CN109174119B - Hierarchical dendritic PtCu electrocatalyst and preparation method thereof - Google Patents
Hierarchical dendritic PtCu electrocatalyst and preparation method thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a hierarchical dendritic PtCu electrocatalyst and a preparation method thereof; mixing oleylamine and oleic acid, and heating and ultrasonically treating to obtain a colorless clear solution; keeping the temperature, continuously adding ethylene glycol, and performing ultrasonic treatment to obtain a colorless clear solution; keeping the temperature, continuously adding platinum acetylacetonate and copper acetylacetonate, and performing ultrasonic treatment to obtain a light blue clear solution; and heating and reducing the light blue clear solution to prepare the graded branched PtCu. The method for preparing the hierarchical dendritic PtCu by the oil phase solvent method has the advantages of simple process, stable and safe reaction and high repeatability. Meanwhile, parameters are simply changed, and the preparation of the PtCu nano particle cubic block assembly and the preparation of the PtCu nano concave cubic block can be realized. The method of the invention also has guiding significance for the preparation of other metal nano structures.
Description
Technical Field
The invention belongs to the field of inorganic nano catalytic material manufacturing, and particularly relates to a hierarchical dendritic PtCu electrocatalyst and a preparation method thereof.
Background
The noble metal platinum catalyst has been widely used due to its high catalytic activity and strong selectivityThe catalyst is applied to industrial catalysis, particularly the field of petroleum and chemical catalysis, and comprises the processes of petroleum hydrocarbon reforming, unsaturated compound oxidation and hydrogenation, and CO and NOxAnd (4) removing and the like. In the field of electrocatalysis, particularly in the cathode oxygen reduction process, the anode fuel oxidation process and the electrolytic water hydrogen evolution process of a fuel cell, a platinum-based catalyst is still the catalyst with highest catalytic activity and best stability in an acid electrolyte at present, but the content of platinum in earth crust is only five parts per million, and the platinum is very expensive due to the rare reserve, thereby greatly restricting the use of metal platinum. Therefore, how to improve the catalytic activity and stability of platinum is always a hot research in the field of catalysis and materials.
Platinum-based metal catalysts have been widely and systematically studied over the last several decades. Researchers research and control the preparation and synthesis of platinum-based nanocrystals from the size, morphology and components to obtain a series of platinum-based metal catalysts with different morphology components, including platinum-based alloy nanoparticles, core-shell structured nanoparticles, octahedral nanoparticles with regular crystal faces, nanodiscs, nanocages, nanoboxes, nanowires and other structures, wherein the platinum-based metal catalysts have three-dimensional or two-dimensional nano dendritic structures, the dendritic structures of the platinum-based metal catalysts expose catalytic sites, and the overall structure can avoid the mutual agglomeration of the nano branches, so that the platinum-based metal catalysts have higher catalytic activity and structural stability in electrocatalysis. Wang (Wang)[1]The panel reports the preparation of graded nano dendritic PtCu materials in aqueous systems using KI as the coordinating ion and PVP as the stabilizer, while Zeng[2]The panel also produced gold-tower-like nano-dendritic PtCu materials in ethylene glycol solution using KI and PVP, both reports underscore the importance of I-as the coordinating ion. At present, few reports on the preparation of the graded dendritic PtCu material exist in an oil phase system of an organic solution.
Disclosure of Invention
The invention aims to provide a PtCu catalyst with novel morphological characteristics and a preparation method thereof.
In order to achieve the purpose, the technical scheme is as follows:
a hierarchical branched PtCu comprising a middle trunk and a nano branch; the middle trunk has a length of 500nm to 1 μm and a width of 10nm to 30 nm; the length of the nano branch is 50nm to 400nm, and the width of the nano branch is 5nm to 20 nm; the nanometer branches are distributed on two sides of the middle trunk in a shape similar to a fishbone.
The preparation method of the hierarchical branched PtCu comprises the following steps:
1) mixing oleylamine and oleic acid, and heating and ultrasonically treating to obtain a colorless clear solution;
2) keeping the temperature, continuously adding ethylene glycol, and performing ultrasonic treatment to obtain a colorless clear solution;
3) keeping the temperature, continuously adding platinum acetylacetonate and copper acetylacetonate, and performing ultrasonic treatment to obtain a light blue clear solution;
4) and heating and reducing the light blue clear solution to prepare the graded branched PtCu.
Wherein the volume ratio of oleylamine to oleic acid is 9: 1-7: 3, the volume ratio of ethylene glycol/oleylamine and oleic acid is 1: (40-10), the concentration of the platinum acetylacetonate in the system is 0.1 mM-4 mM, the molar ratio of the platinum acetylacetonate/copper acetylacetonate is 1/4-4/1, the reduction reaction temperature is 170-180 ℃, and the reaction time is 6-12 h.
A PtCu nanoparticle cube assembly, wherein the cube assembly is formed by stacking irregular PtCu nanoparticles; nanoparticles 5nm to 15nm, cubic assembly size 50nm to 150 nm.
The preparation method of the PtCu nano-particle cubic block assembly comprises the following steps:
1) mixing oleylamine and oleic acid, and heating and ultrasonically treating to obtain a colorless clear solution;
2) keeping the temperature, continuously adding ethylene glycol, and performing ultrasonic treatment to obtain a colorless clear solution;
3) keeping the temperature, continuously adding platinum acetylacetonate and copper acetylacetonate, and performing ultrasonic treatment to obtain a light blue clear solution;
4) and heating and reducing the light blue clear solution to prepare the graded branched PtCu.
Wherein the volume ratio of oleylamine/oleic acid is 9: 1-7: 3, the volume ratio of ethylene glycol/oleylamine and oleic acid is 1: (5-2), the concentration of the platinum acetylacetonate in the total solution is 0.1 mM-4 mM, the molar ratio of the platinum acetylacetonate/copper acetylacetonate is 1/4-4/1, the reduction reaction temperature is 170-180 ℃, and the reaction time is 4-12 h.
A PtCu nano concave cube, the edge length of the cube is 30nm to 50nm, and the outer surface of the cube is concave inwards.
The preparation method of the PtCu nano concave cube comprises the following steps:
1) mixing oleylamine and oleic acid, and heating and ultrasonically treating to obtain a colorless clear solution;
2) keeping the temperature, continuously adding ethylene glycol, and performing ultrasonic treatment to obtain a colorless clear solution;
3) keeping the temperature, continuously adding acetylacetone platinum and copper chloride, and performing ultrasonic treatment to obtain a light blue clear solution;
4) and heating and reducing the light blue clear solution to prepare the graded branched PtCu.
Wherein the volume ratio of oleylamine/oleic acid is 9: 1-7: 3, the volume ratio of ethylene glycol/oleylamine and oleic acid is 1: (40-10), the concentration of the platinum acetylacetonate in the total solution is 0.1 mM-4 mM, the molar ratio of the platinum acetylacetonate/copper chloride is 1/4-4/1, the reduction reaction temperature is 170-180 ℃, and the reaction time is 6-12 h.
The invention adopts an oil phase solvent method, ethylene glycol is added into a mixed solution of oleylamine and oleic acid to synthesize the hierarchical dendritic PtCu, the synthesis method is simple, and the prepared hierarchical dendritic PtCu is applied to electrocatalytic methanol oxidation and has excellent catalytic performance.
The PtCu nano particle cubic assembly can be controllably synthesized by changing the addition of ethylene glycol and regulating the proportion of each component of a solvent system, and the PtCu nano concave cubic can be regulated and controlled only by changing a Cu source.
Compared with the prior art, the invention has the following beneficial effects:
the method for preparing the hierarchical dendritic PtCu by the oil phase solvent method has the advantages of simple process, stable and safe reaction and high repeatability. Meanwhile, parameters are simply changed, and the preparation of the PtCu nano particle cubic block assembly and the preparation of the PtCu nano concave cubic block can be realized. The method of the invention also has guiding significance for the preparation of other metal nano structures.
Drawings
FIG. 1: example 1 SEM picture of graded dendritic PtCu.
FIG. 2: TEM images of dendritic PtCu after concentrated nitric acid treatment in example 1 were fractionated.
FIG. 3: electrocatalytic methanol oxidation performance of the graded dendritic PtCu after concentrated nitric acid treatment in example 1.
FIG. 4: SEM image of the graded dendritic PtCu prepared in example 2.
FIG. 5: SEM picture of the graded dendritic PtCu prepared in example 3.
FIG. 6: SEM image of the graded dendritic PtCu prepared in example 4.
FIG. 7: SEM image of the PtCu nanoparticle cubic assembly prepared in example 5.
FIG. 8: SEM image of PtCu nano-concave cubes produced in example 6.
Detailed Description
The following examples further illustrate the technical solutions of the present invention, but should not be construed as limiting the scope of the present invention.
Example 1
A hierarchical dendritic PtCu electrocatalyst and a preparation method thereof comprise the following steps:
(1) mixing 9mL of oleylamine with 1mL of oleic acid solution, and performing ultrasonic treatment at 55 ℃ to obtain a colorless clear solution to prepare a mixed solution of oleylamine and oleic acid;
(2) adding 0.5mL of glycol solution into the mixed solution of oleylamine and oleic acid in the step (1), and carrying out ultrasonic treatment at 55 ℃ to obtain a colorless clear solution;
(3) adding 8.0mg of platinum acetylacetonate and 5.2mg of copper acetylacetonate into the clear mixed solution obtained in the step (2), and carrying out ultrasonic treatment at 55 ℃ to obtain a colorless clear solution;
(4) and (3) placing the clear mixed solution in an oil bath kettle at 170 ℃ for reaction for 12 h.
(5) The product was washed by centrifugal separation with a mixed solution of ethanol and cyclohexane.
(6) The black product was soaked in 5mL of concentrated nitric acid solution for 1 day and then washed by centrifugation with an aqueous solution.
The electrocatalytic methanol oxidation performance test comprises the following steps:
(1) and preparing the electrocatalyst ink. Ultrasonically dispersing the graded dendritic PtCu aqueous solution, testing the concentration of the graded dendritic PtCu aqueous solution by an inductive coupling plasma spectrometer, and adding a certain amount of commercial carbon powder Vulcan XC-72 into the nano dendritic Pt aqueous solution to ensure that the Pt/C mass ratio is about 20 percent and the Pt/C is uniformly dispersed by ultrasonic for 2 hours.
(2) The electrocatalyst ink is drop coated on the glassy carbon electrode. Firstly, uniformly coating a layer of electrocatalyst ink on a glassy carbon electrode to ensure that the Pt loading capacity is 15.3 mu g/cm2After the drying, 5. mu.L of Nafion solution dissolved in 0.5% isopropyl alcohol was added dropwise thereto, followed by drying.
(3) And (4) testing the oxidation performance of the electrocatalytic methanol. The test is carried out by adopting a three-electrode system of the Shanghai Chenghua electrochemical workstation, taking Ag/AgCl as a reference electrode and a platinum sheet as a counter electrode, and filling saturated N20.1mol/L of HClO4The cyclic voltammetry curve is tested in the middle, the sweep number is 50mV/s, and the saturated N is filled20.1mol/L of HClO4And 1mol/LCH3Methanol oxidation was tested in OH mixed solution with a sweep of 50 mV/s. The stability was tested by chronoamperometry at a voltage of 0.7V versus a standard hydrogen electrode for 3000 s.
From the SEM image of FIG. 1, it can be observed that (a is before the concentrated nitric acid treatment and b is after the concentrated nitric acid treatment), the entire size of the graded dendritic PtCu is about 1 μm to 2 μm, the length of the middle trunk is about 500nm to 1 μm, and polyhedral nanoparticles having a size of 50nm to 80nm, possibly copper nanoparticles, can be also observed in FIG. 1a, and after 1 day of the concentrated nitric acid soaking, it can be observed that only the graded dendritic PtCu remains in FIG. 1b, and the entire structure thereof is hardly changed. From the TEM image of fig. 2, it can be observed that the trunk width of the hierarchical dendritic structure is about 10nm to 30nm, the nano-branches are distributed on both sides of the trunk like "fish bones", the length of the nano-branches is about 50nm to 400nm, and the width is about 5nm to 20 nm. The interplanar spacings measured by high resolution transmission diagrams were 0.225nm and 0.224nm, while the (111) interplanar spacing for pure Pt was 0.227nm, since the Cu atomic size was smaller than the Pt atomic size after alloying Cu and Pt, resulting in a smaller lattice for Pt, thus indicating that the measured interplanar spacing belongs to the (111) interplanar of PtCu alloy, while Pt and Cu form nano-scale alloying.
Fig. 3 is a graph showing the electrocatalytic methanol oxidation performance of the graded dendritic PtCu material of this embodiment. FIG. 3a is a graph showing that the concentration of LHClO is at 0.1mol/LHClO4Saturated N in the electrolyte2Then, the scanning rate is 50mV/s, the abscissa is the voltage relative to the reversible hydrogen electrode (vs. RHE), the ordinate is the current density, dendritic PtCu is graded dendritic PtCu, and commercial Pt/C is commercial Pt/C; the area of the hydrogen adsorption zone of the cyclic voltammogram of FIG. 3a was integrated to obtain the electrochemically active area, which is 62m for commercial Pt/C2(g) the electrochemically active area of the hierarchical branched PtCu was 33.0m2Lower/g than commercial Pt/C. FIG. 3b is a plot of cyclic voltammetry for methanol oxidation, with voltage versus reversible hydrogen electrode on the abscissa and test current on the ordinate; from the methanol oxidation curve of fig. 3b, it can be seen that the mass activity of Pt with the saw-toothed multi-legged structure is greater than that of commercial Pt/C. The mass activity and specific activity of the two catalysts can be found by calculation, as shown in FIG. 3c, and for the calculated histogram of mass activity and specific activity of the catalytic material, the mass activity and specific activity of the graded dendritic PtCu are 1604mA/mg and 4.83mA/cm, respectively210.3 times and 19.3 times, respectively, that of commercial Pt/C. FIG. 3d is a timing current graph showing that the current of the graded dendritic PtCu is higher than that of commercial Pt/C at 0.7V relative to the standard hydrogen electrode within the same time of testing the timing current, and the current is still higher than that of the commercial Pt/C after reaching the steady state from the non-steady state, which shows that the stability of the graded dendritic PtCu is better than that of the commercial Pt/C.
Example 2
A hierarchical dendritic PtCu electrocatalyst and a preparation method thereof comprise the following steps:
(1) mixing 9mL of oleylamine with 1mL of oleic acid solution, and performing ultrasonic treatment at 55 ℃ to obtain a colorless clear solution to prepare a mixed solution of oleylamine and oleic acid;
(2) adding 0.5mL of glycol solution into the mixed solution of oleylamine and oleic acid in the step (1), and carrying out ultrasonic treatment at 55 ℃ to obtain a colorless clear solution;
(3) adding 8.0mg of platinum acetylacetonate and copper acetylacetonate with different content into the clear mixed solution obtained in the step (2) for comparison, wherein the copper acetylacetonate is selected to be 10.4m and 2.6mg in the embodiment, and then carrying out ultrasonic treatment at 55 ℃ to obtain a colorless clear solution;
(4) and (3) placing the clear mixed solution in an oil bath kettle at 170 ℃ for reaction for 12 h.
(5) The product is centrifugally separated and washed by using a mixed solution of ethanol and cyclohexane, and finally dispersed in an ethanol solution.
In this example, the content ratio of the Pt source and the Cu source is controlled, the graded dendritic PtCu can be effectively prepared according to the preparation method, and it can be observed from the SEM image in fig. 4 that after the molar ratio of Pt/Cu is changed, the graded dendritic PtCu can be prepared by the method of the present invention, which has a structure similar to that in example 1, but nano polyhedral particles appear in the product, which is consistent with that before the product in example 1 is subjected to concentrated nitric acid treatment, when the molar ratio of Pt/Cu is decreased, the yield of the formed graded dendritic PtCu is lower than that of the formed polyhedral nanoparticles, and when the molar ratio of Pt/Cu is increased, the yield of the formed graded dendritic PtCu is higher than that of the formed polyhedral nanoparticles, possibly due to the formation of the polyhedral nanoparticles after excessive reduction of the Cu source.
Example 3
A hierarchical dendritic PtCu electrocatalyst and a preparation method thereof comprise the following steps:
(1) mixing oleylamine with different amounts with oleic acid solution, selecting oleylamine with the concentration of 8 mL/oleic acid with the concentration of 2mL and oleylamine with the concentration of 7 mL/oleic acid with the concentration of 3mL respectively, and performing ultrasonic treatment at 55 ℃ to obtain colorless clear solution to prepare mixed solution of oleylamine and oleic acid;
(2) adding 0.5mL of glycol solution into the mixed solution of oleylamine and oleic acid in the step (1), and carrying out ultrasonic treatment at 55 ℃ to obtain a colorless clear solution;
(3) adding 8.0mg of platinum acetylacetonate and 5.2mg of copper acetylacetonate into the clear mixed solution obtained in the step (2), and carrying out ultrasonic treatment at 55 ℃ to obtain a colorless clear solution;
(4) and (3) placing the clear mixed solution in an oil bath kettle at 170 ℃ for reaction for 12 h.
(5) The product is centrifugally separated and washed by using a mixed solution of ethanol and cyclohexane, and finally dispersed in an ethanol solution.
In this embodiment, the content ratio of oleylamine to oleic acid is controlled, the hierarchical dendritic PtCu can be effectively prepared according to the preparation method, and it can be observed from the SEM image in fig. 5 that when the content of oleic acid relative to oleylamine is increased, the hierarchical dendritic PtCu can be prepared by the method of the present invention, the overall size of PtCu is about 1 μm to 2 μm, the length of the middle trunk is about 500nm to 1 μm, the width of the trunk of the hierarchical dendritic structure is about 30nm, the nano-branches are distributed on both sides of the trunk like "fishbone", the length of the nano-branches is about 50nm to 200nm, and the width is about 10 nm.
Example 4
A hierarchical dendritic PtCu electrocatalyst and a preparation method thereof comprise the following steps:
(1) mixing 9mL of oleylamine with 1mL of oleic acid solution, and performing ultrasonic treatment at 55 ℃ to obtain a colorless clear solution to prepare a mixed solution of oleylamine and oleic acid;
(2) adding 0.5mL of glycol solution into the mixed solution of oleylamine and oleic acid in the step (1), and carrying out ultrasonic treatment at 55 ℃ to obtain a colorless clear solution;
(3) adding 8.0mg of platinum acetylacetonate and 5.2mg of copper acetylacetonate into the clear mixed solution obtained in the step (2), and carrying out ultrasonic treatment at 55 ℃ to obtain a colorless clear solution;
(4) the clear mixture was placed in oil baths at different temperatures for 12 hours, 160 ℃ and 175 ℃ being chosen for the example.
(5) The product was washed by centrifugal separation with a mixed solution of ethanol and cyclohexane.
In this embodiment, the hierarchical dendritic PtCu can be effectively prepared according to the preparation method controlled by the reaction temperature, and it can be observed from the SEM image of fig. 6a that when the reaction temperature is increased to 175 ℃, the hierarchical dendritic PtCu can be prepared by the method of the present invention, and the overall morphology thereof is not changed much compared with 170 ℃, but when the reaction temperature is decreased to 160 ℃, only the disordered accumulation body of nanoparticles having a size of about 30nm to 100nm can be obtained as shown in fig. 6 b.
Example 5
The preparation method of the PtCu nano-particle cubic block assembly comprises the following steps:
(1) mixing 9mL of oleylamine with 1mL of oleic acid solution, and performing ultrasonic treatment at 55 ℃ to obtain a colorless clear solution to prepare a mixed solution of oleylamine and oleic acid;
(2) adding 2mL of glycol solution into the mixed solution of oleylamine and oleic acid in the step (1), and performing ultrasonic treatment at 55 ℃ to obtain a colorless clear solution;
(3) adding 8.0mg of platinum acetylacetonate and 5.2mg of copper acetylacetonate into the clear mixed solution obtained in the step (2), and carrying out ultrasonic treatment at 55 ℃ to obtain a colorless clear solution;
(4) and (3) placing the clear mixed solution in an oil bath kettle at 170 ℃ for reaction for 12 h.
(5) The product was washed by centrifugal separation with a mixed solution of ethanol and cyclohexane.
In the embodiment, the volume of the added glycol is regulated, and the PtCu nanoparticle cubic assembly can be effectively prepared according to the preparation method. As can be seen from the SEM image of fig. 7, an assembly having a cubic structure in which PtCu nanoparticles are agglomerated is generated, and a part of the graded dendritic PtCu is generated in the product. Wherein the nano-particles are about 5nm to 15nm, the size of the cubic assembly is about 50nm to 150nm, the assembly integrally shows an obvious cubic structure, edges and side faces can be clearly seen, and the assembly is formed by stacking random nano-particles.
Example 6
The preparation method of the PtCu nano concave cube comprises the following steps:
(1) mixing 9mL of oleylamine with 1mL of oleic acid solution, and performing ultrasonic treatment at 55 ℃ to obtain a colorless clear solution to prepare a mixed solution of oleylamine and oleic acid;
(2) adding 2mL of glycol solution into the mixed solution of oleylamine and oleic acid in the step (1), and performing ultrasonic treatment at 55 ℃ to obtain a colorless clear solution;
(3) adding 8.0mg of platinum acetylacetonate and 2.7mg of anhydrous copper chloride into the clear mixed solution obtained in the step (2), and carrying out ultrasonic treatment at 55 ℃ to obtain a colorless clear solution;
(4) and (3) placing the clear mixed solution in an oil bath kettle at 170 ℃ for reaction for 12 h.
(5) The product was washed by centrifugal separation with a mixed solution of ethanol and cyclohexane.
The embodiment is regulated and controlled by different Cu sources, and the PtCu nano concave cubic block can be effectively prepared according to the preparation method. From the SEM image of FIG. 8, it can be observed that the nano concave cubes with uniform morphology and size, wherein the cube edges are about 30nm to 50nm in length, the outer surfaces are all concave, and the concave faces cause the corners to protrude, the structure is somewhat similar to a nano frame.
It is apparent that the above embodiments are only examples for clearly illustrating and do not limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. It is not necessary or necessary to exhaustively enumerate all embodiments herein, and obvious variations or modifications can be made without departing from the scope of the invention.
Claims (4)
1. A preparation method of hierarchical dendritic PtCu is characterized by comprising the following steps:
1) mixing oleylamine and oleic acid, and heating and ultrasonically treating to obtain a colorless clear solution;
2) keeping the temperature, continuously adding ethylene glycol, and performing ultrasonic treatment to obtain a colorless clear solution;
3) keeping the temperature, continuously adding platinum acetylacetonate and copper acetylacetonate, and performing ultrasonic treatment to obtain a light blue clear solution;
4) heating and reducing the light blue clear solution to prepare graded dendritic PtCu;
wherein the volume ratio of oleylamine/oleic acid is 9: 1-7: 3, the volume ratio of ethylene glycol/oleylamine and oleic acid is 1: (40-10), wherein the concentration of the platinum acetylacetonate in the system is 0.1 mM-4 mM, the molar ratio of the platinum acetylacetonate to the copper acetylacetonate is 1/4-4/1, the reduction reaction temperature is 170-180 ℃, and the reaction time is 6-12 h;
the hierarchical branched PtCu comprises a middle trunk and a nano branch; the middle trunk has a length of 500nm to 1 μm and a width of 10nm to 30 nm; the length of the nano branch is 50nm to 400nm, and the width of the nano branch is 5nm to 20 nm; the nanometer branches are distributed on two sides of the middle trunk in a shape similar to a fishbone.
2. A PtCu nanoparticle cube assembly, characterized in that the cube assembly is formed by stacking random PtCu nanoparticles; nanoparticles 5nm to 15nm, cubic assembly size 50nm to 150 nm.
3. The method of making a PtCu nanoparticle cube assembly of claim 2, comprising the steps of:
1) mixing oleylamine and oleic acid, and heating and ultrasonically treating to obtain a colorless clear solution;
2) keeping the temperature, continuously adding ethylene glycol, and performing ultrasonic treatment to obtain a colorless clear solution;
3) keeping the temperature, continuously adding platinum acetylacetonate and copper acetylacetonate, and performing ultrasonic treatment to obtain a light blue clear solution;
4) heating and reducing the light blue clear solution to obtain a PtCu nano particle cubic assembly;
wherein the volume ratio of oleylamine/oleic acid is 9: 1-7: 3, the volume ratio of ethylene glycol/oleylamine and oleic acid is 1: (5-2), the concentration of the platinum acetylacetonate in the total solution is 0.1 mM-4 mM, the molar ratio of the platinum acetylacetonate/copper acetylacetonate is 1/4-4/1, the reduction reaction temperature is 170-180 ℃, and the reaction time is 4-12 h.
4. A preparation method of PtCu nano concave cubic block is characterized by comprising the following steps:
1) mixing oleylamine and oleic acid, and heating and ultrasonically treating to obtain a colorless clear solution;
2) keeping the temperature, continuously adding ethylene glycol, and performing ultrasonic treatment to obtain a colorless clear solution;
3) keeping the temperature, continuously adding acetylacetone platinum and copper chloride, and performing ultrasonic treatment to obtain a light blue clear solution;
4) heating and reducing the light blue clear solution to obtain PtCu nano concave cubic blocks;
wherein the volume ratio of oleylamine/oleic acid is 9: 1-7: 3, the volume ratio of ethylene glycol/oleylamine and oleic acid is 1: (40-10), wherein the concentration of the platinum acetylacetonate in the total solution is 0.1 mM-4 mM, the molar ratio of the platinum acetylacetonate to the copper chloride is 1/4-4/1, the reduction reaction temperature is 170-180 ℃, and the reaction time is 6-12 h; the length of the edge of the cubic block is 30nm to 50nm, and the outer surface of the cubic block is inwards concave.
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| CN103696016A (en) * | 2013-11-27 | 2014-04-02 | 浙江大学 | Platinoid alloy nano dendritic crystal and preparation method thereof |
| CN108003355A (en) * | 2017-11-23 | 2018-05-08 | 浙江师范大学 | The method of one pot of coreduction PtCu nanometers of frame material of solvent structure hollow cube |
| CN108161025A (en) * | 2018-02-07 | 2018-06-15 | 中南民族大学 | A kind of eight foot-shape Pt-Cu alloy nano-materials and its synthetic method and application |
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| CN103696016A (en) * | 2013-11-27 | 2014-04-02 | 浙江大学 | Platinoid alloy nano dendritic crystal and preparation method thereof |
| CN108003355A (en) * | 2017-11-23 | 2018-05-08 | 浙江师范大学 | The method of one pot of coreduction PtCu nanometers of frame material of solvent structure hollow cube |
| CN108161025A (en) * | 2018-02-07 | 2018-06-15 | 中南民族大学 | A kind of eight foot-shape Pt-Cu alloy nano-materials and its synthetic method and application |
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