Method for preparing a carbon-supported, platinum-cobalt alloy, nanoparticle catalyst

Abstract

A method for preparing a carbon-supported, platinum-cobalt alloy, nanoparticle catalyst includes mixing a solution containing, in combination, a platinum precursor, a transition metal precursor consisting of a transition metal that is cobalt, carbon, a stabilizer that is oleyl amine, and a reducing agent that is sodium borohydride to provide carbon-supported, platinum-cobalt alloy nanoparticles, and washing the carbon-supported, platinum-cobalt alloy, nanoparticles using ethanol and distilled water individually or in combination followed by drying at room temperature to obtain dried carbon-supported, platinum-cobalt alloy, nanoparticles; treating the dried carbon-supported, platinum-cobalt alloy, nanoparticles with an acetic acid solution having a concentration ranging from 1-16M to provide acetic acid-treated nanoparticles, and washing the acetic acid-treated nanoparticles using distilled water followed by drying at room temperature to obtain dried acetic acid-treated nanoparticles; and heat treating the dried acetic acid-treated nanoparticles at a temperature ranging from 600 to 1000 C. under a hydrogen-containing atmosphere.

Claims

1. A method for preparing a carbon-supported, platinum-cobalt alloy, nanoparticle catalyst, comprising the steps of: (a) mixing a solution containing, in combination, a platinum precursor, a transition metal precursor consisting of a transition metal that is cobalt, carbon, a stabilizer that is oleyl amine, and a reducing agent that is sodium borohydride to provide carbon-supported, platinum-cobalt alloy, nanoparticles, and washing the carbon-supported, platinum-cobalt alloy, nanoparticles using ethanol and distilled water individually or in combination followed by drying at room temperature to obtain dried carbon-supported, platinum-cobalt alloy, nanoparticles; (b) treating the dried carbon-supported, platinum-cobalt alloy, nanoparticles with an acetic acid solution having a concentration ranging from 1-16M to provide acetic acid-treated nanoparticles, and washing the acetic-acid nanoparticles using distilled water followed by drying at room temperature to obtain dried acetic acid-treated nanoparticles; and (c) heat treating the dried acetic acid-treated nanoparticles at a temperature ranging from 600 to 1000 C. under a hydrogen-containing atmosphere.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a Co 2p X-ray photoelectron spectroscopic (XPS) spectrum of a carbon-supported, platinum-transition metal alloy, nanoparticle catalyst obtained from Example 1, before and after treatment with acetic acid, i.e., before treatment with acetic acid: 30Pt.sub.3Co/KB-AP, which is KETJENBLACK-AP, a carbon material manufactured by AkzoNobel, after treatment with acetic acid: 30Pt.sub.3Co/KB-1A-AP;

(2) FIGS. 2A and 2B show a transmission electron microscopic (TEM) image of the carbon-supported, platinum-transition metal alloy, nanoparticle catalyst obtained from Example 1, before heat treatment in FIG. 2A and after heat treatment in FIG. 2B;

(3) FIG. 3A shows an oxygen reduction, polarization curve and FIG. 3B shows a graph illustrating the catalytic performance per weight of platinum for the carbon-supported, platinum-transition metal alloy, nanoparticle catalyst obtained from Example 1 and the commercially-available, carbon-supported, platinum catalyst (Pt/C) according to Comparative Example 1;

(4) FIG. 4 is a graph illustrating the polarization curve of a fuel cell using the membrane electrolyte assembly (MEA) obtained from Example 2 before (black color)/after (red color) an accelerated deterioration test; and

(5) FIG. 5 is a graph illustrating the polarization curve of the fuel cell using the MEA of Comparative Example 2 before (black color)/after (red color) an accelerated deterioration test.

DETAILED DESCRIPTION OF THE INVENTION

(6) Hereinafter, various aspects and embodiments of the present disclosure will be explained in more detail.

(7) In one aspect of the present disclosure, there is provided a method for preparing a carbon-supported, platinum-transition metal alloy, nanoparticle catalyst, including the steps of: (a) mixing a platinum precursor, a transition metal precursor, carbon, a stabilizer and a reducing agent in a solution, and carrying out washing and drying to obtain carbon-supported, platinum-transition metal alloy, nanoparticles; (b) mixing the carbon-supported, platinum-transition metal alloy, nanoparticles with an acetic acid solution, and carrying out washing and drying to obtain acetic acid-treated nanoparticles; and (c) heat treating the acetic acid-treated nanoparticles.

(8) According to an embodiment, the transition metal may be at least one transition metal selected from cobalt, palladium, osmium, ruthenium, gallium, titanium, vanadium, chromium, manganese, iron, nickel, copper and zinc, but is not limited thereto. Preferably, cobalt may be used.

(9) According to another embodiment, the stabilizer may be at least one material selected from oleyl amine, octyl amine, hexadecyl amine, octadecyl amine, trialkyl phosphine, oleic acid, lauric acid, linoleic acid, erucic acid and dodecyl acid, but is not limited thereto. Preferably, oleyl amine may be used.

(10) According to still another embodiment, the reducing agent may be at least one material selected from boron hydrides, such as sodium borohydride, lithium borohydride and lithium triethylborohydride; alcohols, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, dirpropylene glycol, propanediol and Ibutanediol; and aldehydes, such as formaldehyde, but is not limited thereto. Preferably, sodium borohydride may be used.

(11) According to still another embodiment, the acetic acid may have a concentration of 1-16M, preferably 1-10M, and more preferably 1-5M.

(12) In the process for preparing a carbon-supported, platinum-transition metal alloy, nanoparticle catalyst according to the related art, both a step of removing the stabilizer through heat treatment and a step of dissolving the transition metal on the surface of alloy nanoparticles with a strong acid are carried out. On the contrary, in the method according to the present disclosure, it is possible to remove the stabilizer and the transition metal on the surface of alloy nanoparticles simultaneously through treatment with acetic acid. Thus, it is possible to obtain a carbon-supported, platinum-transition metal alloy, nanoparticle catalyst in a more simple and eco-friendly process as compared to the process according to the related art.

(13) According to still another embodiment, in step (a) or (b), washing may be carried out by using ethanol, distilled water and a combination thereof, but is not limited thereto. Preferably, ethanol and distilled water may be used in step (a), and distilled water may be used in step (b).

(14) According to still another embodiment, in steps (a) and (b), drying may be carried out at room temperature.

(15) According to still another embodiment, in step (c), heat treatment may be carried out at 600-1000 C., preferably 700-900 C., and more preferably 750-850 C., under hydrogen atmosphere.

(16) Particularly, although there is no clear description in the following Examples and Comparative Examples, the type of stabilizer, the type of reducing agent, the concentration of acetic acid, the washing solvent in step (a) or (b), the drying conditions in steps (a) and (b), and the heat treatment condition in step (c) were varied in the method for preparing a carbon-supported, platinum-transition metal alloy, nanoparticle catalyst according to the present disclosure to obtain different carbon-supported, platinum-transition metal alloy, nanoparticle catalysts. Then, the shapes of the resultant catalysts were determined through transmission electron microscopy (TEM). In addition, the positive electrodes to which the resultant catalysts are applied were used for fuel cells, and charging/discharging was carried out 300 times to determine loss for each of the catalysts applied to the positive electrodes.

(17) As a result, unlike the other conditions and the other numerical ranges, when all of the following conditions are satisfied, the platinum-transition metal alloy, nanoparticles maintained a significantly small particle size of 3-5 nm even after the heat treatment of step (c), similarly to the particle size before the heat treatment. In addition, even after carrying out charging/discharging 300 times, it was shown that no loss for the catalysts applied to the positive electrodes was observed:

(18) (i) the transition metal is cobalt,

(19) (ii) the stabilizer is oleyl amine,

(20) (iii) the reducing agent is sodium borohydride,

(21) (iv) the concentration of acetic acid is 1-16M,

(22) (v) the washing in step (a) is carried out by using ethanol and distilled water,

(23) (vi) the washing in step (b) is carried out by using distilled water,

(24) (vii) the drying in steps (a) and (b) is carried out at room temperature, and

(25) (viii) the heat treatment in step (c) is carried out at 600-1000 C. under hydrogen atmosphere.

(26) However, when any one of the above conditions is not satisfied, the platinum-transition metal alloy, nanoparticles cause a significant increase in particle size to 10 nm or more after the heat treatment of step (c), as compared to the particle size before the heat treatment. In addition, after charging/discharging is carried out 300 times, it is observed that the catalysts applied to the positive electrodes show a significant loss.

(27) In another aspect of the present disclosure, there is provided a carbon-supported, platinum-transition metal alloy, nanoparticle catalyst obtained by the method according to the present disclosure.

(28) According to an embodiment, the carbon-supported, platinum-transition metal alloy, nanoparticle catalyst may be a positive electrode catalyst for a fuel cell.

(29) In still another aspect of the present disclosure, there is provided an electric device including the carbon-supported, platinum-transition metal alloy, nanoparticle catalyst according to the present disclosure, the electric device being any one device selected from electric vehicles, hybrid electric vehicles, plug-in hybrid electric vehicles and power storage systems.

(30) Exemplary embodiments now will be described more fully hereinafter with reference to the accompanying drawings, in which exemplary embodiments are shown.

Example 1

(31) A platinum precursor, cobalt precursor, oleyl amine and carbon were dispersed in dry ethanol and a reducing agent solution containing 0.23 g of sodium borohydride dissolved in 10 mL of dry ethanol was introduced to the dispersed solution. After carrying out agitation for 12 hours, washing was carried out by using ethanol and distilled water, and the resultant product was dried at room temperature to obtain carbon-supported platinum-cobalt alloy nanoparticles (Pt.sub.3Co/KB-AP, which is KETJENBLACK-AP, a carbon material manufactured by AkzoNobel. The carbon-supported platinum-cobalt alloy nanoparticles were dispersed in 1M acetic acid solution. Then, the resultant solution was agitated for 12 hours, washed with distilled water, and dried at room temperature to obtain acetic acid-treated nanoparticles (Pt.sub.3Co/KB-1A-AP), where KB-1A-AP identifies KETJENBLACK-AP, a carbon material manufactured by AkzoNobel, after the acetic acid treatment described above. The acetic acid-treated nanoparticles were heat treated at 800 C. under a 5% hydrogen atmosphere to obtain acetic acid-treated carbon-supported platinum-cobalt alloy nanoparticle catalyst (Pt.sub.3Co/KB-1A-H800), where KB-1A-H800 identifies KB-1A-AP described above after heat treatment at 800 C. under a 5% hydrogen atmosphere.

Example 2

(32) The acetic acid-treated carbon-supported platinum-cobalt alloy nanoparticle catalyst according to Example 1 was used as a negative electrode catalyst to obtain a membrane electrode assembly (MEA) for a fuel cell. A mixture of Pt.sub.3Co/KB-1A-H800 according to Example 1, 5 wt % NAFION (a perfluorinated polymer manufactured by Sigma-Aldrich)) solution and isopropyl alcohol (IPA) were used to form a catalyst slurry, and the catalyst slurry was applied to a NAFION 211 (a perfluorinated membrane manufactured by Sigma-Aldrich) electrolyte by using an air sprayer to obtain a negative electrode. In the same manner, a commercially available carbon-supported, platinum catalyst (Pt/C) was used instead of Pt.sub.3Co/KB-1A-H800 to obtain a positive electrode and to manufacture an MEA.

Comparative Example 1

(33) A commercially available carbon-supported, platinum catalyst (Pt/C) was prepared.

Comparative Example 2

(34) A membrane electrode assembly (MEA) was obtained in the same manner as described in Example 2, except that the commercially available carbon-supported platinum catalyst according to Comparative Example 1 was used not only for a positive electrode but also for a negative electrode, instead of the catalyst according to Example 1.

(35) FIG. 1 shows Co 2p X-ray photoelectron spectroscopic (XPS) spectrum of the carbon-supported, platinum-transition metal alloy, nanoparticle catalyst obtained from Example 1, before and after treatment with acetic acid, i.e., before treatment with acetic acid: 30Pt.sub.3Co/KB-AP, after treatment with acetic acid: 30Pt.sub.3Co/KB)-1A-AP.

(36) Referring to FIG. 1, cobalt oxide is present on the surface of the alloy nanoparticles before the treatment with acetic acid. On the contrary, it can be seen that cobalt on the surface of the alloy nanoparticles is removed after the treatment with 1M acetic acid.

(37) FIGS. 2A and 2B show transmission electron microscopic (TEM) image of a carbon-supported, platinum-transition metal alloy, nanoparticle catalyst obtained from Example 1, before heat treatment in FIG. 2A and after heat treatment in FIG. 2B.

(38) Referring to FIG. 2A, it can be seen that particles having a size of about 3 nm are dispersed in a carbon support in the catalyst before heat treatment.

(39) In addition, referring to FIG. 2B, it can be seen that the catalyst after heat treatment maintains a significantly small particle size of 3-5 nm even though heat treatment is carried out at a high temperature of 800 C.

(40) FIG. 3A shows an oxygen reduction polarization curve and FIG. 3B shows a graph illustrating the catalytic performance per weight of platinum, for the carbon-supported, platinum-transition metal alloy, nanoparticle catalyst obtained from Example 1 and the commercially available carbon-supported platinum catalyst (Pt/C) according to Comparative Example 1.

(41) Referring to FIG. 3A, it can be seen from the polarization curve that the alloy nanoparticle catalyst according to the present disclosure has higher performance as compared to a commercially-available, carbon-supported, platinum catalyst.

(42) In addition, referring to FIG. 3B, it can be seen that the alloy nanoparticle catalyst according to the present disclosure shows performance approximately 4.8 times higher than the performance of the commercially-available, carbon-supported, platinum catalyst.

(43) FIG. 4 is a graph illustrating the polarization curve of the fuel cell using the membrane electrolyte assembly (MEA) obtained from Example 2 before (black color)/after (red color) an accelerated deterioration test. FIG. 5 is a graph illustrating the polarization curve of the fuel cell using the MEA of Comparative Example 2 before (black color)/after (red color) an accelerated deterioration test.

(44) An accelerated deterioration test was carried out through 30,000 times of cyclic voltammetry in a cell voltage range of 0.6-1.0V according to the accelerated deterioration condition of a catalyst defined by United States Department of Energy.

(45) Referring to FIG. 4 and FIG. 5, after the accelerated deterioration test, the fuel cell using the MEA according to Example 2 shows a decrease in current density of 10.3% at 0.76V (FIG. 4). This demonstrates that the fuel cell has higher durability corresponding to 29.9% based on the fuel cell using the MEA according to Comparative Example 2 which shows a decrease in current density of 34.5% under the same condition (FIG. 5).

(46) Therefore, according to the present disclosure, a carbon-supported, platinum-transition metal alloy, nanoparticle catalyst is obtained through a more simple and eco-friendly process as compared to the related art by removing the transition metal and the stabilizer on the surface of the nanoparticles simultaneously through treatment with acetic acid, and the catalyst may be used as a catalyst for a fuel cell having high performance and high durability.