KR100703675B1 - Carbon nanofiber structures, method for preparing carbon nanofiber structures, and electrode catalyst for fuel cell using the same - Google Patents

Abstract

The present invention relates to a carbon nanofiber structure, a method of manufacturing the same, and a fuel cell catalyst using the same. The carbon nanofiber structure according to the present invention comprises a bundle of carbon nanofibers, each carbon nanofiber is a regular structure interconnected by short connecting carbon spacers or irregularly arranged structures by collapse of the connecting carbon spacers. . Such a carbon nanofiber structure may be manufactured through replication using a silica template, and such carbon nanofiber structure may be used for an electrode catalyst support for a fuel cell.

Carbon nanofibers, fuel cells, catalysts, supports

Description

CARBON NANOFIBER STRUCTURES, METHOD FOR PREPARING CARBON NANOFIBER STRUCTURES, AND ELECTRODE CATALYST FOR FUEL CELL USING THE SAME}

1 is a TEM image of a) a scanning electron microscope (SEM), b) a transmission electron microscope (TEM), and c) catalyst particles of a carbon nanofiber structure in a regular arrangement according to one embodiment of the present invention.

FIG. 2 is a TEM image of a) SEM, b) TEM and c) catalyst particles supported on irregularly arranged carbon nanofiber structures according to one embodiment of the invention.

3 is a diagram schematically showing an example of a method of manufacturing a carbon nanofiber structure in a regular arrangement according to the present invention.

4 is a diagram schematically showing an example of a method of manufacturing a carbon nanofiber structure having an irregular arrangement according to the present invention.

5 is a graph showing the N ₂ adsorption and desorption performance of the carbon nanofiber structure according to the present invention and an electrode catalyst using the carbon nanofiber structure as a catalyst support.

6 and 7 show the electrocatalytic activity of the electrode catalyst using the regularly arranged or regularly arranged carbon nanofiber structure as the support for the catalyst and the commercially available E-TEK catalyst at 30 ° C. and 70 ° C., respectively. It is a graph showing the current density relationship.

8 is a chronoampogram of an electrode catalyst using a regular or irregularly arranged carbon nanofiber structure according to the present invention as a catalyst support and a commercially available E-TEK catalyst.

9 is a cyclic voltagram of an electrode catalyst and a commercially available E-TEK catalyst using a carbon nanofiber structure in a regular or irregular arrangement according to the present invention as a support for a catalyst.

10 is a graph comparing an X-ray diffraction pattern of an electrode catalyst and a commercially available E-TEK catalyst using a carbon nanofiber structure having a regular or irregular arrangement according to the present invention as a catalyst support.

* Short description of drawing symbols *

1. Silica wall 2. Surfactant

3. Mesopore Channel 4. Micropore Channel

5. Carbon precursor 6. Carbon

The present invention relates to a carbon nanofiber structure, a method for producing the same, and a catalyst for a fuel cell using the same, and more particularly, to a carbon nanofiber structure, a method for producing the same, and a catalyst for a fuel cell using the same. It is about.

Nanostructured carbon materials are academically and technically important materials that can be applied to various fields, including catalysts, supports, separation systems, adsorbents, electronic materials and hydrogen storage materials. In particular, carbon is an important material that can be used in low temperature fuel cells, and is an inexpensive material capable of realizing cheap fuel cells as well as excellent electrical conductivity, corrosion resistance and surface properties, and there is no alternative material yet having such an advantage. .

Direct Methanol Fuel Cells are an area of recent interest for their potential utility for stationary and mobile applications. In general, the metal of the electrode catalyst constituting the fuel cell is supported by an electrically conductive material having a high surface area that enables high dispersion of the catalyst. It is known that the performance and stability of a fuel cell depends closely on the carbon support used as well as the catalytic metal which is the catalytically active factor.

Carbon black, aka Vulcan XC-72, has been intensively used as a support material for the production of electrode catalysts for fuel cells. Vulcan XC-72 carbon generally consists of aggregates of amorphous carbon nanoparticles having a BET surface area of about 232 m 2 / g and a total pore volume of about 0.32 ml / g. In fact, a commercially available E-TEK catalyst is a Pt-Ru alloy catalyst supported on Vulcan XC-72. Recently, great advances have been made in the synthesis of porous carbon with periodic porosity using various template replicas.

Recently, several different carbon materials such as mesostructured carbon, graphitic carbon nanofibers, and mesocarbon microbeads have been developed for higher dispersion of metal catalysts. And as a support of Pt or Pt-Ru alloy catalysts for improved synergy. The size of the catalyst particles adsorbed on the support surface decreases as the specific surface area of the carbon support increases, and the reduction of the catalyst particle size can lead to high dispersibility and high electrical activity.

However, it is still a very difficult task to synthesize carbon materials having a high surface area and a uniformly interconnected uniform porous structure.

We have reported a new type of porous carbon support with regularly uniform mesos or macropores (range from 10 to 800 nm) interconnected three-dimensionally. More recently, a hollow core / mesoporous shell structure structure with a hollow core and mesoporous shell has been found to be an excellent support for electrocatalysts in direct methanol fuel cells. When this support was used as a support for the Pt-Ru catalyst, it showed about 10 to 80% higher activity against methanol oxidation than the commercial E-TEK catalyst.

 The inventors of the present invention have found that the carbon nanofiber structure is easy to synthesize, and the structure is uniform, while studying a more efficient carbon support that can be used as a support for an electrocatalyst and can increase methanol oxidation performance in a direct methanol fuel cell. The present invention has been completed and found that it can have a high degree of regularity and can be preferably used as a support for an electrode catalyst because it is pure in terms of composition.

Accordingly, the first object of the present invention is to provide a regularly arranged carbon nanofiber structure.

It is also a second object of the present invention to provide an irregularly arranged carbon nanofiber structure.

It is also a third object of the present invention to provide a method for producing a regularly arranged carbon nanofiber structure.

It is a fourth object of the present invention to provide a method for producing an irregularly arranged carbon nanofiber structure.

A fifth object of the present invention is to provide an electrode catalyst for a fuel cell using a regularly arranged or irregularly arranged carbon nanofiber structure as a catalyst support.

In order to achieve the first object, the present invention provides a regularly arranged carbon nanofiber structure, wherein the carbon nanofibers are arranged regularly, each carbon nanofiber is interconnected by a short connecting carbon spacer. do.

In order to achieve the second object, the present invention provides a carbon nanofiber structure comprising a bundle of carbon nanofibers arranged irregularly by the collapse of the connecting carbon spacer.

In order to achieve the third object, the present invention provides a) a plurality of mesopore channels separated by silica walls and a plurality of micropore channels connecting between mesopore channels, and the pores are filled with a surfactant. Preparing a silica template; b) extracting a surfactant from the silica template; c) injecting a carbon precursor into the silica mold from which the surfactant has been extracted, polymerizing and carbonizing; And d) provides a method for producing a carbon nanofiber structure in a regular arrangement comprising the step of removing the silica template.

In order to achieve the fourth object, the present invention provides a) a plurality of mesopore channels separated by silica walls and a plurality of micropore channels connecting between the mesopore channels are formed, and the pore includes a surfactant Preparing a filled silica template; b) extracting a surfactant from the silica template; c) calcining at high temperature to shrink the pores of the surfactant extracted silica template; d) injecting a carbon precursor into the calcined silica template, polymerizing and carbonizing; And e) provides a method for producing a carbon nanofiber structure of irregular arrangement comprising the step of removing the silica template.

In order to achieve the fifth object, the present invention provides an electrode catalyst for a fuel cell comprising a carbon nanofiber structure in a regular or irregular arrangement as a support.

Hereinafter, the present invention will be described in more detail.

Carbon nanofiber structures according to the present invention comprise a bundle of carbon nanofibers, each carbon nanofiber being a regular structure interconnected by short connecting carbon spacers. Therefore, the carbon nanofiber structure has a regularly distributed three-dimensionally interconnected mesopore structure.

The diameter of each carbon nanofiber ranges from 3 to 10 nm and is very uniform. In addition, the aspect-ratio of each carbon nanofiber is very high, and preferably 1000 to 5000. In addition, the diameter of each carbon nanofiber is meso size, the diameter of the connecting carbon spacer is a micro size, specifically, the ratio of the diameter of each carbon nanofiber and the connecting carbon spacer is 5: 1 to 15: 1, the length The ratio of is preferably 1.0X10 ³ : 1 to 1.0X10 ⁴ : 1. The BET specific surface area of the carbon nanofiber structures in this ordered arrangement is 600 to 800 m 2 / g, and the total pore volume is 0.6 ml / g to 0.9 ml / g.

1A and 1B are SEM and TEM images of a carbon nanofiber structure in a regular arrangement according to the present invention, and FIG. 1C is a TEM image after catalyst supported on a carbon nanofiber structure in a regular arrangement according to the present invention.

1A and 1B, the regularly arranged carbon nanofiber structures according to the present invention show that the nanofibers uniformly separated by the gap channel are arranged in a highly regular array. Also, referring to FIG. 1C In addition, it can be seen that after the catalyst metal is supported on the carbon nanofiber structure of the regular arrangement according to the present invention, small spherical uniform black dots are dispersed in sequence. As measured directly from the TEM image of FIG. 1C, the particles have a diameter in the range of 2.5-4.5 nm.

Another carbon nanofiber structure according to the present invention is a carbon nanofiber bundle structure in which carbon nanofibers are arranged irregularly, respectively, due to the collapse of a connecting carbon spacer. Thus, the carbon nanofiber structure has a biporous structure having randomly distributed three-dimensionally interconnected macropores and macropores.

In the irregularly arranged carbon nanofiber structure, each carbon nanofiber diameter is in a range of 3 to 10 nm, an aspect ratio is 1.0X10 ³ to 7.0X10 ³ , and a BET specific surface area is 250 to 450 m 2 / g, The total pore volume is 0.3 ml / g to 0.5 ml / g.

2A and 2B are SEM and TEM images of an irregularly arranged carbon nanofiber structure according to the present invention, and FIG. 2C is a TEM image of a carbon nanofiber structure having an irregular arrangement according to the present invention after catalyst support.

Referring to FIGS. 2A and 2B, the irregularly arranged carbon nanofiber structure according to the present invention shows that loose nanofibers with several clusters have a random (large irregularity) arrangement. In addition, referring to Figure 2c, it can be seen that after the catalyst metal is supported on the irregularly arranged carbon nanofiber structure according to the present invention, small spherical uniform black dots are uniformly dispersed. As measured directly from the TEM image of FIG. 2C, the particles have a diameter in the range of 2.0-4.0 nm.

Comparing FIGS. 1 and 2, it can be seen that irregularly arranged carbon nanofibers are slightly smaller in diameter than regular carbon nanofibers because the structure shrinks during the firing process involved in the synthesis process. Interestingly, when the catalyst metal is supported, it can be seen that the irregularly arranged carbon nanofibers have a particle size distribution slightly smaller than that of the regularly arranged carbon nanofiber structures.

3 is a diagram schematically showing an example of a method of manufacturing a carbon nanofiber structure of a regular arrangement according to the present invention, Figure 4 is a diagram showing an example of a method of manufacturing a carbon nanofiber structure of an irregular arrangement according to the present invention. to be.

3, the carbon nanofiber structure in a regular arrangement,

a) a plurality of mesopore channels (3) separated by silica walls (1) and a plurality of micropore channels (4) connecting between the mesopore channels (3), the pores having a surfactant (2) Preparing a silica mold filled with;

b) extracting a surfactant from the silica template;

c) polymerizing by injecting a carbon precursor (5) into the silica template from which the surfactant is extracted, and then carbonizing; And

d) prepared by a process comprising the step of removing the silica template to leave only carbon (6).

In step a) of the manufacturing method according to the present invention, the silica template is connected to a plurality of mesopore channels (3) and mesopore channels (3) separated by silica walls (1). Has (4) Here, the size of the mesopore channel 3 has a diameter of 4 to 10 nm, it is preferable that the aspect ratio is 1.0X10 ³ to 5.0X10 ³ . In addition, the size of the micropore channel 4 has a diameter of 0.4 to 0.8 nm, it is preferred that the aspect ratio is 5 to 10. The size of the mesopore channel and the size of the micropore channel may determine the size of each carbon nanofiber and the size of the carbon spacer connecting the carbon nanofibers.

SBA-15 silica may be used as the silica template having the above structure.

The silica template may be synthesized through the following synthesis method. That is, the method of synthesizing a silica template dissolves a surfactant of an amphoteric substance having a hydrophilic portion and a lipophilic portion in a polar solvent to form a micelle in which the hydrophilic portion of the surfactant faces out, and then introduces a silica precursor to Proceeding the hydrolysis and condensation reaction of the silica precursor in the hydrophilic portion. Through this synthesis method, it is possible to obtain a silica template in which surfactants are filled in pores (pores) of mesoporous silica.

The specific method is as follows: Pluronic P123 (EO ₂₀ PO ₇₀ EO _20; amphiphilic triblock copolymer, 4 g) is dissolved in 2M HCl (145 ml) and distilled water (36 ml), and the reaction mixture is stirred under 35 Heated to ° C. Subsequently, tetraethylorthosilicate (TEOS, 11 ml) was added thereto, and maintained for 20 hours under the same conditions. Then, after stopping the stirring and aging for 24 hours at a temperature of 35 to 100 ℃, the solvent used is filtered off and dried to obtain a template consisting of silica and surfactant.

In step b) of the present invention, the surfactant 2 filled in the mesopore channel 3 and the micropore channel 4 is removed. The method for removing the surfactant (2) can be used in various ways depending on the type of the surfactant, a method that can remove the surfactant without damaging the silica template is preferred. There are two preferred methods of removing the surfactant. Firstly, there is a method of refluxing a mixture of silica and a surfactant (as-synthesized sample) in 0.1M acidic alcohol while stirring, and secondly, the mold is in air using a tube furnace. There is a method of removing by heat treatment (calcination).

In step c) of the manufacturing method according to the present invention, the carbon precursor 5 is injected into the silica mold from which the surfactant is extracted, followed by polymerization and carbonization.

The carbon precursor may be divinylbenzene, acrylonitrile, vinyl chloride, vinyl acetate, styrene, methacrylate, methyl methacrylate, ethylene glycol dimethacrylate, urea, melamine, or CH ₂ = Monomers such as CRR '(where R and R' represent alkyl or aryl groups) include azobisisobutyronitrile (AIBN), t-butyl peracetate, benzoyl peroxide (BPO), Polymers prepared by addition polymerization using acetyl peroxide or lauryl peroxide initiators, phenol-formaldehyde, phenol, furfuryl alcohol, resorcinol-formaldehyde Polymer or graphite C ₃ N ₄ , mesophase pitch (mes) produced by condensation polymerization of (RF), aldehyde, sucrose, glucose or xylose using an acid catalyst such as sulfuric acid or hydrochloric acid ophase pitch or other carbon precursors that form graphitic carbon by a carbonation reaction.

The addition polymerizable monomers may be used alone or in a mixture of two or more monomers. At this time, the molar ratio of the monomer and the initiator is 15: 1 to 35: 1 but ideally 25: 1. The condensation polymerizable monomer may also be used alone or as a mixture of two or more monomers, wherein the molar ratio of the monomer and acid catalyst is about 5: 1 to 15: 1 and ideally 10: 1.

The monomer and the initiator or monomer and acid catalyst mixture is injected in an amount of 20 to 30% by volume with respect to the silica template, and the injection of the mixture may be in the liquid or gas phase. More specifically, the mixture may be added in the liquid phase to the silica mold or the solid precursor material may be heated in a vacuum to be injected into the pores of the silica mold in a gaseous phase. Here, the impregnation method may be used as the injection method.

The silica mold into which the mixture of the addition-polymerizable monomer and the necessary initiator are injected is polymerized under other known optimum conditions depending on the polymerizable compound used, but is preferably polymerized for 3 to 30 hours at a temperature of 60 to 120 ° C. Let's do it. In the case of the condensation-polymerizable monomer and the acid catalyst mixture, the polymerization may be carried out under other known optimum conditions depending on the condensation-polymerizable compound used, but is preferably polymerized at a temperature of 80 to 140 ° C for 3 to 30 hours. In both cases, upon completion of the polymerization, a mold-polymer composite is obtained. The acid, which is a catalyst during the condensation polymerization, may form an acidic site on the surface of the silica mold to exhibit acid catalyst properties on its own, or may be added as an acid catalyst (hydrochloric acid, sulfuric acid, etc.) from the outside to act as a catalyst during the condensation reaction of the monomer.

The silica mold into which the carbon precursor polymer is injected is heat-treated at a temperature of 800 to 2500 ° C. for 5 to 15 hours under an inert gas such as Ar or N ₂ to carbonize the polymer to obtain a template-carbon composite. At this time, the temperature increase rate is in the range of 1 ° C / minute to 10 ° C / minute.

Step e) of the manufacturing method according to the present invention uses a method that can remove the silica template without modifying the carbon (6) formed to remove the silica template. Such a method includes an etching method using an HF solution or an alkali solution (eg, NaOH solution).

Referring to Figure 4, irregularly arranged carbon nanofiber structure is

a) a plurality of mesopore channels (3) separated by a silica wall (1) and a plurality of micropore channels (4) connecting between the mesopore channels (3), the pores filled with a surfactant Preparing a silica template;

b) extracting the surfactant (2) from the silica template;

c) calcining the surfactant extracted silica template at high temperature to shrink the pores;

d) polymerizing by injecting a carbon precursor (5) into the silica template from which the surfactant is extracted, and then carbonizing; And

e) is produced by a manufacturing method comprising the step of removing the silica template to leave only carbon (6).

In the above, steps a), b), d) and e) are the same as described in the method for producing the carbon nanofiber structure in the above regular arrangement.

However, the irregularly arranged carbon nanofiber structure is further calcined at a high temperature to shrink the pores of the silica template from which the surfactant is extracted. This step proceeds to shrink the size of the mesopores and micropores of the silica template, and as a result, the shrinkage of the micropores (connecting spacers) during the carbonization process causes collapse of each carbon nanofiber. It is arranged. At this time, the calcining temperature can control the degree of irregularity, the temperature of about 450 to 750 ℃ is preferred.

The regular or irregular arrangement of carbon nanofiber structures prepared as described above has a high pore volume and thus a high surface area. Therefore, such a carbon nanofiber structure can be used as a support for an electrode catalyst for a fuel cell.

The present invention also provides an electrode catalyst for a fuel cell comprising a regularly arranged or regularly arranged carbon nanofiber structure as a support.

The electrode catalyst for a fuel cell according to the present invention is a fuel cell that uses a liquid alcohol such as a direct methanol fuel cell (DMFC) and a direct ethanol fuel cell (DEFC) as a direct fuel, as well as oxidation (fuel electrode) and reduction of a hydrogen fuel cell ( Air cathode) electrode can also be applied.

The active metal used in the electrode catalyst for a fuel cell according to the present invention may be any metal having an activity in the oxidation reaction of the fuel of the fuel cell, for example, platinum (Pt), ruthenium (Ru), rhodium (Rh) ), Molybdenum (Mo), osmium (Os), iridium (Ir), rhenium (Re), palladium (Pd), vanadium (V), cobalt (Co) and tungsten (W) It includes. For example, known catalytic metals such as monocomponent systems such as platinum (Pt) or bicomponent systems such as platinum-ruthenium (Pt-Ru) alloys, as well as three-component systems such as Pt-Ru-Rh alloys, four-component systems, For example, it may include a Pt-Ru-Co-W alloy or a Pt-Ru-Mo-W alloy and other multicomponent catalyst metals. These metals may be loaded in an amount of 80% or more in the carbon nanofiber structure according to the present invention.

In other words, the electrode catalyst for a fuel cell of the present invention may carry a metal corresponding to about 10 times the weight of the carbon support. This is because the carbon nanofiber structure used in the electrode catalyst for fuel cell of the present invention has a surface area of about 2 to 4 times per unit mass as compared to the conventional carbon black support, so that the surface area on which the metal catalyst particles can be loaded is increased. In addition to supporting a larger amount of metal catalyst particles compared to carbon black of the same weight, the metal can be supported on a support with a very small size of 2 to 3 nm in diameter, so that expensive precious metals can be efficiently used. It is also economically advantageous.

On the other hand, in general, in the preparation of the electrode catalyst, the smaller the supporting ratio of the catalyst metal to the support, the higher the amount of support to be used to support the same amount of the catalyst metal, so that it is used to obtain the same amount of the active catalyst. The amount of support to be increased also. In this case, in preparing the electrode of the fuel cell, a large amount of catalyst must be applied thickly to the carbon sheet, which causes cracking during drying or during use, thereby degrading the performance of the fuel cell. However, the catalyst system of the present invention has a higher metal loading ratio compared to the catalyst system using a conventional carbon black as a support, for example, compared with the 60% loading ratio of a commercially available E-TEK catalyst. Since the carbon nanofiber structure has 80% or more of the amount of metal supported, the amount of the support used to support the same amount of metal is only 1/2, so that a small amount of catalyst is used to prevent the above cracking phenomenon. can do. This can eventually realize miniaturization of the fuel cell. Of course, it is possible to support the amount of the catalyst metal as much as 5% of the total weight of the catalyst. As a result, the relative weight of the metal can be widely chosen depending on the intended use.

Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to an Example.

Synthesis Example 1

Regular array of carbon nanofiber structures

The SBA-15 silica template (as-synthesized sample) was removed using an acidic ethanol solution (0.1 M HCl) and then dried in a 70 ° C. drying oven. After removing the surfactant and drying the dried SBA-15, the DVB / AIBN mixture (molar ratio of approximately 25), which is a polymer precursor, was introduced into the mesopore of the silica mold through vacuum, and then the polymer reaction was performed overnight in a 70 ° C reaction oven. The obtained silica template / polymer composite was placed in a tubular furnace and carbonized at 900 ° C. for 7 hours in an inert gas atmosphere. The silica template / carbon composite thus obtained is a regular array of carbon nanofiber structures by removing silica mold using HF solution or 1M NaOH solution, followed by filtering, washing with excess distilled water, and drying. Got.

The regular arrangement of carbon nanofiber structures prepared in Synthesis Example 1 is shown by SEM and TEM images in FIGS. 1A and 1B.

Synthesis Example 2

Irregularly Arranged Carbon Nanofiber Structures

The SBA-15 silica template (as-synthesized sample) was removed using an acidic ethanol solution (0.1 M HCl) and then dried in a 70 ° C. drying oven. The surfactant was removed and dried SBA-15 was calcined in air for 7 hours at 300 ~ 750 ℃ using a mandarin furnace. DVB / AIBN mixture (molar ratio of approximately 25), which is a polymer precursor, was placed in the mesopores of the silica mold through vacuum, and then the polymer reaction was allowed to proceed overnight in a 70 ° C reaction oven. The obtained silica template / polymer composite was placed in a tubular furnace and carbonized at 900 ° C. for 7 hours in an inert gas atmosphere. The silica template / carbon composite thus obtained is removed by using HF solution or 1M NaOH solution, followed by filtering, washing with excess distilled water, and then dispersing it in ethanol to ultrasonically 2-3. After treatment for a period of time (drying) to obtain a carbon nanofiber structure of irregular arrangement.

Irregularly arranged carbon nanofiber structures prepared in Synthesis Example 2 are shown in SEM and TEM images in FIGS. 2A and 2B.

Example 1

Preparation of Pt-Ru Alloy Catalyst Supported on Regularly Arranged Carbon Nanofiber Structures

The Pt-Ru alloy catalyst supported on the regularly arranged carbon nanofiber structure prepared in Synthesis Example 1 was As the metal precursor H ₂ PtCl ₆ .6H ₂ O (Aldrich) and RuCl ₃ .xH ₂ O (Aldrich) using (Pt / Ru molar ratio of 1), and using as the reducing agent NaBH ₄ was synthesized at room temperature.

That is, by dissolving an equimolar (2 × 10 ^-3 _{mol) H 2 PtCl 6 .6H2O (40.88} % Pt) 1.0976g and _{RuCl 3 .xH 2 O (40.71%} Ru) 0.4965g of the deionized water, the metal salt solution 100㎖ Prepared. 0.1481 g of the regularly arranged carbon nanofiber structure obtained in Synthesis Example 1) was suspended in 100 ml of deionized water and stirred for 1 hour to form a uniform carbon slurry. Subsequently, 100 ml of the carbon slurry was added to 100 ml of the metal salt solution, stirred for about 30 minutes, and 2.8 L of deionized water was added to dilute the metal salt-carbon mixed solution, followed by stirring for about 1 hour. The pH of the mixed solution was adjusted to about 8 using a 3.0 M NaOH solution, and 50 ml of excess NaBH ₄ solution (NaBH ₄ / metal molar ratio was approximately 10) was rapidly added to the carbon-metal salt mixed solution under vigorous stirring for 2 hours. The metal salt was reduced by stirring at ambient temperature over to prepare a Pt ₅₀ -Ru ₅₀ catalyst with 80% by weight metal loading based on the total weight of the catalyst.

In addition, the TEM photograph of the catalyst is shown in Figure 1c. As shown in FIG. 1C, it can be seen that the small, spherical, uniform black dots corresponding to the Pt-Ru alloy nanoparticles are uniformly distributed. The particle size measured directly from the TEM photograph in a randomly selected region for the sample was approximately 2.5-4.5 nm. This was further confirmed through average particle size analysis from the (220) X-ray diffraction peak of the Pt fcc grating by Scharrer's equation, as shown in FIG. 10.

Example 2

Preparation of Pt-Ru Alloy Catalyst Supported on Irregularly Arranged Carbon Nanofiber Structures

It was prepared in the same manner as in Example 1 except for using the irregularly arranged carbon nanofiber structure prepared in Synthesis Example 2.

In addition, the TEM photograph of the catalyst is shown in Figure 2c. As shown in FIG. 2C, it can be seen that the small, spherical, uniform black dots corresponding to the Pt-Ru alloy nanoparticles are uniformly distributed. The particle size measured directly from the TEM photograph in a randomly selected region for the sample was approximately 2-4 nm. This was further confirmed through average particle size analysis from the (220) X-ray diffraction peak of the Pt fcc grating by Scharrer's equation, as shown in FIG. 10.

Comparative example

Commercially available E-TEK catalysts were used. (Manufacturer E-TEK)

Test Example 1

Approximately 100 mg of each prepared in Synthesis Examples 1 and 2, Examples 1 and 2, respectively, were weighed and degassed from 423 K to 20 μTorr for 4 to 6 hours, followed by Micrometries ASAP 2010 at 77 K. Adsorption tests were performed using a gas adsorption analyzer. The results are shown as adsorption isotherms in FIG. 5. At this time, the surface area, pore volume, and pore size distribution of the sample were measured using the BET equation (relative pressure 0.05 to 0.2) and the BJH method (relative pressure 0.987) using the volume of the adsorbed nitrogen gas molecules. Is shown in Table 1.

BET surface area (㎡ / g) Total Pore Volume (ml / g) Pore size distribution (nm) Synthesis Example 1 602 0.64 3.6 Synthesis Example 2 325 0.36 Not measurable * Example 1 156 0.26 Not measurable Example 2 123 0.29 Not measurable

* In Synthesis Example 2, the carbon is released and there are no mesopores of a certain size, and the pores are distributed over a wide range. Because of the distribution, pore size distribution measurement is not possible.

As can be seen in Table 1, it can be seen that the surface area and the pore volume of the carbon nanofiber structure is large, and also that the regular carbon nanofiber structure has a larger surface area and pore volume than the irregular carbon nanofiber structure. have.

Test Example 2

In order to evaluate the electrode catalyst activity of the carbon-supported catalysts obtained in Examples 1 and 2 and Comparative Examples, a DMFC (Direct Methanol Fuel Cell) unit cell having a 2 cm 2 catalyst area was used, and a potentiometer (WMPG-1000 ) Was measured at 30 ° C. and 70 ° C., and the results are shown in Table 2 and FIGS. 6 and 7. The potentiometer records the cell potential under constant current conditions. The catalyst was stirred for 24 hours to homogeneously mix the catalyst ink made by mixing distilled water, isopropyl alcohol and an appropriate amount of Nafion ionomer solution (Aldrich, 5% by weight). The catalyst layer was prepared by uniformly hand-painting an appropriate amount of anode (anode) or cathode (cathode) ink on teflonized carbon paper (TGPH-090) and drying at 110 ° C. for 30 minutes. . In this case, Johnson Matthey Pt Black (5.0 mg / cm 2) as a catalyst, a catalyst obtained in Examples 1 and 2 and Comparative Example as an anode, and Nafion 117 (DuPont) as an electrolyte were used. MEA (membrane electrode assembly) was prepared by hot-pressing pretreated Nafion 117 with anode and cathode catalyst on each side at 130 ° C. under a pressure of 100 kg / cm 2. Catalyst loadings at the metal based anode and cathode were 2.5 mg / cm 3 and 5.0 mg / cm 3, respectively. The Nafion 117 membrane was pretreated by boiling in 3% by weight H ₂ O ₂ for 1 hour followed by boiling in 0.5MH ₂ SO ₄ for 1 hour. All measurements were made with the same amount of metal loading under the same test conditions. The single cell test apparatus consisted of two copper end plates and two graphite plates with a lip-channel pattern to provide a methanol passage to the anode and an oxygen gas passage to the cathode. A 2.0 M methanol solution was provided to the anode at a rate of 1.0 mL / min by a masterplex liquid micro-pump and dry O2 was injected into the cathode at a rate of 300 mL / min using a flow meter.

 division Metal loading (% by weight * 1)  30 ℃ 70 ℃ Current density (0.4V) Power density Current density (0.4V) Power density Example 1 80 115 mA / ㎠ 59 mW / ㎠ 358 mA / ㎠ 160 mW / ㎠ Example 2 80 152 mA / ㎠ 78 mW / ㎠ 452 mA / ㎠ 199 mW / ㎠ Comparative example 60 81 mA / ㎠ 44 mW / ㎠ 178 mA / ㎠ 124 mW / ㎠

1.Weight%: Based on the total weight of the catalyst

As can be seen from Table 2 and FIGS. 6 and 7, when the carbon nanofiber structure having a regular and irregular arrangement is used, superior catalyst stability in terms of catalytic activity and fuel cell performance compared to using a commercially available E-TEK catalyst It can be seen that it has. This improvement in catalytic activity and stability is believed to be due to the structural and morphological properties of the carbon nanofiber structure as a support, such as surface area, pore connectivity, pore structure and electrical conductivity.

Test Example 3

In order to evaluate the stability of the catalysts obtained in Examples 1 and 2 and Comparative Examples, each electrode was subjected to several voltametric cycles (20 mV, -0.35 V to +0.35 V, 0.5 MH ₂ SO) until a reproducible reaction was reached. ₄ ) to apply. The cyclic voltammogram was then used with a WMPG-1000 potentiometer and -0.35V to +/- 0.35V for the Ag / AgCl reference electrode in an N ₂ degassed mixed solution of 0.5MH ₂ SO ₄ and 1.0M CH ₃ OH. Recordings were made at room temperature with a scan rate of 20 mV / s in the range of 0.35 V. A chronoampogram was then obtained while maintaining a potential of 0.4 V relative to the Ag / AgCl reference electrode for 4 hours. The effective geometric area of the working electrode is 1 cm 2, and the electrode has a catalyst support of 2 mg / cm 2. The results are shown in Table 3 and FIG. 8.

Relative current density (after 30 minutes) Relative current density (after 4 hours) Example 1 80% 68% Example 2 85% 78% Comparative example 69% 48%

According to Table 3 and FIG. 8, the comparative example (E-TEK catalyst) shows that after 30 minutes, the methanol oxidation current reaches 69% of the initial methanol oxidation current, whereas in Examples 1 and 2, after the first 30 minutes It has been shown that it reaches about 80-85% of the current. After 4 hours, the catalysts of Example 2 and Example 1 retained 78% and 68%, respectively, while the catalyst of the comparative example was only 48% initially. This result shows that the catalyst using the carbon nanofiber structure according to the present invention as a support has a very small decrease in current density with time in methanol oxidation, which shows that the catalyst is excellent in stability.

Test Example 4

In order to evaluate the electrochemical activity of the catalysts obtained in Examples 1 to 2 and Comparative Examples, a cyclic voltammeter was used to evaluate the results.

As can be seen from FIG. 9, when the carbon nanofiber structure according to the present invention is used, that is, the methanol oxidation current density at 0.4 V of the catalysts of Examples 1 and 2 is greater than that of E-TEK (Comparative Example). This indicates that the activity of the catalysts of Examples 1 and 2 is better.

As can be seen from Test Examples 1 to 4 above, the carbon nanofiber structure in a regular or irregular arrangement according to the present invention has a larger surface area and a larger surface area compared to Vulcan XC-72, which is a conventional support for electrode catalysts. It can be seen that it has a pore volume, and this structural feature of the carbon nanofiber structure makes it possible to support catalyst particles having a smaller particle size distribution with higher dispersibility when used as a support for an electrode catalyst.

Compared to Vulcan XC-72 carbon, the carbon nanofiber support according to the present invention has pores of various sizes distributed randomly and has many dead ends, which makes the dispersion of fuel and products less efficient. It has three-dimensionally interconnected mesopores and / or macropores, which provide an open network around the active catalyst site for efficient diffusion of fuel and products to and from the catalyst. Thus, the catalyst supported on the carbon nanofiber structure performs better electrocatalytic oxidation of methanol compared to the E-TEK catalyst supported on Vulcan XC-72 carbon. This is consistent with the results of the chronoampogram (CA) and the cyclic voltammogram (CV) as well as the unit cell performance data.

Also, in terms of surface area, pore uniformity, and interconnectivity, the regular array of carbon nanofiber structures may be considered to be a better support candidate than the irregular array of carbon nanofiber structures, but interestingly the irregular array of carbon nanofiber structures- Supported Pt-Ru catalysts showed higher electrocatalytic activity than regular arrays of carbon nanofiber structure-supported Pt-Ru catalysts.

This result is because a structure comprising a regular array of carbon nanofiber bundles has a larger internal unexposed mesopore surface area, but a relatively small external exposed surface area.

The results by TEM and XRD show that the surface area of the regularly arranged carbon nanofiber structures is larger than that of the irregularly arranged carbon nanofiber structures, but the catalyst particle size is slightly larger than that of the irregularly arranged carbon nanofiber structures. In general, in view of the fact that larger surface areas result in smaller particle size distributions due to higher particle dispersibility, the result for this unexpected surface area and particle size is that the Pt-Ru alloy nanoparticles have a regular array of carbon nanoparticles. This is because it is not evenly distributed in the fiber structure (ie, it is not evenly distributed in the external exposed surface area and the internal unexposed surface area). In fact, metal nanoparticles are supported closer to the outer surface area than to the deep inner surface area due to the gradual increase in hydrophobic field components in the regular array of carbon nanofiber structures. Therefore, the metal particles are more densely distributed in the outer surface area of the regular array of carbon nanofiber structures and thus increase in size. This is also confirmed by TEM and XRD measurements. However, a significant amount of Pt-Ru alloy catalyst is still supported on the larger internal array regions of the regular array of carbon nanofiber structures. A significant reduction in BET surface area after catalyst loading proves this fact. However, the catalyst particles inside cannot contact Nafion ionomers, which migrate protons into the electrolyte membrane during the methanol oxidation reaction, because ionomers having an average diameter of about 50 nm cannot penetrate into the fine regular mesopore region inside. to be.

That is, the regularly arranged carbon nanofiber supported PtRu catalyst has a relatively dense distribution on the outer surface, has a large particle size distribution, and the catalyst inside does not come into contact with the Nafion ionomer.

In comparison, irregularly arranged carbon nanofiber structures have a very low amount of unexposed internal carbon fibers and mostly have externally exposed surfaces because almost all carbon nanofibers are released from regular carbon nanofiber bundles.

Thus, PtRu-alloy nanoparticles are mostly well supported with even and small particle size distribution on the accessible carbon surface of irregularly arranged carbon nanofiber structures, where the catalytic metal particles are also relatively compatible with Nafion ionomers as well as methanol fuel. It can be easily contacted. As a result, irregularly arranged carbon nanofiber structures show better catalytic utility than regularly arranged carbon nanofiber structures, although their surface area is small. Thus, better catalyst availability ensures better electrocatalytic activity for methanol oxidation in irregularly arranged carbon nanofiber systems.

It can be seen from the chronoampogram of FIG. 8 that the catalyst using a regularly arranged carbon nanofiber structure is also less stable compared to the catalyst using a randomly arranged carbon nanofiber structure. This is because an irregularly arranged carbon nanofiber structure has a large outer surface area where almost all fibers are loosened, thus providing a more easily accessible network around the active catalyst for efficient transport of fuel to and removal of products from and to the catalyst. It is believed that almost all of the catalysts can be used, resulting in a high catalyst utilization, thus facilitating a more reaction between the fuel and the catalyst and showing more stable reaction characteristics.

In conclusion, Pt-Ru catalysts supported on regularly arranged or irregularly arranged carbon nanofiber structures with high surface area and well-developed interconnected porosity were 34-78% relative to methanol oxidation compared to commercially available E-TEK catalysts. Shows high electrocatalytic activity. Therefore, carbon nanofiber structures are excellent supports that can be preferably used in electrode catalysts of fuel cells such as DMFC. In addition, the surface properties as well as the degree of regularity and irregularity of the carbon nanofiber structure can be easily adjusted by controlling methodological conditions such as plasticization temperature and the like.

 As described above, the electrode catalyst using the carbon nanofiber structure according to the present invention can be seen that the catalytic activity is significantly improved.

This improvement is due to the unique structural properties of the carbon nanofiber structures according to the present invention. That is because of the higher surface area and larger pore volume. In addition, the carbon nanofiber structure according to the present invention having a high surface area and highly developed interconnected porosity facilitates the movement and diffusion of fuel and products in the catalyst than Vulcan carbon due to its structural features. Thus, catalyst dispersion is improved and catalyst utilization is increased, thus further having high catalytic activity.

The carbon nanofiber structure having such a structure can also be used to control the amount of active metal to be more or less than a conventional support when preparing a catalyst.

In addition, the carbon nanofiber structure according to the present invention can be applied in various fields in which efficient transport of materials and high surface area are very large advantages such as in a direct methanol fuel cell.

Claims (15)

a) preparing a silica mold having a plurality of mesopore channels separated by silica walls and a plurality of micropore channels connecting between mesopore channels, the pores filled with a surfactant; b) extracting a surfactant from the silica template; c) polymerizing by injecting a carbon precursor into the silica template from which the surfactant has been extracted and carbonizing it; And d) manufacturing a carbon nanofiber structure comprising the step of removing the silica template. The method of claim 1, The silica template is an SBA-15 silica template, a mesopore channel having a diameter of 4 to 10 nm and an aspect ratio of 1000 to 5000, and a micropore channel having a diameter of 0.4 to 0.8 nm and an aspect ratio of 5 to 10. Method for producing a carbon nanofiber structure having a. The method of claim 1, The surfactant is removed by carrying out in an ethanol solution acidified with 0.1M HCl, or removed through a calcination process. The method of claim 1, The removal of the silica template is a method of producing a carbon nanofiber structure will be removed by etching. a) preparing a silica mold having a plurality of mesopore channels separated by silica walls and a plurality of micropore channels connecting between mesopore channels, the pores filled with a surfactant; b) extracting a surfactant from the silica template; c) calcining at high temperature to shrink the pores of the surfactant extracted silica template; d) carbonizing the carbon precursor by injecting a carbon precursor into the calcined silica template; And e) manufacturing a carbon nanofiber structure comprising removing the silica template. The method of claim 5, The silica template is an SBA-15 silica template, a mesopore channel having a diameter of 4 to 10 nm and an aspect ratio of 1000 to 5000, and a micropore channel having a diameter of 0.4 to 0.8 nm and an aspect ratio of 5 to 10. Method for producing a carbon nanofiber structure having a. The method of claim 5, The surfactant is removed by carrying out in an ethanol solution acidified with 0.1M HCl, or removed through a calcination process. The method of claim 5, The removal of the silica template is a method of producing a carbon nanofiber structure will be removed by etching. The method of claim 5, wherein the step of calcining at a temperature of 450 to 750 ℃ in step c). A carbon nanofiber structure comprising regularly arranged carbon nanofiber bundles prepared according to any one of claims 1 to 4, wherein each carbon nanofiber is interconnected by a connecting carbon spacer. 10. A carbon nanofiber structure comprising a bundle of carbon nanofibers arranged irregularly by the collapse of a connection spacer made according to claim 5. delete An electrode catalyst for a fuel cell comprising the carbon nanofiber structure according to claim 10 as a support. The method of claim 13, wherein the electrode catalyst for the fuel cell is 5 to 95% by weight based on the total weight of the catalyst (Pt), ruthenium (Ru), rhodium (Rh), molybdenum (Mo), osmium (Os), iridium An electrode catalyst for a fuel cell comprising at least one active metal selected from the group consisting of (Ir), rhenium (Re), palladium (Pd), vanadium (V), cobalt (Co) and tungsten (W). The electrode catalyst of claim 13, wherein the electrode catalyst for a fuel cell is used in a direct methanol fuel cell (DMFC), a direct ethanol fuel cell (DEFC), or a polymer electrolyte membrane fuel cell.

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