CN110993973A - Platinum-palladium-phosphorus dendritic nano-particle for catalyzing formic acid oxidation reaction and preparation method thereof - Google Patents
Platinum-palladium-phosphorus dendritic nano-particle for catalyzing formic acid oxidation reaction and preparation method thereof Download PDFInfo
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Abstract
A platinum-palladium-phosphorus dendritic nano particle for catalyzing formic acid oxidation reaction and a preparation method thereof are disclosed, wherein a chloroplatinic acid solution with the concentration of 10-100 mM and an ascorbic acid solution with the concentration of 0.05-0.5M are respectively prepared; taking a chloroplatinic acid solution with the volume of 5mL, adding 20-100 mg of Brij58, adding 1-10 mL of ascorbic acid solution, and mixing; carrying out ultrasonic reaction for 5-60 min at room temperature, centrifuging and washing to obtain dendritic platinum nanoparticles, and dispersing the dendritic platinum nanoparticles in 2mL of aqueous solution; dissolving 5-80 mg of tetrakis (triphenylphosphine) palladium and dendritic platinum nanoparticles in 22mL of oleylamine; carrying out hydrothermal reaction for 5-20 h at 100-200 ℃. And centrifuging and washing to obtain the platinum-palladium-phosphorus dendritic nanoparticles. The synthesis method is simple, the product yield is high, and the prepared platinum-palladium-phosphorus nanoparticles have excellent electrocatalytic formic acid oxidation performance.
Description
(I) technical field
The invention relates to a platinum-palladium-phosphorus dendritic nano particle for catalyzing formic acid oxidation reaction and a preparation method thereof.
(II) background of the invention
The direct formic acid fuel cell has the advantages of high energy density, environmental friendliness and the like, and is an energy conversion device with full potential. Currently, platinum-based materials are a class of formic acid oxidation catalysts that are widely used. Studies have shown that formic acid oxidation occurs mainly through two pathways. One is direct oxidation, i.e. formic acid is oxidized directly to carbon dioxide. Another is that formic acid is first oxidized to carbon monoxide and then to carbon dioxide (hong Sheng Fan, Ming Cheng, LeiWang, Yuanjun Song, Yimin Cui, Rongming Wang, mapping electrochemical performance for the purpose of forming acid oxidation by the synthetic effect of Pt and Au supported carbon black for electrocatalytic formic acid oxidation), Nano Energy 2018,48, 1-9). In the second route, when carbon monoxide accumulates on the surface of the platinum-based material, it results in deactivation of the active sites on the surface, and ultimately, in a decrease in the performance of the catalyst. In general, the composition, morphology and electronic structure of the catalyst can be adjusted to effectively promote the catalytic performance and stability of the catalyst.
According to literature reports, formic acid is more susceptible to direct oxidation reactions when the platinum atom is not continuous. Platinum can therefore be alloyed with other metallic or non-metallic materials to achieve atomic separation of platinum, while the introduction of other elements can regulate the electronic structure of platinum, facilitating the progress of the direct Oxidation Pathway (xiaan Jiang, xiaoao Yan, Wangyu Ren, yufeng jia, Jianian Chen, Dongmei Sun, Lin Xu, and Yawen Tang, ports AgPt @ ptnoctahedra as an effective Catalyst heated for chemical Oxidation reaction Pathway (Porous AgPt nano-octahedrons catalyze Formic Acid Oxidation by Dehydrogenation step), ACS application. Among the platinum-based alloy materials, the platinum-palladium alloy shows excellent catalytic formic acid oxidation performance and carbon monoxide poisoning resistance. Meanwhile, researches show that the introduction of non-metallic elements into the noble metal catalyst can promote the electrocatalytic performance and stability of the noble metal catalyst. For example, the introduction of phosphorus atoms can provide abundant valence electrons, change the electronic structure of the original material, and thus improve the electrocatalytic performance and carbon monoxide tolerance (Jingfang Zhang, Kaidan Li and Bin Zhang, Synthesis of dendritic Pt-Ni-P alloynoptical fibers with enhanced electrocatalytic properties (synthesized Pt-Ni-P alloy nanoparticles for enhancing electrocatalytic activity), chem. Commun.2015,51, 12012-charge 12015). Therefore, the introduction of phosphorus atoms into platinum-palladium based materials is an effective way to prepare highly efficient electrocatalysts.
Besides, adjusting the morphology structure of the platinum-based material is another effective way to improve the electrocatalytic activity of the platinum-based material. Much research has been directed to increasing the specific surface area of platinum-based materials to produce catalysts of various morphologies, such as nanowires, nanoflowers, nano-dendritic structures, nanotubes, and the like. Among them, the nano-dendritic structure has a larger specific Surface area and abundant Surface defects, so that it has more catalytic active sites (Liang Wang, Masataka Impura, and Yusuke Yamauchi, Tailored Design of Integrated control Pt Nanoparticles with big Surface area heated Superior materials synthesized Pt Nanoparticles with large Surface area as excellent Unsupported Electrocatalysts), ACS applied. Material interface 2012,4, 2865-2869). At present, although a plurality of phosphorus-doped platinum-based materials are reported, most of the phosphorus-doped platinum-based materials have irregular solid structures, low specific surface area and complicated preparation process. Therefore, the preparation of novel phosphorus-doped dendritic platinum-based nano materials has profound significance.
Disclosure of the invention
The invention aims to provide platinum-palladium-phosphorus dendritic nanoparticles for catalyzing formic acid oxidation reaction, a preparation method thereof and a research on the performance of the platinum-palladium-phosphorus dendritic nanoparticles for catalyzing formic acid oxidation reaction.
The technical scheme adopted by the invention is as follows:
a platinum-palladium-phosphorus dendritic nanoparticle for catalyzing formic acid oxidation reaction is prepared by the following steps:
(1) respectively preparing chloroplatinic acid solution with the concentration of 10-100 mM and ascorbic acid solution with the concentration of 0.05-0.5M;
(2) taking a chloroplatinic acid solution with the volume of 5mL, adding 20-100 mg of Brij58, finally adding 1-10 mL of ascorbic acid solution, and uniformly mixing;
(3) after the solutions are fully mixed, placing the mixture in an ultrasonic cleaning machine, reacting for 5-60 min at room temperature, carrying out centrifugal separation, collecting precipitates, washing to obtain dendritic platinum nanoparticles, and dispersing the precipitates in 2mL of aqueous solution again;
(4) dissolving 5-80 mg of tetrakis (triphenylphosphine) palladium in 22mL of oleylamine, and mixing with the dendritic platinum nanoparticle solution; and transferring the mixed solution into a hydrothermal reaction kettle, reacting for 5-20 h at 100-200 ℃, performing centrifugal separation, collecting precipitates, and washing with ethanol to remove residual tetrakis (triphenylphosphine) palladium and oleylamine to obtain the platinum-palladium-phosphorus dendritic nanoparticles.
The selection of reaction conditions is crucial to the preparation of platinum palladium phosphorus dendritic nanoparticles. In the first stage, Brij58 is selected as a structure directing agent, so that the growth of the particles can be effectively controlled and agglomeration can be prevented. In addition, ascorbic acid, as a reducing agent, plays a decisive role in the structure of the dendritic platinum nanoparticles. In the second stage, tetrakis (triphenylphosphine) palladium is used as a palladium source and a phosphorus source at the same time, and palladium and phosphorus can be simultaneously doped into the dendritic platinum nanoparticles through high-temperature reaction decomposition in an oleylamine solution.
A preparation method of a dendritic platinum-palladium-phosphorus nano electro-catalyst for catalyzing oxidation reaction of formic acid comprises the following steps:
(1) respectively preparing chloroplatinic acid solution with the concentration of 10-100 mM and ascorbic acid solution with the concentration of 0.05-0.5M;
(2) taking a chloroplatinic acid solution with the volume of 5mL, adding 20-100 mg of Brij58, finally adding 1-10 mL of ascorbic acid solution, and uniformly mixing;
(3) after the solutions are fully mixed, placing the mixture in an ultrasonic cleaning machine, reacting for 5-60 min at room temperature, carrying out centrifugal separation, collecting precipitates, washing to obtain dendritic platinum nanoparticles, and dispersing the precipitates in 2mL of aqueous solution again;
(4) dissolving 5-80 mg of tetrakis (triphenylphosphine) palladium in 22mL of oleylamine, and mixing with the dendritic platinum nanoparticle solution; and transferring the mixed solution into a hydrothermal reaction kettle, reacting for 5-20 h at 100-200 ℃, performing centrifugal separation, collecting precipitates, and washing with ethanol to remove residual tetrakis (triphenylphosphine) palladium and oleylamine to obtain the platinum-palladium-phosphorus dendritic nanoparticles.
Further, the concentration and volume of chloroplatinic acid and ascorbic acid, the addition amount of Brij58 and tetrakis (triphenylphosphine) palladium, and the temperature and time of the hydrothermal reaction are controlled to control the morphology and structure of platinum, palladium and phosphorus.
The electrochemical catalysis formic acid oxidation reaction test is carried out at normal temperature and normal pressure, and the specific performance test operation process is as follows:
(1) ultrasonically dissolving and dispersing the dried platinum-palladium-phosphorus dendritic nano particles in ultrapure water to obtain a uniform solution of 1-5 mg/mL, dripping 1-10 mu L of the solution on the surface of a glassy carbon electrode, drying in a 50 ℃ oven, and then dripping 1-10 mu L of an LNafion solution (0.5 wt%) to cover the surface of a catalyst to prepare a working electrode. Meanwhile, a platinum wire electrode is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode to form a three-electrode system for carrying out an electro-catalytic formic acid oxidation test;
(2) prior to testing, 0.5M sulfuric acid and 0.5M sulfuric acid +0.5M formic acid electrolyte were prepared. Selecting a test program of cyclic voltammetry, setting the sweep rate to be 50mV/s, firstly scanning 10 circles in sulfuric acid solution to activate the catalyst, then selecting linear sweep voltammetry, carrying out electrochemical performance test in sulfuric acid + formic acid solution, and monitoring the current change condition of a working electrode by using a computer. And calculating the electrochemical active area, the mass activity and the specific activity according to the measured data and a corresponding formula to evaluate the performance of the catalyst in the process of catalyzing the formic acid oxidation reaction. Detecting the stability of the catalyst in the catalytic reaction process through a polarographic current time curve; the CO desorption test is carried out in a 0.5M sulfuric acid solution, and the CO poisoning resistance of the catalyst is judged by the CO oxidation peak position.
The platinum-palladium-phosphorus dendritic nano particle for catalyzing formic acid oxidation reaction and the preparation method thereof provided by the invention have the following advantages:
(1) the phosphorization method provided by the invention has simple steps and easy operation, and can simultaneously introduce palladium and phosphorus elements in one step by using tetrakis (triphenylphosphine) palladium, thereby providing a new idea for the preparation of the phosphorus-containing catalyst.
(2) The platinum-palladium-phosphorus catalyst prepared by the method is of a dendritic structure, is regular in structural morphology and large in specific surface area, and can expose more catalytic active sites in the electrocatalysis process.
(3) The platinum-palladium-phosphorus catalyst provided by the invention has excellent catalytic performance and stability in the catalytic formic acid oxidation reaction, and promotes the development of formic acid fuel cells.
(IV) description of the drawings
Fig. 1 is a TEM image of platinum palladium phosphorous dendritic nanoparticles of specific example 1 of the present invention.
FIG. 2 is HRTEM and Fourier transform images of platinum palladium phosphorous dendritic nanoparticles of specific example 1 of the present invention.
Fig. 3 is an XRD pattern and XPS pattern of different elements of platinum palladium phosphorous dendritic nanoparticles according to embodiment 1 of the present invention.
Fig. 4 is a linear sweep voltammetry curve of platinum palladium phosphorus dendritic nanoparticles in 0.5M sulfuric acid +0.5M formic acid electrolyte, according to embodiment 1 of the present invention, with electrochemical activity area and mass normalization of metals in the catalyst, respectively, to obtain specific activity and mass activity.
FIG. 5 is a time plot of polarographic current and cyclic voltammetry curves for CO stripping of platinum palladium phosphorous dendritic nanoparticles of specific example 1 of the present invention.
Fig. 6 is a TEM image of dendritic platinum nanoparticles according to embodiment 2 of the present invention.
Fig. 7 is an XRD pattern of dendritic platinum nanoparticles and an XPS pattern of platinum according to example 2 of the present invention.
Fig. 8 shows linear sweep voltammetry curves, specific activities, and mass activities of dendritic platinum nanoparticles in 0.5M sulfuric acid +0.5M formic acid electrolyte according to embodiment 2 of the present invention.
FIG. 9 is a time plot of polarographic current and cyclic voltammetry curves for branched platinum nanoparticles and CO stripping, according to example 2 of the present invention.
(V) detailed description of the preferred embodiments
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto:
referring to fig. 1 to 9, the performance test of the platinum-palladium-phosphorus nano electrocatalytic oxidation reaction of formic acid is performed on a CHI 660D electrochemical workstation, and the operation process is as follows:
firstly, ultrasonically dispersing and dissolving dried platinum-palladium-phosphorus dendritic nano particles in ultrapure water to obtain a uniform solution of 2mg/mL, dripping 5 mu L of the solution on the surface of a glassy carbon electrode, drying in an oven at 50 ℃, and then dripping 5 mu L of Nafion solution (0.5 wt%) to cover the surface of a catalyst to prepare a working electrode. Meanwhile, a platinum wire electrode is used as a counter electrode, and an Ag/AgCl electrode is used as a reference electrode to form a three-electrode system for carrying out electrocatalytic formic acid oxidation performance test;
second, 0.5M sulfuric acid and 0.5M sulfuric acid +0.5M formic acid electrolyte were prepared before testing. Firstly, adopting cyclic voltammetry to scan 10 circles in sulfuric acid solution to activate the catalyst, then carrying out electrochemical performance test in sulfuric acid + formic acid solution, and monitoring the current change condition of a working electrode by using a computer. And calculating the electrochemical active area, the mass activity and the specific activity according to the measured data and a corresponding formula to evaluate the performance of the catalyst in the process of catalyzing the formic acid oxidation reaction. Detecting the stability of the catalyst in the catalytic reaction process through a polarographic current time curve; the CO desorption test was performed in a 0.5M sulfuric acid solution, and the CO poisoning resistance of the catalyst was judged by the position of the CO oxidation peak.
Example 1:
a preparation method of dendritic platinum-palladium-phosphorus nanoparticles for catalyzing formic acid oxidation reaction comprises the following steps:
(1) respectively preparing a chloroplatinic acid solution with the concentration of 20mM and an ascorbic acid solution with the concentration of 0.1M;
(2) taking a chloroplatinic acid solution with the volume of 5mL, then adding 50mg of Brij58, finally adding 5mL of ascorbic acid solution, and uniformly mixing;
(3) after the solutions are fully mixed, the mixture is placed in an ultrasonic cleaning machine, after reaction is carried out for 20min at room temperature, the centrifugal separation, the collection and the washing are carried out to obtain dendritic platinum nano particles, and the precipitate is dispersed in 2mL of aqueous solution again;
(4) dissolving 30mg of tetrakis (triphenylphosphine) palladium in 22mL of oleylamine, and mixing with the dendritic platinum nanoparticle solution; and transferring the mixed solution into a hydrothermal reaction kettle, reacting for 10h at 180 ℃, centrifugally separating, collecting precipitate, and washing with ethanol to remove residual tetrakis (triphenylphosphine) palladium and oleylamine to obtain the platinum-palladium-phosphorus dendritic nanoparticles.
A TEM image of the resulting platinum palladium phosphorous dendritic nanoparticles is shown in fig. 1. The TEM, HRTEM and fourier transform images of the platinum palladium phosphorous dendrites obtained are shown in fig. 2. The XRD pattern of the obtained platinum palladium phosphorus dendritic nanoparticles is shown in fig. 3. The linear scanning voltammetry curve, the specificity activity and the mass activity of the forward peak potential of the obtained platinum-palladium-phosphorus dendritic nanoparticles at the scanning speed of 50mV/s are shown in figure 4, and the polarographic current-time curve and the cyclic voltammetry curve of CO detachment of the obtained platinum-palladium-phosphorus dendritic nanoparticles are shown in figure 5.
According to a TEM image, the obtained platinum, palladium and phosphorus are in a nano multi-branched structure, and the insides of the platinum, the palladium and the phosphorus are mutually connected. The dendritic nano particles have rough surfaces, large specific surface areas and more catalytic active sites, so that the electrocatalytic performance is promoted. The product was polycrystalline by HRTEM, electron diffraction rings and XRD analysis. The platinum palladium phosphorus dendritic nano particles form an alloy structure through XRD and XPS analysis. The specific activity and the mass activity of the sample can be obtained by normalizing the linear scanning voltammetry curves by the electrochemical active area and the mass of the metal respectively, and the figure shows that the platinum-palladium-phosphorus dendritic nanoparticles have higher specific activity and mass activity, which shows that the platinum-palladium-phosphorus dendritic nanoparticles have good electrocatalytic formic acid oxidation performance. There are two oxidation peaks in the linear sweep voltammogram, peak 1 being due to dehydrogenation (direct oxidation), peak 2 being due to dehydration, and the ratio of peak 1 to peak 2 currents reflects the path of the formic acid oxidation. A larger ratio indicates a more pronounced enhancement of the dehydrogenation pathway. The graph shows that the platinum-palladium-phosphorus dendritic nanoparticles mainly take dehydrogenation paths in the catalytic reaction process, and are more favorable for catalyzing the oxidation reaction of formic acid. As can be seen from the polarographic current-time curve, the platinum-palladium-phosphorus dendritic nano-particles have good stability in the catalysis process. In a cyclic voltammetry curve of CO stripping, a CO oxidation peak of the platinum-palladium-phosphorus dendritic nanoparticles has a more negative potential, which indicates that the platinum-palladium-phosphorus dendritic nanoparticles have better CO resistance.
Example 2:
a method for preparing dendritic platinum nanoparticles for catalyzing oxidation of formic acid, the method comprising the steps of:
1) respectively preparing a chloroplatinic acid solution with the concentration of 20mM and an ascorbic acid solution with the concentration of 0.1M;
2) taking a chloroplatinic acid solution with the volume of 5mL, then adding 50mg of Brij58, finally adding 5mL of ascorbic acid solution, and uniformly mixing;
3) and after the solutions are fully mixed, placing the mixture in an ultrasonic cleaning machine, reacting for 20min at room temperature, centrifugally separating, collecting precipitates and washing to obtain the dendritic platinum nanoparticles.
A TEM image of the resulting dendritic platinum nanoparticles is shown in fig. 6. The XRD and XPS patterns of platinum of the resulting dendritic platinum nanoparticles are shown in fig. 7. The linear scanning voltammetry curve, the specificity activity and the mass activity of the forward peak potential of the obtained dendritic platinum nanoparticles at the scanning speed of 50mV/s are shown in figure 8, and the polarographic current time curve and the cyclic voltammetry curve of CO detachment of the obtained dendritic platinum nanoparticles are shown in figure 9.
As can be seen from the TEM image, the platinum-palladium-phosphorus alloy has the same dendritic structure as the single metal platinum. Dendritic platinum has electrocatalytic formic acid oxidation performance as can be seen from linear sweep voltammograms. As can be seen from the polarographic current-time curve, the dendritic platinum has good stability in the catalysis process; the dendritic platinum has better CO poisoning resistance as can be seen from the cyclic voltammetry curve of CO stripping.
Example 3:
a preparation method of dendritic platinum-palladium-phosphorus nanoparticles for catalyzing formic acid oxidation reaction comprises the following steps:
(1) respectively preparing a chloroplatinic acid solution with the concentration of 10mM and an ascorbic acid solution with the concentration of 0.05M;
(2) taking a chloroplatinic acid solution with the volume of 5mL, then adding 20mg of Brij58, finally adding 1mL of ascorbic acid solution, and uniformly mixing;
(3) after the solutions are fully mixed, the mixture is placed in an ultrasonic cleaning machine, after 5min of reaction at room temperature, the mixture is centrifugally separated, precipitates are collected and washed to obtain dendritic platinum nano particles, and the precipitates are dispersed in 2mL of aqueous solution again;
(4) dissolving 5mg of tetrakis (triphenylphosphine) palladium in 22mL of oleylamine, and mixing with the dendritic platinum nanoparticle solution; and transferring the mixed solution into a hydrothermal reaction kettle, reacting for 5 hours at 100 ℃, centrifugally separating, collecting precipitates, and washing with ethanol to remove residual tetrakis (triphenylphosphine) palladium and oleylamine to obtain a product.
In the first step, the concentration of chloroplatinic acid is low, and thus little catalyst product is synthesized. The amount of the surfactant Brij58 in the reaction is small, the appearance of a sample cannot be effectively regulated, the reaction time is short, and the reduction effect is not ideal, so that the dendritic platinum nanoparticles are difficult to synthesize. In the second step of reaction, the added amount of the tetrakis (triphenylphosphine) palladium is less, the heating temperature is lower, and the tetrakis (triphenylphosphine) palladium is not easy to decompose, so that palladium and phosphorus elements are difficult to be doped into platinum elements, and the platinum-palladium-phosphorus dendritic nanoparticles are difficult to obtain.
Example 4:
a preparation method of dendritic platinum-palladium-phosphorus nanoparticles for catalyzing formic acid oxidation reaction comprises the following steps:
(1) respectively preparing a chloroplatinic acid solution with the concentration of 100mM and an ascorbic acid solution with the concentration of 0.5M;
(2) taking 5mL of chloroplatinic acid solution, then adding 100mg of Brij58, finally adding 10mL of ascorbic acid solution, and uniformly mixing;
(3) after the solutions are fully mixed, the mixture is placed in an ultrasonic cleaning machine, reaction is carried out for 60min at room temperature, centrifugal separation, precipitation collection and washing are carried out to obtain dendritic platinum nano particles, and the precipitation is dispersed in 2mL of aqueous solution again;
(4) dissolving 80mg of tetrakis (triphenylphosphine) palladium in 22mL of oleylamine, and mixing with the dendritic platinum nanoparticle solution; and transferring the mixed solution into a hydrothermal reaction kettle, reacting for 20h at 200 ℃, centrifugally separating, collecting precipitate, and washing with ethanol to remove residual tetrakis (triphenylphosphine) palladium and oleylamine to obtain a product.
In the first step of reaction, the concentration of chloroplatinic acid is high, the reduction rate of the metal precursor is influenced, and the product is easy to generate nanoparticles with irregular shapes and nonuniform particle diameters, which is not beneficial to controlling the morphology structure of the dendritic platinum. In the second step, the added amount of the tetrakis (triphenylphosphine) palladium is excessive, and the decomposed excessive tetrakis (triphenylphosphine) palladium is easy to generate irregular agglomerated particles, so that the specific surface area and the exposed catalytic active sites of the catalyst are reduced, and the electrocatalytic formic acid oxidation reaction is not facilitated.
Claims (3)
1. A platinum-palladium-phosphorus dendritic nanoparticle for catalyzing formic acid oxidation reaction is prepared by the following steps:
(1) respectively preparing chloroplatinic acid solution with the concentration of 10-100 mM and ascorbic acid solution with the concentration of 0.05-0.5M;
(2) taking a chloroplatinic acid solution with the volume of 5mL, adding 20-100 mg of Brij58, finally adding 1-10 mL of ascorbic acid solution, and uniformly mixing;
(3) after the solutions are fully mixed, placing the mixture in an ultrasonic cleaning machine, reacting for 5-60 min at room temperature, carrying out centrifugal separation, collecting precipitates, washing to obtain dendritic platinum nanoparticles, and dispersing the precipitates in 2mL of aqueous solution again;
(4) dissolving 5-80 mg of tetrakis (triphenylphosphine) palladium in 22mL of oleylamine, and mixing with the dendritic platinum nanoparticle solution; and transferring the mixed solution into a hydrothermal reaction kettle, reacting for 5-20 h at 100-200 ℃, performing centrifugal separation, collecting precipitates, and washing with ethanol to remove residual tetrakis (triphenylphosphine) palladium and oleylamine to obtain the platinum-palladium-phosphorus dendritic nanoparticles.
2. A method for the preparation of platinum palladium phosphorous dendritic nanoparticles for catalysing formic acid oxidation according to claim 1, characterized in that said method comprises the following steps:
(1) respectively preparing chloroplatinic acid solution with the concentration of 10-100 mM and ascorbic acid solution with the concentration of 0.05-0.5M;
(2) taking a chloroplatinic acid solution with the volume of 5mL, adding 20-100 mg of Brij58, finally adding 1-10 mL of ascorbic acid solution, and uniformly mixing;
(3) after the solutions are fully mixed, placing the mixture in an ultrasonic cleaning machine, reacting for 5-60 min at room temperature, carrying out centrifugal separation, collecting precipitates, washing to obtain dendritic platinum nanoparticles, and dispersing the precipitates in 2mL of aqueous solution again;
(4) dissolving 5-80 mg of tetrakis (triphenylphosphine) palladium in 22mL of oleylamine, and mixing with the dendritic platinum nanoparticle solution; and transferring the mixed solution into a hydrothermal reaction kettle, reacting for 5-20 h at 100-200 ℃, performing centrifugal separation, collecting precipitates, and washing with ethanol to remove residual tetrakis (triphenylphosphine) palladium and oleylamine to obtain the platinum-palladium-phosphorus dendritic nanoparticles.
3. The method of claim 2, wherein the morphology and structure of the platinum-palladium-phosphorus dendritic nanoparticles are controlled by controlling the concentration of chloroplatinic acid, the amount of surfactant, the concentration and volume of ascorbic acid, the amount of tetrakis (triphenylphosphine) palladium added, and the temperature and time of the reaction.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112366327A (en) * | 2020-11-04 | 2021-02-12 | 湖北大学 | GO-MOF (Al) -supported palladium-bismuth-phosphorus alloy nano catalyst and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105552394A (en) * | 2015-12-09 | 2016-05-04 | 郑州轻工业学院 | Method for solid phase reaction one-step preparation of reduced graphene oxide/palladium composite nanometer electrocatalyst |
| CN109364964A (en) * | 2018-11-27 | 2019-02-22 | 浙江工业大学 | A kind of platinum palladium nickel-phosphorus alloy porous nano microballoon and preparation method thereof of catalytic oxidation-reduction reaction |
| CN110224149A (en) * | 2019-05-31 | 2019-09-10 | 东华大学 | A kind of nano carbon composite material is palladium catalyst and its preparation and the application of carrier |
-
2019
- 2019-11-21 CN CN201911145214.7A patent/CN110993973A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105552394A (en) * | 2015-12-09 | 2016-05-04 | 郑州轻工业学院 | Method for solid phase reaction one-step preparation of reduced graphene oxide/palladium composite nanometer electrocatalyst |
| CN109364964A (en) * | 2018-11-27 | 2019-02-22 | 浙江工业大学 | A kind of platinum palladium nickel-phosphorus alloy porous nano microballoon and preparation method thereof of catalytic oxidation-reduction reaction |
| CN110224149A (en) * | 2019-05-31 | 2019-09-10 | 东华大学 | A kind of nano carbon composite material is palladium catalyst and its preparation and the application of carrier |
Non-Patent Citations (1)
| Title |
|---|
| CHUNJIE LI等: "Facile dual tuning of PtPdP nanoparticles by metal–nonmetal co-incorporation and dendritic engineering for enhanced formic acid oxidation electrocatalysis", 《NANOTECHNOLOGY》 * |
Cited By (1)
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| CN112366327A (en) * | 2020-11-04 | 2021-02-12 | 湖北大学 | GO-MOF (Al) -supported palladium-bismuth-phosphorus alloy nano catalyst and preparation method thereof |
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