nanocrystalline is of an ordered intermetallic alloy structure;
the volume ratio of the ethylene glycol to the oleylamine in the first mixed solution is 1: (5-10);
the ratio of the amounts of the substances among the palladium precursor, the copper acetylacetonate and the potassium bromide is (1-3): (1-3): (1-5);
the concentration of the palladium precursor in the second solution is 1.67-5.00 mg/mL, the concentration of the copper acetylacetonate is 1.67-5.00 mg/mL, and the concentration of the potassium bromide is 1.67-8.33 mg/mL.
2. The method for synthesizing intermetallic palladium copper nanocrystals in one step as recited in claim 1, wherein the palladium precursor is sodium chloropalladate or palladium chloride.
3. The method for synthesizing intermetallic palladium-copper nanocrystals in one step according to claim 2, comprising the steps of:
1) Dispersing 10mg of sodium chloropalladate, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine to obtain a reaction solution; wherein the volume ratio of the ethylene glycol to the oleylamine is 1:5;
2) Heating the reaction solution to 140 ℃ while stirring, and reacting for 180 minutes at a heating rate of 6 ℃/min;
and after the reaction is finished, obtaining palladium-copper nanocrystalline through centrifugation and washing.
4. The method for synthesizing intermetallic palladium-copper nanocrystals in one step according to claim 2, comprising the steps of:
1) Dispersing 10mg of palladium chloride, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine to obtain a reaction solution; wherein the volume ratio of the ethylene glycol to the oleylamine is 1:5;
2) Heating the reaction solution to 140 ℃ while stirring, and reacting for 180 minutes at a heating rate of 6 ℃/min;
and after the reaction is finished, obtaining palladium-copper nanocrystalline through centrifugation and washing.
5. The method for synthesizing intermetallic palladium-copper nanocrystals in one step according to claim 2, comprising the steps of:
1) Dispersing 10mg of sodium chloropalladate, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine to obtain a reaction solution; wherein the volume ratio of the ethylene glycol to the oleylamine is 1:8;
2) Heating the reaction solution to 140 ℃ while stirring, and reacting for 180 minutes at a heating rate of 6 ℃/min;
and after the reaction is finished, obtaining palladium-copper nanocrystalline through centrifugation and washing.
6. The method for synthesizing intermetallic palladium-copper nanocrystals in one step according to claim 2, comprising the steps of:
1) Dispersing 10mg of sodium chloropalladate, 10mg of copper acetylacetonate and 20mg of potassium bromide in 6mL of a mixed solution of ethylene glycol and oleylamine to obtain a reaction solution; wherein the volume ratio of the ethylene glycol to the oleylamine is 1:10;
2) Heating the reaction solution to 140 ℃ while stirring, and reacting for 180 minutes at a heating rate of 6 ℃/min;
and after the reaction is finished, obtaining palladium-copper nanocrystalline through centrifugation and washing.
7. The application of one-step synthesized intermetallic palladium-copper nanocrystalline as a catalyst is characterized in that the intermetallic palladium-copper nanocrystalline is used as a catalyst in formic acid oxidation electrocatalytic reaction; the intermetallic palladium-copper nanocrystalline is prepared by the synthesis method of any one of claims 1-6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110840957.7A CN113560594B (en) | 2021-07-23 | 2021-07-23 | Synthesis method for synthesizing intermetallic palladium copper nanocrystalline in one step and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202110840957.7A CN113560594B (en) | 2021-07-23 | 2021-07-23 | Synthesis method for synthesizing intermetallic palladium copper nanocrystalline in one step and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN113560594A CN113560594A (en) | 2021-10-29 |
| CN113560594B true CN113560594B (en) | 2023-07-21 |
Family
ID=78167099
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110840957.7A Active CN113560594B (en) | 2021-07-23 | 2021-07-23 | Synthesis method for synthesizing intermetallic palladium copper nanocrystalline in one step and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN113560594B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117102477A (en) * | 2023-08-01 | 2023-11-24 | 淮安中顺环保科技有限公司 | Copper-palladium alloy nano-particle and preparation method and application thereof |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101992302B (en) * | 2009-08-21 | 2012-08-15 | 中国科学院大连化学物理研究所 | Method for preparing high-dispersion precious metal and alloy nanoparticles thereof |
| CN105618784A (en) * | 2016-01-08 | 2016-06-01 | 浙江大学 | Preparation method for dendritic copper-palladium nanocrystalline alloy and product of preparation method |
| CN106180747B (en) * | 2016-07-07 | 2019-01-22 | 王荔 | A kind of palladium copper binary alloy nano material, preparation method and its CO is restored as catalyst electro-catalysis2Application |
| WO2018179005A1 (en) * | 2017-03-25 | 2018-10-04 | Jawaharlal Nehru Centre For Advanced Scientific Research | Shape tailored ordered pdcu3 nanoparticle surpassing the activity of state-of-the-art fuel cell catalyst |
| CN108672717A (en) * | 2018-05-25 | 2018-10-19 | 苏州大学 | The method of one-step synthesis cluster type palladium copper nano-particle and the application of cluster type palladium copper nano-particle |
| CN109088078B (en) * | 2018-06-12 | 2021-11-02 | 三峡大学 | Preparation method of electrochemical de-alloyed PdCu catalyst for fuel cell |
| CN110581281B (en) * | 2019-09-11 | 2021-11-02 | 江南大学 | PdCu alloy nano catalyst applied to fuel cell field and preparation method thereof |
| CN113042069A (en) * | 2021-03-31 | 2021-06-29 | 泉州师范学院 | Synthetic method and application of palladium-copper nano catalyst for formic acid reduction |
-
2021
- 2021-07-23 CN CN202110840957.7A patent/CN113560594B/en active Active
Non-Patent Citations (2)
| Title |
|---|
| Michelle M. 等.Compressed Intermetallic PdCu for Enhanced Electrocatalysis.ACS Energy Letters.2020,第12卷(第5期),3672-3680. * |
| Qiang Gao等.Shape-Controlled Synthesis of Monodisperse PdCu Nanocubes and Their Electrocatalytic Properties.ChemSusChem.2013,第6卷(第10期),1878-1882. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN113560594A (en) | 2021-10-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109014237B (en) | Platinum-non-noble metal alloy nanowire and aqueous phase synthesis method and application thereof | |
| CN105431230B (en) | Method for forming noble metal nanoparticles on a support | |
| CN111224117A (en) | Pt alloy catalyst with nanowire structure and preparation method and application thereof | |
| CN109108303B (en) | Preparation method of high-dispersity Pt-Cu alloy nanoparticles | |
| KR20180129307A (en) | A method for preparing copper electrocatalyst for carbon dioxide reduction | |
| CN112473691A (en) | Preparation method of low-platinum hollow polyhedral nano-structured catalyst | |
| CN110627030A (en) | Platinum phosphide nano-catalyst, preparation method thereof and application thereof in electrocatalytic oxygen reduction | |
| CN113707897A (en) | Anti-reversal catalyst for fuel cell and preparation method thereof | |
| CN113782757A (en) | PtPd alloy nanowire catalyst and preparation method thereof | |
| CN113560594B (en) | Synthesis method for synthesizing intermetallic palladium copper nanocrystalline in one step and application thereof | |
| CN112086648A (en) | Method for synthesizing AuPd @ C material for oxygen reduction reaction electrocatalysis | |
| CN109599570B (en) | Dendritic PdPt nano-particles for electrocatalytic methanol oxidation and preparation method thereof | |
| KR20190035653A (en) | A method for preparing copper electrocatalyst for carbon dioxide reduction | |
| CN105870469A (en) | Pt-Au/GR-RuO2 core-shell-structured methanol fuel cell catalyst and application thereof | |
| CN115557469B (en) | Amorphous noble metal oxide material and preparation method and application thereof | |
| CN109599571B (en) | Dendritic PtPdCu nano-particle for electrocatalytic oxygen reduction and preparation method thereof | |
| CN114082972B (en) | Method for green preparation of Rh ultrathin nanosheets and low crystallinity nanoparticles | |
| CN114931946A (en) | Pt/C composite catalyst and preparation method and application thereof | |
| CN110867588B (en) | PdAu alloy nanoparticle catalyst with core-shell structure and preparation method thereof | |
| CN112323086A (en) | Nickel-platinum composite nano catalyst, preparation method and application thereof, and carbon-supported composite electrocatalyst | |
| CN110676475A (en) | Pt-Ni alloy electrocatalyst with layered framework structure and preparation method thereof | |
| CN111804314A (en) | Sugarcoated haw-shaped rhodium-tellurium nanochain catalyst for catalyzing methanol oxidation reaction and preparation method thereof | |
| CN114653935B (en) | Au@Pt@Ru multilayer core-shell nanomaterial and synthesis method thereof | |
| CN114570384B (en) | Preparation and application of platinum-cobalt alloy catalyst | |
| CN114411191B (en) | Preparation method of high-dispersion graphene oxide supported ruthenium catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |