CN113948729A - Preparation method of binary metal platinum-palladium prismatic catalyst and application of catalyst in direct methanol fuel cell - Google Patents
Preparation method of binary metal platinum-palladium prismatic catalyst and application of catalyst in direct methanol fuel cell Download PDFInfo
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Abstract
The invention belongs to the technical field of fuel cell catalysts, and relates to a preparation method of a binary metal platinum-palladium prismatic catalyst, which comprises the following steps: dissolving a platinum precursor and a palladium precursor in a solvent containing a reducing agent, uniformly stirring, adding a surfactant for dispersion, then adding a carbon carrier, and uniformly mixing by ultrasonic to obtain a precursor solution; and then transferring the precursor solution to a reaction kettle, carrying out hydrothermal reaction at 120-200 ℃ for 16-28 h, cooling to room temperature, centrifuging, washing with deionized water and absolute ethyl alcohol until no impurities exist, and drying to obtain the catalyst. The invention has simple synthetic process, easy operation, good repeatability, high yield and excellent product performance, can be produced in large scale and is beneficial to commercial popularization. The synthesized platinum-palladium direct methanol fuel cell alloy catalyst has a prism shape, has higher activity and durability compared with commercial platinum carbon and platinum-ruthenium carbon, is obviously superior to the catalytic performance of commercial Pt/C catalysts, and has good application prospect and economic value.
Description
Technical Field
The invention belongs to the technical field of fuel cell catalysts, relates to a methanol fuel cell catalyst, and particularly relates to a preparation method of a binary metal platinum-palladium prismatic catalyst and application of the binary metal platinum-palladium prismatic catalyst to a direct methanol fuel cell.
Background
Since the human beings enter the modern society, the rapid development of science and technology promotes industrialization, the process of urbanization is accelerated continuously, and the traditional energy sources including coal, petroleum, natural gas and the like are reduced rapidly due to large consumption and non-regeneration. In order to promote the long-term well-being of human beings, the search for clean and renewable new energy sources becomes a hot topic of research of people at present. The fuel cell is a promising traditional substitute in the development of new energy due to the characteristics of easy fuel acquisition, renewability, environmental friendliness and the like. One of the types is a direct methanol fuel cell using methanol as fuel, which has high energy density, and the product only contains water and carbon dioxide, and does not contain toxic gases such as nitrogen oxides which can cause serious harm to the environment. However, slow cathode reaction kinetics restrict the industrial development of the direct methanol fuel cell, and the industry competitiveness of the direct methanol fuel cell needs to be enhanced by reducing the platinum loading and improving the utilization rate of the platinum-based catalyst.
Platinum-based catalysts are known to be the most intrinsically active material in fuel cell catalysts, but they also have some considerable disadvantages that need to be addressed. On one hand, carbon monoxide generated in the methanol oxidation reaction process can be adsorbed on platinum metal active sites, so that a subsequent reaction intermediate cannot be oxidized in time to influence the overall reaction progress; on the other hand, as a precious metal with a very small storage amount in the earth crust, the development price of the precious metal is high, which also greatly increases the cost of the fuel cell, and further development of the fuel cell is a great challenge. Therefore, some improvement methods are needed to enhance the carbon monoxide poisoning resistance of platinum, increase the utilization rate of platinum metal, reduce the use cost, and promote the commercialization and generalization of fuel cells.
In the current research progress, alloying doping by adopting transition metal and platinum becomes an important means for improving the utilization rate of platinum, enhancing the short-term catalytic stability and improving the long-term catalytic durability. Firstly, the transition metal alloying can adjust the electronic structure of platinum through electron donation, and properly reduce the d-band center, thereby influencing the binding energy of platinum and an intermediate and enhancing the poisoning resistance of the catalyst material. And secondly, the transition metal is added to form a catalyst with low platinum load, so that the use cost of the battery is reduced.
Chinese patent 202110400965. X discloses a synthesis method of a high-efficiency Pt-based methanol nano-catalyst, and a PtNi nano-particle is synthesized by a solvothermal method and used for methanol catalytic reaction. The method has the advantages of simple synthesis process, mild conditions, environmental friendliness and good reproducibility, and indicates that the catalyst synthesized by the method effectively improves the methanol oxidation performance by three times compared with the commercial catalyst. However, the pure alloy nanoparticles can cause a certain amount of platinum metal to be buried in the alloy, and cannot contact with reactants to play a catalytic role, thereby causing cost waste. In order to further improve the utilization of platinum metals, researchers have been working on the synthesis of alloy catalyst materials with specific morphologies. Especially, the alloy material with a platinum-rich surface is synthesized, and the catalytic performance is exerted to the maximum extent by increasing the electrochemical active surface area.
Chinese patent 201910962000.2 discloses a preparation method of platinum-rhodium-yttrium nanowires applied to the field of electrocatalysis. The ternary alloy nanowire is prepared in the hydrothermal reaction by combining the surfactant and the structure directing agent, has larger specific surface area, a large number of active sites and high electron transmission efficiency, and has higher catalytic performance, and meanwhile, compared with a platinum catalyst, the platinum-rhodium-yttrium nanowire reduces the content of metal platinum, enhances the CO poisoning resistance, and thus improves the capability of electrochemically catalyzing methanol oxidation.
Therefore, the combination of alloying and special morphology to take the greatest advantage of platinum-based catalysts is a promising direction of improvement. There are related studies to summarize the relationship between intrinsic catalytic activity and binding energy of a large number of metals, and a volcano diagram of metal catalytic reaction is drawn, and palladium is the second element to platinum, which is closest to the top of the volcano diagram, and has received extensive attention from researchers. Palladium is taken as an element in the same group with platinum, the palladium and the platinum have similar electronic structures, the lattice adaptation rate with platinum is as high as 97%, and palladium metal serving as a catalyst material has certain catalytic capability, so that the preparation of a platinum-palladium alloy with a special morphology to improve the activity and stability of the catalyst becomes an intelligent means.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to synthesize the binary alloy catalyst with the platinum-rich surface and the nano prism structure by an in-situ preparation method, improve the catalytic performance of platinum by doping palladium element, improve the utilization rate and the adhesive force of noble metal raw materials, reduce the preparation cost of the catalyst and apply the catalyst to a fuel cell.
A preparation method of a binary metal platinum-palladium prismatic catalyst comprises the following steps:
(1) dissolving a platinum precursor and a palladium precursor in a solvent containing a reducing agent, uniformly stirring, adding a surfactant for dispersion, then adding a carbon carrier, and uniformly mixing by ultrasonic to obtain a precursor solution; wherein the mole and volume ratio of the platinum precursor to the palladium precursor to the solvent containing the reducing agent is 1-4 mmol: 10-50 mL, preferably 1mmol:1mmol:30 mL; the molar ratio of the metal precursor to the surfactant is 1mmol: 3-6 mmol, preferably 1mmol:5 mmol; the solid-to-liquid ratio of the carbon carrier to the solvent containing the reducing agent is 1-5 mg: 1-2 ml, preferably 2mg:1 ml;
(2) and transferring the precursor solution to a reaction kettle, carrying out hydrothermal reaction at 120-200 ℃ for 16-28 h, preferably at 160 ℃ for 24h, cooling to room temperature, centrifuging, washing with deionized water and absolute ethyl alcohol until no impurities exist, and drying to obtain the platinum-palladium alloy catalyst.
In a preferred embodiment of the present invention, the platinum precursor in step (1) is any one of chloroplatinic acid hexahydrate, ammonium chloroplatinate, sodium chloroplatinate, platinum bis (acetylacetonate) or potassium chloroplatinate, preferably platinum bis (acetylacetonate); the palladium precursor is any one of sodium tetrachloropalladate, ammonium chloropalladate, palladium chloride, bis (acetylacetone) palladium, potassium chloropalladate or potassium chloropalladite, and preferably bis (acetylacetone) palladium.
In a preferred embodiment of the present invention, the solvent in step (1) is one or more of ultrapure water, deionized water, absolute ethanol, isopropanol, acetone, oleylamine, dimethyl sulfoxide, toluene, or N, N-dimethylformamide, preferably N, N-dimethylformamide.
In the preferred embodiment of the present invention, the surfactant in step (1) is one or more of cetyltrimethylammonium bromide, cetyltrimethylammonium chloride, polyvinylpyrrolidone, pluronic-F127 or tetradecyltrimethylammonium bromide, preferably tetradecyltrimethylammonium bromide.
In a preferred embodiment of the present invention, the reducing agent in step (1) is one or more of sodium citrate, glucose, ascorbic acid, L-ascorbic acid, ethylene glycol, N-dimethylformamide or sodium borohydride, preferably N, N-dimethylformamide.
In a preferred embodiment of the present invention, the molar ratio of the reducing agent to the solvent in step (1) is 1-5: 1-5, preferably 1:1.
In a preferred embodiment of the present invention, the carbon carrier in step (1) is any one of carbon powder, short multi-walled carbon nanotubes, oxygen-reduced graphene, carbon aerogel, carbon nanofibers, hollow carbon, mesoporous carbon, and carbon nano molecular sieves, and is preferably carbon powder.
In the preferred embodiment of the invention, in the step (1), the mass ratio of the total mass of the platinum and the palladium obtained by reduction to the carbon carrier is 1: 1.5-5, preferably 1: 4.
The binary metal platinum-palladium nanometer prismatic catalyst prepared by the method is formed by alloying two noble metals platinum and palladium loaded on a carbon carrier, has the size of 5-10nm, and is nanometer prismatic particles uniformly dispersed on the carbon carrier.
It is still another object of the present invention to apply the prepared catalyst to a direct methanol fuel cell.
Advantageous effects
The invention has simple synthetic process, easy operation and good repeatability. When the catalyst is used for a methanol oxidation test, the results show that: the synthesized platinum-palladium direct methanol fuel cell alloy catalyst has a prism shape, and has higher activity and durability compared with commercial platinum carbon and commercial platinum-ruthenium carbon. The simple synthesis steps can be used for mass production, and the high yield and the product performance are favorable for commercial popularization. Has better catalytic performance than commercial Pt/C catalyst, and has good application prospect and economic value.
Drawings
FIG. 1 is a TEM image of different magnifications of a binary metal platinum-palladium direct methanol fuel cell catalyst prepared in example 1;
FIG. 2 methanol Oxidation analytical characterization of example 1, comparative example 1 (CV characterization, 0.1M HClO)4 +0 .5 M CH3Testing in OH mixed solution);
FIG. 3 electrochemical stability characterization of example 1, comparative example 1 (chronoamperometric curve, 0.1M HClO)4 +0 .5 M CH3Test in OH mixed solution).
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. It is emphasized that the embodiments described below are merely some, but not all embodiments of the invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A preparation method of a binary metal platinum-palladium prismatic catalyst comprises the following steps:
(1) taking 0.05mmol (19.665 mg) of platinum acetylacetonate and 0.05mmol (15.232 mg) of palladium acetylacetonate as metal precursors, adding the metal precursors into a beaker containing 30mL of DMF and 200mg of TTAB, and stirring for 10-20 min to mix uniformly; adding 60mg carbon powder, performing ultrasonic treatment for 20min, and stirring for 20min to obtain a mixed solution;
(2) transferring the mixed solution to a reaction kettle, and reacting for 24 hours at 160 ℃; cooling to room temperature, washing and drying to obtain the binary metal platinum palladium prism catalyst.
The noble metal in the prepared catalyst is in a low-loading range, and the overall loading is about 20 wt%.
The prepared Pt-based metal nano prism is prismatic in appearance and 5-10nm in size.
And (3) characterizing by using a low-power scanning transmission electron microscope and a high-power scanning transmission electron microscope:
as shown in FIG. 1, the prepared product is clear in prism shape, is uniformly dispersed on a carbon carrier, and has an average size of 4.9 nm. Typical HRTEM images show an interplanar spacing of 0.231 nm, significantly smaller than the lattice spacing of pure Pt (111) planes (0.24 nm), which clearly indicates the formation of trimetallic alloy nanoprisms with an induced synergistic effect.
The methanol oxidation electrochemical performance was tested in a conventional three-electrode system.
FIG. 2 shows a binary platinum palladium prismatic catalyst with platinum ruthenium carbon and platinum carbon at 0.1M HClO4 +0 .5 M CH3Cyclic voltammogram in OH, wherein dashed dotted lines represent platinum carbon (Pt/C), dotted dashed lines represent platinum ruthenium carbon (PtRu/C), and thin solid lines represent the binary metal platinum palladium prismatic catalyst (PtPd/C). As is clear from the CV graphs, all catalysts exhibited two distinct oxidation peaks. The forward oxidation peak (anode) is associated with the electro-oxidation of methanol on the active surface of the metal catalyst, while the reverse oxidation peak (cathode) is the further oxidation of the carbon-containing intermediate species formed during the forward scan. Among them, the Mass Activity (MA) corresponding to the forward peak was used to evaluate the catalytic performance on methanol, as is evident from the graph, with PtRu/C (0.574A. mg)-1) And commercial Pt/C (0.386A. mg)-1) In contrast, the electrocatalytic properties of PtPd/C show improved mass activity (1.11A. mg)-1). Compared with Pt/C and PtRu/C catalysts, the catalyst is approximately 1.33 times and 1.20 times higher, thereby proving that the prepared catalyst has higher catalytic activity in acidic methanol solution.
FIG. 3 shows a binary platinum palladium prismatic catalyst with platinum ruthenium carbon and platinum carbon at 0.1M HClO4 +0 .5 M CH3Stability test chart in OH, wherein dashed line indicates platinum carbon (Pt/C), dotted line indicates platinumRuthenium carbon (PtRu/C), and the thin solid line represents the binary metal platinum palladium direct methanol fuel cell catalyst (PtPd/C). Figure 3 shows chronoamperometric curves for three catalysts to compare their short term stability. The current density of all the catalysts initially decreased rapidly due to the adsorption of intermediates on the catalyst surface, but the PtPd/C catalyst showed a relatively low rate of decrease compared to the Pt/C and PtRu/C catalysts, indicating that PtPd/C has excellent activity and resistance to methanol oxidation, further confirming the advantage of this alloy catalyst system with a special morphology.
Example 2
A preparation method of a binary metal platinum-palladium direct methanol fuel cell catalyst comprises the following steps:
(1) taking 0.05mmol (25.9 mg) of chloroplatinic acid hexahydrate and 0.05mmol (15.232 mg) of palladium acetylacetonate as metal precursors, adding the metal precursors into a beaker containing 30mL of ultrapure water, 50mg of AA and 200mg of TTAB, and stirring for 10-20 min to mix uniformly; adding 60mg carbon powder, performing ultrasonic treatment for 20min, and stirring for 20min to obtain a mixed solution;
(2) transferring the mixed solution to a reaction kettle, and reacting for 16h at 200 ℃; cooling to room temperature, washing and drying to obtain the binary metal platinum palladium prism catalyst.
The methanol oxidation activity of the binary metal platinum palladium catalyst is 0.960 A.mg through electrochemical test-1Is superior to PtRu/C (0.574A. mg)-1) And standard Pt/C (0.386A. mg)-1）。
Example 3
A preparation method of a binary metal platinum-palladium direct methanol fuel cell catalyst comprises the following steps:
(1) taking 0.05mmol (19.665 mg) of platinum acetylacetonate and 0.05mmol (8.87 mg) of palladium chloride as metal precursors, adding the metal precursors into a beaker containing 30mL of DMF and 200mg of CTAB, and stirring for 10-20 min to mix uniformly; adding 75mg carbon powder, performing ultrasonic treatment for 40min, and stirring for 40min to obtain a mixed solution;
(2) transferring the mixed solution to a reaction kettle, and reacting for 18h at 180 ℃; cooling to room temperature, washing and drying to obtain the binary metal platinum palladium prism catalyst.
The methanol oxidation activity of the binary metal platinum palladium catalyst is 0.980 A.mg through electrochemical tests-1Is superior to PtRu/C (0.574A. mg)-1) And standard Pt/C (0.386A. mg)-1）。
Example 4
A preparation method of a binary metal platinum-palladium direct methanol fuel cell catalyst comprises the following steps:
(1) taking 0.05mmol (25.9 mg) of chloroplatinic acid hexahydrate and 0.05mmol (8.87 mg) of palladium chloride as metal precursors, adding the metal precursors into a beaker containing 30mL of DMF, absolute ethyl alcohol and 200mg of TTAB, and stirring for 10-20 min to mix uniformly; adding 30mg of mesoporous carbon, performing ultrasonic treatment for 10min, and stirring for 10min to obtain a mixed solution;
(2) transferring the mixed solution to a reaction kettle, and reacting for 20 hours at 160 ℃; cooling to room temperature, washing and drying to obtain the binary metal platinum palladium prism catalyst.
Through electrochemical tests, the methanol oxidation activity of the obtained binary metal platinum-palladium catalyst is 0.991 A.mg-1Is superior to PtRu/C (0.574A. mg)-1) And standard Pt/C (0.386A. mg)-1）。
Example 5
A preparation method of a binary metal platinum-palladium direct methanol fuel cell catalyst comprises the following steps:
(1) taking 0.05mmol (25.9 mg) of chloroplatinic acid hexahydrate and 0.05mmol (8.87 mg) of palladium chloride as metal precursors, adding the metal precursors into a beaker containing 20mL of oleylamine, 50mg of AA and 300mg of TTAB, and stirring for 10-20 min to mix uniformly; adding 60mg carbon powder, performing ultrasonic treatment for 20min, and stirring for 20min to obtain a mixed solution;
(2) transferring the mixed solution to a reaction kettle, and reacting for 22 hours at 140 ℃; cooling to room temperature, washing and drying to obtain the binary metal platinum palladium prism catalyst.
The methanol oxidation activity of the binary metal platinum palladium catalyst is 0.910 A.mg through electrochemical tests-1Is superior to PtRu/C (0.574A. mg)-1) And standard Pt/C (0.386A. mg)-1）。
Example 6
A preparation method of a binary metal platinum-palladium direct methanol fuel cell catalyst comprises the following steps:
(1) taking 0.05mmol (20.5 mg) of potassium chloroplatinate and 0.05mmol (14.71 mg) of sodium chloropalladate as metal precursors, adding the metal precursors into a beaker containing 20mL of isopropanol, 50mg of sodium borohydride and 300mg of PVP, and stirring for 10-20 min to mix uniformly; then adding 45mg of oxygen to reduce the graphene, carrying out ultrasonic treatment for 20min, and stirring for 30min to obtain a mixed solution;
(2) transferring the mixed solution to a reaction kettle, and reacting for 24 hours at 160 ℃; cooling to room temperature, washing and drying to obtain the binary metal platinum palladium prism catalyst.
The methanol oxidation activity of the binary metal platinum palladium catalyst is 0.830 A.mg through electrochemical test-1Is superior to PtRu/C (0.574A. mg)-1) And standard Pt/C (0.386A. mg)-1）。
Example 7
A preparation method of a binary metal platinum-palladium direct methanol fuel cell catalyst comprises the following steps:
(1) taking 0.05mmol (25.9 mg) of chloroplatinic acid hexahydrate and 0.15mmol (26.61 mg) of palladium chloride as metal precursors, adding the metal precursors into a beaker containing 30mL of acetone, 20mg of sodium hydroxide, 40mg of sodium borohydride and 300mg of F127, and stirring for 10-20 min to mix uniformly; adding 45mg carbon powder, performing ultrasonic treatment for 20min, and stirring for 30min to obtain a mixed solution;
(2) transferring the mixed solution to a reaction kettle, and reacting for 28 hours at 120 ℃; cooling to room temperature, washing and drying to obtain the binary metal platinum palladium prism catalyst.
Through electrochemical tests, the methanol oxidation activity of the obtained binary metal platinum-palladium catalyst is 0.875 A.mg-1Is superior to PtRu/C (0.574A. mg)-1) And standard Pt/C (0.386A. mg)-1）。
Example 8
A preparation method of a binary metal platinum-palladium direct methanol fuel cell catalyst comprises the following steps:
(1) taking 0.2mmol (103.6 mg) of chloroplatinic acid hexahydrate and 0.05mmol (8.87 mg) of palladium chloride as metal precursors, adding the metal precursors into a beaker containing 30mLDMF, 20mg of ascorbic acid and 150mg of TTAB, and stirring for 10-20 min to mix uniformly; adding 75mg carbon aerogel, performing ultrasonic treatment for 40min, and stirring for 40min to obtain a mixed solution;
(2) transferring the mixed solution to a reaction kettle, and reacting for 26 hours at 140 ℃; cooling to room temperature, washing and drying to obtain the binary metal platinum palladium prism catalyst.
The methanol oxidation activity of the binary metal platinum-palladium catalyst is 0.896 A.mg through electrochemical tests-1Is superior to PtRu/C (0.574A. mg)-1) And standard Pt/C (0.386A. mg)-1）。
Example 9
A preparation method of a binary metal platinum-palladium direct methanol fuel cell catalyst comprises the following steps:
(1) taking 0.2mmol (103.6 mg) of chloroplatinic acid hexahydrate and 0.05mmol (8.87 mg) of palladium chloride as metal precursors, adding the metal precursors into a beaker containing 30mL of ultrapure water, 40mg of sodium citrate and 100mg of CTAC, and stirring for 10-20 min to mix uniformly; adding 45mg of carbon nano tube, performing ultrasonic treatment for 20min, and stirring for 30min to obtain a mixed solution;
(2) transferring the mixed solution to a reaction kettle, and reacting for 16h at 200 ℃; cooling to room temperature, washing and drying to obtain the binary metal platinum palladium prism catalyst.
Through electrochemical tests, the methanol oxidation activity of the obtained binary metal platinum-palladium catalyst is 0.871A mg-1Is superior to PtRu/C (0.574A. mg)-1) And standard Pt/C (0.386A. mg)-1）。
Example 10
A preparation method of a binary metal platinum-palladium direct methanol fuel cell catalyst comprises the following steps:
(1) taking 0.1mmol (51.8 mg) of chloroplatinic acid hexahydrate and 0.05mmol (8.87 mg) of palladium chloride as metal precursors, adding the metal precursors into a beaker containing 30mL of ultrapure water, 40mg of glucose and 200mg of CTAC, and stirring for 10-20 min to mix uniformly; adding 45mg carbon powder, performing ultrasonic treatment for 20min, and stirring for 30min to obtain a mixed solution;
(2) transferring the mixed solution to a reaction kettle, and reacting for 22 hours at 140 ℃; cooling to room temperature, washing and drying to obtain the binary metal platinum palladium prism catalyst.
Through electrochemical tests, the methanol oxidation activity of the binary metal platinum-palladium catalyst is 0.864 A.mg-1Is superior to PtRu/C (0.574A. mg)-1) And standard Pt/C (0.386A. mg)-1）。
Example 11
A method for preparing a direct methanol fuel cell catalyst can be used for preparing a platinum-ruthenium-carbon catalyst, and comprises the following steps:
(1) taking 0.2mmol (103.6 mg) of chloroplatinic acid hexahydrate and 0.05mmol (10.37 mg) of ruthenium chloride hydrate as metal precursors, adding the metal precursors into a beaker containing 30mLDMF, 20mg of ascorbic acid and 200mg of TTAB, and stirring for 10-20 min to mix uniformly; adding 75mg carbon powder, performing ultrasonic treatment for 40min, and stirring for 40min to obtain a mixed solution;
(2) transferring to a reaction kettle, reacting for 24h at 160 ℃, centrifuging, washing for several times until no impurities exist, drying and collecting to obtain the platinum ruthenium carbon catalyst. Wherein the Pt-based metal nano prism has a size of 5-10 nm.
The methanol oxidation activity of the obtained platinum-ruthenium-carbon catalyst is 0.881 A.mg through electrochemical tests-1Is superior to PtRu/C (0.574A. mg)-1) And standard Pt/C (0.386A. mg)-1）。
Comparative example 1
A preparation method of a direct methanol fuel cell catalyst can be used for preparing a platinum carbon catalyst, and comprises the following steps:
mixing chloroplatinic acid hexahydrate and carbon powder, ultrasonically stirring uniformly, placing into a three-neck flask, adding 30ml of DMF organic solvent, and taking DMF as a solvent and a reducing agent; then adding 40mg of carbon powder, and reducing to obtain pure platinum and carbon powder with the mass ratio of 1: 4; and uniformly mixing, transferring to a high-pressure reaction kettle, reacting at 160 ℃ for 24 hours, centrifuging, washing, drying and collecting to obtain the platinum-carbon ethanol fuel cell catalyst. The size of the obtained platinum-carbon metal particles is 6-10 nm.
The methanol oxidation activity of the obtained platinum-carbon catalyst is 0.875A-mg through electrochemical tests-1Is superior to PtRu / C（0.574A·mg-1) And standard Pt/C (0.386A. mg)-1）。
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (10)
1. A preparation method of a binary metal platinum-palladium prismatic catalyst is characterized by comprising the following steps:
(1) dissolving a platinum precursor and a palladium precursor in a solvent containing a reducing agent, uniformly stirring, adding a surfactant for dispersion, then adding a carbon carrier, and uniformly mixing by ultrasonic to obtain a precursor solution; wherein the mole and volume ratio of the platinum precursor to the palladium precursor to the solvent containing the reducing agent is 1-4 mmol: 10-50 mL, preferably 1mmol:1mmol:30 mL; the molar ratio of the metal precursor to the surfactant is 1mmol: 3-6 mmol, preferably 1mmol:5 mmol; the solid-to-liquid ratio of the carbon carrier to the solvent containing the reducing agent is 1-5 mg: 1-2 ml, preferably 2mg:1 ml;
(2) and transferring the precursor solution to a reaction kettle, carrying out hydrothermal reaction at 120-200 ℃ for 16-28 h, preferably 160 ℃ for 24h, cooling to room temperature, centrifuging, washing with deionized water and absolute ethyl alcohol until no impurities exist, and drying to obtain the catalyst.
2. The method of preparing a binary platinum palladium prismatic catalyst as claimed in claim 1, wherein: the platinum precursor in the step (1) is any one of chloroplatinic acid hexahydrate, ammonium chloroplatinate, sodium chloroplatinate, bis (acetylacetone) platinum or potassium chloroplatinate, and preferably bis (acetylacetone) platinum; the palladium precursor is any one of sodium tetrachloropalladate, ammonium chloropalladate, palladium chloride, bis (acetylacetone) palladium, potassium chloropalladate or potassium chloropalladite, and preferably bis (acetylacetone) palladium.
3. The method of preparing a binary platinum palladium prismatic catalyst as claimed in claim 1, wherein: in the step (1), the solvent is one or more of ultrapure water, deionized water, absolute ethyl alcohol, isopropanol, acetone, oleylamine, dimethyl sulfoxide, toluene or N, N-dimethylformamide, and preferably the N, N-dimethylformamide.
4. The method of preparing a binary platinum palladium prismatic catalyst as claimed in claim 1, wherein: the surfactant in the step (1) is one or more of cetyl trimethyl ammonium bromide, cetyl trimethyl ammonium chloride, polyvinylpyrrolidone, pluronic-F127 or tetradecyl trimethyl ammonium bromide, preferably tetradecyl trimethyl ammonium bromide.
5. The method of preparing a binary platinum palladium prismatic catalyst as claimed in claim 1, wherein: in the step (1), the reducing agent is one or more of sodium citrate, glucose, ascorbic acid, L-ascorbic acid, ethylene glycol, N-dimethylformamide or sodium borohydride, and preferably N, N-dimethylformamide.
6. The method of preparing a binary platinum palladium prismatic catalyst as claimed in claim 1, wherein: the molar ratio of the reducing agent to the solvent in the step (1) is 1-5: 1-5, preferably 1:1.
7. The method of preparing a binary platinum palladium prismatic catalyst as claimed in claim 1, wherein: the carbon carrier in the step (1) is any one of carbon powder, short multi-walled carbon nanotubes, oxygen-reduced graphene, carbon aerogel, carbon nanofibers, hollow carbon, mesoporous carbon and carbon nano molecular sieves, and preferably carbon powder.
8. The method of preparing a binary platinum palladium prismatic catalyst as claimed in claim 1, wherein: in the step (1), the mass ratio of the total mass of the platinum and the palladium obtained by reduction to the carbon carrier is 1: 1.5-5, preferably 1: 4.
9. A binary metal platinum palladium prismatic catalyst prepared according to the method of any one of claims 1 to 8.
10. Use of a catalyst according to claim 9, wherein: it is applied to a direct methanol fuel cell.
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