CN107342427B - Preparation method of Pd/Ag nano alloy catalyst for direct ethanol fuel cell - Google Patents
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Abstract
The invention discloses a preparation method of a Pd/Ag nano alloy catalyst for a direct ethanol fuel cell. Adding alcohol into water according to the volume ratio of 3-7: 1, stirring, respectively adding polyvinylpyrrolidone, a metal palladium salt precursor, a metal silver salt precursor and sodium citrate, stirring at 20-25 ℃ for 1.5-2.5 h, reacting for 1.8-12 h under the illumination condition, centrifugally separating, collecting precipitate, washing and drying to obtain the Pd/Ag nano alloy catalyst. The invention takes polyvinylpyrrolidone as a stabilizer and a guiding agent, and utilizes the reduction action of alcohol and sodium citrate to synthesize the Pd/Ag nano alloy catalyst in one step under mild conditions, thereby not only improving the synthesis efficiency and the yield, but also having controllability of the morphology of the catalyst, better catalytic activity on ethanol, being capable of being used as a catalyst of a direct ethanol fuel cell, and having simple preparation process, short production period, easy large-scale production and good application prospect.
Description
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of a Pd/Ag nano alloy catalyst for a direct ethanol fuel cell.
Background
Direct Alcohol Fuel Cells (DAFC) are a type of electrochemical reaction device that directly converts chemical energy of Fuel (methanol, ethanol, etc.) into electrical energy. Because the DAFC has the characteristics of rich fuel resources, low operating temperature, high specific energy density, convenience in storage and carrying and the like, the DAFC becomes one of new energy technologies for international fuel cell research and development at present. However, this technology still has a few technological bottlenecks, and the performance and cost of its catalyst have been two key factors that hinder its commercialization process. DAFC belongs to low-temperature fuel cells, and the operating temperature of the DAFC generally does not exceed 100 ℃, and at the temperature, most transition metals have low catalytic oxidation activity to hydrogen and organic small molecules, so that noble metal platinum (Pt) is generally adopted as a catalyst, however, Pt is a scarce resource, the price of Pt is very high, and Pt is easily poisoned in the catalytic reaction process, so that the large-scale application of DAFC is limited to a certain extent. The palladium (Pd) catalyst is excellent in activity, comparable to Pt, and only 1/3, which is the latter price, and this is advantageous in reducing the cost of the catalyst; in addition, research shows that Pd has better electrocatalytic performance than Pt for organic small molecules such as methanol and ethanol, and is considered to be one of important alternative materials for Pt. Meanwhile, on the basis of the research of the single metal Pd, another metal is introduced into the system to form the nano alloy, so that the dosage of the Pd is reduced, the introduced second metal is favorable for the oxidation of strong adsorption residues, a certain synergistic effect is shown, and the catalytic activity, the anti-poisoning property, the selectivity and the stability of the catalyst can be improved. In recent years, the Pd-containing single/double metal catalyst has been actively researched scientifically for electrocatalysis of organic small molecules, and particularly, the Pd/Ag alloy nano catalyst has attracted extensive attention in the research of fuel cells.
For example, chinese patent application 201510569877.7 discloses a method for preparing nano-palladium-silver alloy for fuel cell, which comprises preparing PVP solution and AgNO respectively with ethylene glycol as solvent3A solution and a glycol solution of sodium chloride; using deionized water as solvent to respectively prepare saturated sodium chloride aqueous solution and PdCl2Mixing ethylene glycol and sodium chloride ethylene glycol solution, stirring for 0.9-1.1 h at 155-165 ℃, and then adding the first part of AgNO3The solution is uniformly dripped into the solution, and after dripping is finished within two minutes, dripping of a second part of AgNO is started simultaneously3Uniformly dripping the solution and the PVP solution within 5 min; stirring the obtained solution at 155-165 ℃ for 40-50 min, and cooling at room temperature to obtain silver nanowires; adding deionized water into the obtained solution containing the silver nanowires, and then dropwise adding freshly prepared PdCl into the solution at room temperature2After the solution is dropwise added, continuously stirring at room temperature for 11.5-12.5 h; separating solid from liquid in the obtained solution, washing the obtained product with saturated sodium chloride water solution, and purifying with sodium chloride water solutionWashing with water and ethanol to obtain the Pd/Ag alloy nanotube catalyst. Chinese patent application 201510194588.3 also discloses a method for preparing a carbon-supported palladium-silver nano composite catalyst for a direct methanol fuel cell, wherein Vulcan XC-72R activated carbon, polyvinylpyrrolidone, PdCl are respectively added into a three-neck flask2Completely dissolving polyvinylpyrrolidone by ultrasonic dispersion for 30 min and uniformly dispersing active carbon in the mixed solution; adding NaOH aqueous solution under the condition of continuous stirring; continuously stirring for 10 min, adding AgNO into the three-neck flask3An aqueous solution; continuously stirring for 10 min, and quickly adding 20 ml of 128-256 mgNaBH into a three-neck flask4Preparing a solution; stirring for 24 h continuously, stopping stirring, and standing for 24 h; filtering, fully washing, and drying for 6 hours at 80 ℃ by using a vacuum drying oven to obtain the carbon-supported palladium-silver nano composite catalyst.
However, the existing technologies for synthesizing Pd/Ag nano-alloys generally have the problems of harsh reaction conditions, complex procedures, addition of a large amount of reducing agents during the preparation process, difficulty in controlling the reaction conditions during the preparation process, or high-energy radiation and other test conditions during the preparation process, which results in high cost, uneven products, difficulty in industrial production and the like, and limit further application of Pd/Ag nano-alloys in direct alcohol fuel cells to a certain extent.
In addition, it has been reported recently that the synthesis of palladium-silver nano-alloy catalyst by photochemical and light irradiation synthesis using high-energy radiation as radiation source has the characteristics of simplicity, easy operation and good uniformity of the product, and the growth mechanism of the material synthesized by the method is easy to understand, thus becoming a new method for controlling and synthesizing nano-catalyst with various sizes and shapes. However, laser, ultraviolet light and gamma radiation are easy to damage the body of an operator, and the cost is high, so that the application and popularization have certain limitations. Therefore, there is a need to find a safe, cheap, simple and feasible method for controllably synthesizing palladium-silver nano-alloy catalyst.
Disclosure of Invention
The invention aims to solve the technical problems of the prior art and provides a preparation method of a Pd/Ag nano alloy catalyst for a direct ethanol fuel cell, which has mild process conditions, low requirements on equipment and good product uniformity, is synthesized in one step.
The invention also aims to provide the Pd/Ag nano alloy catalyst obtained by the preparation method.
The invention further aims to provide application of the Pd/Ag nano alloy in serving as a catalyst for a direct ethanol fuel cell.
The above purpose of the invention is realized by the following technical scheme:
a preparation method of a Pd/Ag nano alloy catalyst for a direct ethanol fuel cell comprises the following steps: adding alcohol into water according to the volume ratio of 3-7: 1, stirring, respectively adding polyvinylpyrrolidone, a metal palladium salt precursor, a metal silver salt precursor and sodium citrate, stirring at 20-25 ℃ for 1.5-2.5 h, reacting for 1.8-12 h under the illumination condition, centrifuging, collecting precipitate, washing and drying to obtain the Pd/Ag nano alloy catalyst; wherein the weight ratio of polyvinylpyrrolidone: metal palladium salt precursor: metal silver salt precursor: the mass ratio of the sodium citrate is 8-60: 0.5-3.5: 0.1-6: 0-0.5.
Preferably, the polyvinylpyrrolidone: the mass ratio of the metal palladium salt precursor to the metal silver salt precursor to the sodium citrate is 9.8-58.92: 0.7-3: 0.2-5.2: 0.1-0.4.
More preferably, the polyvinylpyrrolidone: the mass ratio of the metal palladium salt precursor to the metal silver salt precursor to the sodium citrate is 9.82:0.7:1.2: 0.4.
Preferably, the volume ratio of alcohol to water is 5: 1.
Preferably, the alcohol is ethanol or ethylene glycol.
Preferably, the metal palladium salt precursor is palladium nitrate.
Preferably, the metal silver salt precursor is silver nitrate.
Preferably, the lighting condition is visible light irradiation.
Preferably, the light source for illumination is an incandescent lamp or an energy-saving lamp.
More preferably, the light source for illumination is an incandescent lamp, and the illumination condition is 200W illumination for 2 h.
Preferably, the washing conditions are 2 times of centrifugal washing with absolute ethyl alcohol and deionized water, respectively.
Preferably, the drying is vacuum drying, the drying temperature is 35-45 ℃, and the drying time is 12-48 h.
More preferably, the drying is vacuum drying at 35 ℃ for 48 h.
The Pd/Ag nano-alloy catalyst prepared by the method and the application of the Pd/Ag nano-alloy catalyst in the aspect of being used as a catalyst for a direct ethanol fuel cell are also within the protection scope of the invention.
Compared with the prior art, the invention has the following outstanding advantages:
1. the Pd/Ag nano alloy catalyst for the direct ethanol fuel cell, which is prepared in the normal-temperature and normal-pressure environment, has the advantages of mild process conditions, low requirement on equipment, short production period and good product uniformity;
2. the Pd/Ag nano alloy catalyst is synthesized in one step by virtue of the reduction action of alcohol and sodium citrate, so that the method is low in cost, environment-friendly and simple and easy to operate;
3. the common visible light source is adopted as an auxiliary means, so that the defects that high-energy radiation such as laser, ultraviolet light, gamma radiation and the like causes harm to the body of an operator and the cost is high are overcome, and the limitations that the requirements on instruments and equipment are high, the production cost is high and the like are overcome;
4. the method synthesizes the Pd/Ag nano-alloy catalysts with different shapes and sizes in one step by changing the concentration of the precursor and the dosage of the reducing agent, and realizes the shape and size regulation of the nano-alloy catalyst;
5. the Pd/Ag nano alloy modified electrode prepared by the method has good electro-catalytic activity on ethanol under alkaline conditions, can be used as a catalyst for a direct ethanol fuel cell, and has good application prospect;
6. the nano Pd/Ag alloy catalyst prepared by the method has high yield of 90-96 percent, and is suitable for industrial production.
Drawings
FIG. 1 is an XRD diffraction pattern of the Pd/Ag nano-alloy catalyst prepared in example 1 of the present invention.
FIG. 2 is an EDS diagram of a Pd/Ag nano-alloy catalyst prepared in example 1 of the present invention.
FIG. 3 is a TEM image of the Pd/Ag nano-alloy catalyst prepared in example 1 of the present invention.
FIG. 4 is a TEM image of the Pd/Ag nano-alloy catalyst prepared in example 2 of the present invention.
FIG. 5 is a TEM image of the Pd/Ag nano-alloy catalyst prepared in example 3 of the present invention.
FIG. 6 is a TEM image of the Pd/Ag nano-alloy catalyst prepared in example 4 of the present invention.
FIG. 7 is a graph illustrating the electrocatalytic activity of the Pd/Ag nano-alloy catalysts prepared in examples 1, 2, 3 and 4 of the present invention on ethanol oxidation (nano-Pd/Ag nano-alloy loading on the surface of the electrode is 48 μ g/cm)2The electrolyte is 1mol/L ethanol solution in 1mol/L KOH, the scanning speed is 50 mV/s, and the three-electrode system comprises: a nano Pd/Ag nano alloy modified glassy carbon electrode (Pd/GCE) is used as a working electrode, a Saturated Calomel Electrode (SCE) is used as a reference electrode, and a platinum wire electrode is used as an auxiliary electrode); in the figure, a, b, c, d represent the catalysts prepared in examples 1 to 4, respectively.
Detailed Description
The invention is further explained by combining the attached drawings and the specific examples in the specification (the electro-catalytic activity of ethanol is used for evaluating the catalytic performance of the Pd/Ag nano alloy). The following examples are preferred embodiments of the present invention, but are not intended to limit the scope of the present invention in any manner. The invention mainly describes the catalyst and the application idea based on the catalyst, and the simple parameter replacement in the embodiment can not be described in detail in the embodiment, but the invention is not limited thereby, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the invention should be regarded as equivalent replacement ways which are included in the scope of the invention.
Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated. Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
Example 1
1. Preparation method
A Pd/Ag nano alloy catalyst for a direct ethanol fuel cell is prepared by the following method:
(1) sequentially adding 4 mL of water and 20 mL of ethanol into a reaction container, and stirring to obtain a water-ethanol mixed solution system;
(2) 0.007 g of Pd (NO)3)2Powder, 0.012 g AgNO3Adding 0.004 g of sodium citrate and 0.0982 g of PVP into a water-ethanol mixed solution system, and stirring the prepared solution in a constant-temperature magnetic stirrer at 20 ℃ for 2 hours;
(3) placing the uniformly stirred reaction solution in a self-designed illumination reaction box, and placing the reaction solution under the common commercial incandescent light of 200W for parallel illumination for 2 hours;
(4) centrifugally separating the obtained black precipitate, centrifugally washing the black precipitate for 2 times by using absolute ethyl alcohol and deionized water respectively, and drying the black precipitate in a vacuum oven at the temperature of 35 ℃ for 48 hours to obtain the Pd/Ag nano alloy catalyst material.
The yield of the Pd/Ag nano-alloy catalyst prepared by the method is 96%.
2. Product characteristics and physicochemical properties of Pd/Ag nano alloy catalyst
Transmission Electron Micrograph (TEM) and EDS were obtained from a JEOL-2010 transmission electron microscope, Japan Electron Co., Ltd; the X-ray diffraction (XRD) pattern of the sample was measured by an X-ray diffraction analyzer model XD-3, a general instruments ltd, beijing prosperous analysis (Cu target, Ka radiation, λ =0.15406 nm), the operating voltage was 36 kV, the tube current was 30 mA, and the Cyclic Voltammogram (CV) was obtained from electrochemical workstation CHI-660E, chenhua instruments ltd.
(1) The X-ray diffraction structure of the obtained Pd/Ag nano alloy catalyst is a face-centered cubic structure. As shown in fig. 1, the diffraction angle 2 θ of the nano Pd shows 5 diffraction peaks at 40.13 °, 46.44 °, 68.08 °, 81.98 ° and 86.30 °, which are characteristic peaks of the elemental diffraction crystal planes (111), (200), (220), (311) and (222) of the metallic Pd. The Pd/Ag nano alloy has a diffraction peak slightly shifted due to the existence of Ag, and the diffraction peak is between the diffraction peaks of Pd and Ag, indicating the generation of the alloy.
(2) As shown in fig. 2, the EDX spectrum of the catalyst indicated the presence of both Pd and Ag elements in the alloy.
(3) The microscopic morphology of the catalyst is shown in FIG. 3 and is in a nanowire structure.
(4) The electrocatalytic activity of the prepared Pd/Ag nano-alloy catalyst on ethanol oxidation is shown in fig. 7 (a): the initial oxidation potential for oxidizing the ethanol is-0.68V, the current of the nano Pd modified glassy carbon electrode in an ethanol solution is gradually increased in forward potential scanning, and a first oxidation peak I appears near-0.20V; during negative scanning, the current is gradually reduced until a second oxidation peak II appears near-0.38V; the current of the oxidation peak I is 1.22X 10-3A。
Example 2
1. Preparation method
A Pd/Ag nano alloy catalyst for a direct ethanol fuel cell is prepared by the following method:
(1) sequentially adding 4 mL of water and 20 mL of ethanol into a reaction container, and stirring to obtain a water-ethanol mixed solution system;
(2) 0.007 g of Pd (NO)3)2Powder, 0.005 g AgNO3Adding 0.001 g of sodium citrate and 0.098 g of PVP into a water-ethanol mixed solution system, and stirring the prepared solution in a constant-temperature magnetic stirrer at 23 ℃ for 2 hours;
(3) placing the uniformly stirred reaction solution in a self-designed illumination reaction box, and placing the reaction solution under the common commercial incandescent light of 200W for parallel illumination for 2 hours;
(4) centrifugally separating the obtained black precipitate, respectively centrifugally washing the black precipitate for 2 times by using absolute ethyl alcohol and deionized water, and drying the black precipitate in a vacuum oven at the temperature of 45 ℃ for 12 hours to obtain the Pd/Ag nano alloy catalyst material.
The yield of the Pd/Ag nano-alloy catalyst prepared by the method is 93%.
2. Product characteristics and physicochemical properties of Pd/Ag nano alloy catalyst
The experimental materials and experimental methods for the characteristics and physicochemical properties of the product were the same as those of example 1.
(1) The micro-morphology of the obtained Pd/Ag nano-alloy catalyst is shown in figure 4 and is in the shape of a nano-wire.
(2) The electrocatalytic activity of the prepared Pd/Ag nano-alloy catalyst on ethanol oxidation is shown in fig. 7 (b): the initial oxidation potential for oxidizing the ethanol is-0.65V, the current of the nano Pd modified glassy carbon electrode in an ethanol solution is gradually increased in forward potential scanning, and a first oxidation peak I appears near-0.28V; during negative scanning, the current is gradually reduced until a second oxidation peak II appears near-0.41V; the current of oxidation peak I is 4.56X 10-4A。
Example 3
1. Preparation method
A Pd/Ag nano alloy catalyst for a direct ethanol fuel cell is prepared by the following method:
(1) sequentially adding 6 mL of water and 12 mL of glycol into a reaction container, and stirring to obtain a water-alcohol mixed solution system;
(2) 0.007 g of Pd (NO)3)2、0.002 g AgNO3Adding 0.004 g of sodium citrate and 0.098 g of PVP into a water-ethanol mixed solution system, and stirring the prepared solution in a constant-temperature magnetic stirrer at 25 ℃ for 2 hours;
(3) placing the uniformly stirred reaction solution in a self-designed illumination reaction box, and placing the reaction solution under 15W of common commercial energy-saving lamp light for parallel illumination for 12 hours;
(4) centrifugally separating the obtained black precipitate, respectively centrifugally washing the black precipitate for 2 times by using absolute ethyl alcohol and deionized water, and drying the black precipitate in a vacuum oven at the temperature of 40 ℃ for 24 hours to obtain the Pd/Ag nano alloy catalyst material.
The yield of the Pd/Ag nano-alloy catalyst prepared by the method is 93%.
2. Product characteristics and physicochemical properties of Pd/Ag nano alloy catalyst
The experimental materials and experimental methods for the characteristics and physicochemical properties of the product were the same as those of example 1.
(1) The obtained Pd/Ag nano-alloy catalyst has a granular morphology as shown in figure 5.
(2) The electrocatalytic activity of the prepared Pd/Ag nano-alloy catalyst on ethanol oxidation is shown in fig. 7 (c): the initial oxidation potential for oxidizing the ethanol is-0.67V, the current of the nano Pd/Ag modified glassy carbon electrode in an ethanol solution is gradually increased in forward potential scanning, and a first oxidation peak I appears near-0.20V; during negative scanning, the current is gradually reduced until a second oxidation peak II appears near-0.36V; the current of oxidation peak I was 9.43X 10-4A。
Example 4
1. Preparation method
A Pd/Ag nano alloy catalyst for a direct ethanol fuel cell is prepared by the following method:
(1) sequentially adding 8 mL of water and 40 mL of ethanol into a reaction container, and stirring to obtain a water-ethanol mixed solution system;
(2) 0.030 g of Pd (NO)3)2Powder, 0.052 g AgNO3Adding 0.5892 g of PVP into a water-ethanol mixed solution system, and stirring the prepared solution in a constant-temperature magnetic stirrer at 25 ℃ for 2 h;
(3) placing the uniformly stirred reaction solution in a self-designed illumination reaction box, and placing the reaction solution under the common commercial incandescent light of 200W for parallel illumination for 2 hours;
(4) centrifugally separating the obtained black precipitate, washing the black precipitate for multiple times by using ethanol and deionized water, and drying the black precipitate in a vacuum oven at the temperature of 40 ℃ for 24 hours to obtain the Pd/Ag nano alloy catalyst material.
The yield of the Pd/Ag nano-alloy catalyst prepared by the method is 90%.
2. Product characteristics and physicochemical properties of Pd/Ag nano alloy catalyst
The experimental materials and experimental methods for the characteristics and physicochemical properties of the product were the same as those of example 1.
(1) The micro-morphology of the obtained Pd/Ag nano-alloy catalyst is shown in figure 6 and is in a cluster shape.
(2) The electrocatalytic activity of the prepared Pd/Ag nano-alloy catalyst on ethanol oxidation is shown in fig. 7 (d): the initial oxidation potential for oxidizing the ethanol is-0.56V, the current of the nano Pd modified glassy carbon electrode in an ethanol solution is gradually increased in forward potential scanning, and a first oxidation peak I appears near-0.28V; during negative scanning, the current is gradually reduced until a second oxidation peak II appears near-0.39V; the current of oxidation peak I is 4.06X 10-4A。
In summary, comparing the electrocatalytic performance of the Pd/Ag nano-alloy catalyst of the present embodiment with the Pd/Ag nano-alloy catalysts synthesized in examples 1, 2 and 3 respectively on ethanol, the experimental results show that: compared with the nanowires and nanoparticles prepared in examples 1-3, the electrocatalytic activity of the cluster-shaped Pd/Ag nano alloy catalyst on ethanol is obviously reduced, which shows that the catalytic activity of the Pd/Ag nano alloy catalyst prepared under the condition of not adding a reducing agent sodium citrate is obviously reduced on ethanol.
EXAMPLE 5 optimization of Process conditions for Pd/Ag Nanoalloy catalyst preparation
1. Influence of water-ethanol mixed solutions with different proportions on preparation of Pd/Ag nano alloy catalyst
Adding ethanol and water into a reaction vessel according to the volume ratio of 1:10, 1:7, 1:5, 1:3, 1:1, 3:1, 5:1, 7:1 and 10:1 respectively, stirring to obtain water-ethanol mixed solution systems with different proportions, and examining the influence of the water-ethanol mixed solutions with different proportions on the preparation of the Pd/Ag nano alloy catalyst in the same way as in example 1.
Experimental results show that when the volume ratio of ethanol to water is 3-7: 1, the yield and catalytic activity of the prepared Pd/Ag nano alloy catalyst are high, wherein when the volume ratio of ethanol to water is 5:1, the efficiency and catalytic activity of the prepared Pd/Ag nano alloy catalyst are highest, and when the volume ratio of ethanol to water is 1: 1-10, the yield of the Pd/Ag nano alloy catalyst is only about 40%.
2. Influence of different illumination conditions on preparation of Pd/Ag nano alloy catalyst
The reaction solution obtained in step (3) of example 1 was placed under light conditions of 15W1h, 15W 2h, 15W 4h, 15W 8h, 15W 12h, 15W 16h, 100W 1h, 100W 2h, 100W 4h, 100W 5h, 200W1h, 200W 2h and 200W 4h, respectively, using a common commercial incandescent lamp as a light source, and the influence of different light conditions on the preparation of the Pd/Ag nano-alloy catalyst was examined, in the same manner as in example 1.
Experimental results show that the yield of the Pd/Ag nano alloy catalyst is highest under the condition of illumination of 200W for 2 hours, and the obtained product has the best electro-catalytic performance on ethanol.
Claims (6)
1. A preparation method of a Pd/Ag nano alloy catalyst for a direct ethanol fuel cell is characterized by adding alcohol into water according to a volume ratio of 3-7: 1, stirring, respectively adding polyvinylpyrrolidone, a metal palladium salt precursor, a metal silver salt precursor and sodium citrate, stirring for 1.5-2.5 h at 20-25 ℃, reacting for 2h under an illumination condition, centrifuging, collecting precipitate, washing and drying to obtain the Pd/Ag nano alloy catalyst; wherein the weight ratio of polyvinylpyrrolidone: metal palladium salt precursor: metal silver salt precursor: the mass ratio of the sodium citrate is 9.8-58.92: 0.7-3: 0.2-5.2: 0.1-0.4;
the alcohol is ethanol or ethylene glycol;
the illumination condition is visible light illumination; the illumination condition is 200W illumination for 2 h;
the metal palladium salt precursor is palladium nitrate; the precursor of the metal silver salt is silver nitrate.
2. The method according to claim 1, wherein the volume ratio of the alcohol to the water is 5: 1.
3. The method according to claim 1, wherein a light source for the illumination is an incandescent lamp or an energy saving lamp.
4. The preparation method according to claim 1, wherein the drying condition is vacuum drying at 35-45 ℃ for 12-48 h.
5. The Pd/Ag nano-alloy catalyst obtained by the preparation method of any one of claims 1 to 4.
6. Use of the Pd/Ag nano-alloy catalyst of claim 5 as a catalyst for a direct ethanol fuel cell.
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| CN105073254A (en) * | 2013-02-25 | 2015-11-18 | 日产自动车株式会社 | Catalyst particles for fuel cells and method for producing same |
| CN105594035A (en) * | 2013-08-09 | 2016-05-18 | 日产自动车株式会社 | Catalyst particles, electrocatalyst using the same, electrolyte membrane-electrode assembly, and fuel cell using the catalyst particles |
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| CN102794172A (en) * | 2012-07-26 | 2012-11-28 | 安徽理工大学 | Photosynthesis preparation method of nano palladium catalyst |
| CN105073254A (en) * | 2013-02-25 | 2015-11-18 | 日产自动车株式会社 | Catalyst particles for fuel cells and method for producing same |
| CN105594035A (en) * | 2013-08-09 | 2016-05-18 | 日产自动车株式会社 | Catalyst particles, electrocatalyst using the same, electrolyte membrane-electrode assembly, and fuel cell using the catalyst particles |
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