KR20220101799A - Platinum catalyst complex comprising carbon shell and manufacturing method thereof - Google Patents

Abstract

The present invention relates to a platinum catalyst composite comprising a carbon shell and having a low platinum content, and a method for preparing the same. Specifically, the method includes the steps of: preparing polystyrene-based copolymer particles by adding an initiator to starting materials including a monomer, a first crosslinking agent and a surfactant and crosslinking the same through ultraviolet irradiation; performing hyper crosslinking on the polystyrene-based copolymer particles; doping a resulting product with metal atoms and then carbonizing the same to obtain metal atom/carbonized polystyrene-based copolymer particles; and obtaining polystyrene-based copolymer particles carbonized by dissolving the metal atom/carbonized polystyrene-based copolymer particles in a mixture containing a platinum precursor and thermally reducing the carbonized polystyrene-based copolymer particles, a catalyst layer comprising a catalytic metal supported on the particles, and a catalyst comprising a carbon shell formed on the catalyst layer.

Description

Platinum catalyst composite comprising a carbon shell and method for preparing the same

The present invention relates to a platinum catalyst composite including a carbon shell and having a low platinum content and a method for preparing the same.

In general, a polymer electrolyte membrane fuel cell (PEMFC) is applied as a fuel cell for automobiles, and this polymer electrolyte membrane fuel cell normally exhibits high output performance of at least several tens of kW under various driving conditions of automobiles. To do this, it must be able to operate reliably over a wide current density range. The reaction for generating electricity of the fuel cell is a membrane-electrode assembly (MEA) composed of a Perfluorinated Sulfonic Acid (PFSA) Ionomer-Based Membrane and an anode/cathode electrode. : Occurs in Membrane-Electrode Assembly. After the hydrogen supplied to the anode, which is the oxidation electrode of the fuel cell, is separated into hydrogen ions (protons) and electrons (electrons), the hydrogen ions move through the membrane toward the cathode, the cathode, and electrons It moves to the cathode through an external circuit, and at the cathode, oxygen molecules, hydrogen ions, and electrons react together to generate electricity and at the same time generate water (H ₂ O) and heat as reaction byproducts.

Korean Patent No. 10-1393493 Korean Patent No. 10-2125652

An object of the present invention is to provide a catalyst composite capable of increasing the performance of a membrane-electrode assembly.

An object of the present invention is to improve the performance and durability of catalysts in membrane-electrode assemblies.

An object of the present invention is to provide a catalyst composite exhibiting excellent performance when applied to a membrane-electrode assembly while minimizing the amount of platinum.

An object of the present invention is to provide a method capable of mass-producing a catalyst composite in a uniform size.

The object of the present invention is not limited to the object mentioned above. The objects of the present invention will become more apparent from the following description, and will be realized by means and combinations thereof recited in the claims.

The catalyst composite according to an embodiment of the present invention includes carbonized polystyrene-based copolymer particles; a catalyst layer comprising a catalyst metal supported on the particles; and a carbon shell formed on the catalyst layer.

The particles may have a spherical shape.

The particles may have an average particle diameter (D50) of 50 nm to 1 μm.

The catalyst metal is platinum; And it may include at least one selected from the group consisting of iron, nickel, cobalt, and combinations thereof.

The carbon shell may have a thickness of 5 nm or less.

The method for preparing a catalyst composite according to an embodiment of the present invention comprises the steps of adding an initiator to a starting material including a monomer, a first crosslinking agent and a surfactant and crosslinking through ultraviolet irradiation to prepare polystyrene-based copolymer particles; hyper-crosslinking the polystyrene-based copolymer particles; Doping a metal atom to the resultant, followed by carbonization to obtain a metal atom/carbonized polystyrene-based copolymer particles; and polystyrene-based copolymer particles carbonized by dissolving the metal atom/carbonized polystyrene-based copolymer particles in a mixture containing a platinum precursor and thermal reduction, a catalyst layer comprising a catalyst metal supported on the particles, and on the catalyst layer It may include; obtaining a catalyst including the formed carbon shell.

The monomer is styrene (Styrene), 4-vinylbiphenyl (4-vinylbiphenyl), 2-vinyl pyridine (2-vinyl pyridine), N-ethyl-2-vinylcarbazole (N-ethyl-2-vinylcarbazole), It may include at least one selected from the group consisting of benzyl methacrylate, benzyl acrylate, and combinations thereof.

The first crosslinking agent may include at least one selected from the group consisting of divinylbenzene, vinylbenzyl azide, and combinations thereof.

The monomer includes styrene, the first crosslinking agent includes divinylbenzene and vinylbenzyl azide, and the starting material is styrene 75 in 100 mol% of styrene, divinylbenzene, and vinylbenzyl azide. It may include mol% to 90 mol%, 5 mol% to 10 mol% of divinylbenzene, and 5 mol% to 20 mol% of vinylbenzyl azide.

The surfactant is polyvinylpyrrolidone, sodium dodecyl sulfate, cetrimonium bromide, dodecyltrimethylammonium bromide, polyvinyl alcohol, and It may include at least one selected from the group consisting of combinations thereof.

The hyper crosslinking may be immersing the polystyrene-based copolymer particles in a mixture of a crosslinking catalyst, a second crosslinking agent and a solvent at a temperature of 30°C to 90°C for 12 hours to 48 hours.

The cross-linking catalyst may include at least one selected from the group consisting of FeCl ₃ , FeCl ₃ .6H ₂ O, AlCl ₃ , CoCl ₃ , ZnCl ₃ , CrCl ₄ and combinations thereof.

The second crosslinking agent may include at least one selected from the group consisting of formaldehyde dimethyl acetal, trichloromethane, carbon tetrachloride, and combinations thereof.

The metal atom may include at least one selected from the group consisting of iron, nickel, cobalt, and combinations thereof.

The carbonization may be performed for 1 hour to 3 hours at a temperature range of 600° C. to 1100° C. under a nitrogen atmosphere.

The thermal reduction may be performed for 10 minutes to 2 hours at a temperature range of 300° C. to 700° C. under H ₂ /N ₂ atmosphere.

According to the present invention, it is possible to obtain a catalyst composite having improved performance and durability.

The use of the catalyst composite according to the present invention can increase the performance of the membrane-electrode assembly.

According to the present invention, it is possible to obtain a catalyst composite exhibiting excellent performance when applied to a membrane-electrode assembly while minimizing the amount of platinum.

According to the present invention, it is possible to mass-produce the catalyst composite in a uniform size.

The effects of the present invention are not limited to the above-mentioned effects. It should be understood that the effects of the present invention include all effects that can be inferred from the following description.

1 is a cross-sectional view showing a catalyst composite according to the present invention.
FIG. 2 is a reference diagram illustrating the catalyst layer and the carbon shell included in the catalyst composite on an atomic scale.
3 is a reference diagram illustrating a state when the starting material is stirred for a predetermined time in the method for preparing a catalyst composite according to the present invention.
4 is a scanning electron microscope analysis result of the emulsion polymerization result in Example 1 of the present invention.
5A is a scanning electron microscope analysis result of the carbonized product in Example 1 of the present invention.
Figure 5b is a scanning electron microscope analysis result of the result when the emulsion-polymerized product is carbonized without hyper-crosslinking.
6 is a scanning electron microscope result of the FePt / cPS particle catalyst obtained in Example 1 of the present invention.
7A and 7B are half-cell test results using the catalyst obtained in Example 1 of the present invention.
8A and 8B are full-cell test results using the catalyst obtained in Example 1 of the present invention.
9a to 9c are scanning electron microscope analysis results of the catalysts obtained through Examples 2 to 4 of the present invention.

The above objects, other objects, features and advantages of the present invention will be easily understood through the following preferred embodiments in conjunction with the accompanying drawings. However, the present invention is not limited to the embodiments described herein and may be embodied in other forms. Rather, the embodiments introduced herein are provided so that the disclosed subject matter may be thorough and complete, and that the spirit of the present invention may be sufficiently conveyed to those skilled in the art.

In describing each figure, like reference numerals have been used for like elements. In the accompanying drawings, the dimensions of the structures are enlarged than the actual size for clarity of the present invention. Terms such as first, second, etc. may be used to describe various elements, but the elements should not be limited by the terms. The above terms are used only for the purpose of distinguishing one component from another. For example, without departing from the scope of the present invention, a first component may be referred to as a second component, and similarly, a second component may also be referred to as a first component. The singular expression includes the plural expression unless the context clearly dictates otherwise.

In the present specification, terms such as “comprise” or “have” are intended to designate that a feature, number, step, operation, component, part, or combination thereof described in the specification exists, but one or more other features It is to be understood that it does not preclude the possibility of the presence or addition of numbers, steps, operations, components, parts, or combinations thereof. Also, when a part of a layer, film, region, plate, etc. is said to be “on” another part, this includes not only cases where it is “directly on” another part, but also cases where another part is in between. Conversely, when a part, such as a layer, film, region, plate, etc., is "under" another part, this includes not only cases where it is "directly under" another part, but also cases where there is another part in between.

Unless otherwise specified, all numbers, values, and/or expressions expressing quantities of ingredients, reaction conditions, polymer compositions and formulations used herein contain, among other things, those numbers that essentially occur in obtaining such values. Since they are approximations reflecting various uncertainties in the measurement, it should be understood as being modified by the term "about" in all cases. Also, where the disclosure discloses numerical ranges, such ranges are continuous and inclusive of all values from the minimum to the maximum inclusive of the range, unless otherwise indicated. Furthermore, when such ranges refer to integers, all integers inclusive from the minimum to the maximum inclusive are included, unless otherwise indicated.

1 is a cross-sectional view showing a catalyst composite according to the present invention. Referring to this, the catalyst composite includes carbonized polystyrene-based copolymer particles 10 , a catalyst layer 20 including a catalyst metal supported on the particles 10 , and a carbon shell 30 formed on the catalyst layer 20 . ) is included.

The carbonized polystyrene-based copolymer particles 10 are characterized in that they are spherical particles having a uniform size. In particular, the present invention proposes a method capable of providing particles that do not lose their morphology and maintain a spherical shape even through a carbonization step. This will be described later.

The carbonized polystyrene-based copolymer particles 10 may have an average particle diameter (D50) of 50 nm to 1 μm. When the catalyst composite is prepared according to the emulsion polymerization method presented in the present invention, it is easier to control the size compared to the conventional membrane emulsification method, etc. can do.

The catalyst metal constituting the catalyst layer 20 is platinum; and an alloy including at least one selected from the group consisting of iron, nickel, cobalt, and combinations thereof.

The content of the platinum is not particularly limited, but may be 10 wt% or less, or 5 wt% or less, or 3 wt% or less, or 1 wt% or less based on the total weight of the catalyst composite. According to the present invention, it is possible to obtain a catalyst composite exhibiting equivalent or superior performance even when the platinum content is greatly reduced compared to a commercial platinum catalyst.

2 is a reference diagram illustrating the catalyst layer 20 and the carbon shell 30 on an atomic scale. According to this, since the carbon shell 30 is formed by forming a kind of lattice structure of carbon elements, the catalyst layer 20 is not disconnected from the outside. In addition, the carbon shell 30 improves electrical conductivity and participates in the reaction together with the catalyst layer 20 to exhibit excellent reaction activity. Therefore, when the catalyst composite is used for the electrode of a fuel cell, oxygen gas, hydrogen gas, etc. may come into contact with the catalyst layer 20 , and the oxidation-reduction reaction of oxygen may occur more easily. As a result, even if the content of platinum is lowered, it is possible to obtain a catalyst composite having performance equivalent to or superior to that of the prior art.

The carbon shell 30 may have a thickness of 5 nm or less. The thickness of the carbon shell 30 may be adjusted according to the content of the first crosslinking agent in the manufacturing method according to the present invention. This will be described later.

The method for preparing a catalyst composite according to the present invention comprises the steps of preparing polystyrene-based copolymer particles by adding an initiator to a starting material including a monomer, a first crosslinking agent, and a surfactant and crosslinking through ultraviolet irradiation, the polystyrene-based copolymer particles A step of hyper-crosslinking, doping a metal atom to the resultant and carbonizing to obtain a metal atom/carbonized polystyrene-based copolymer particle, and a platinum precursor with the metal atom/carbonized polystyrene-based copolymer particle and heat-reducing by dissolving the mixture in a mixture containing carbonized polystyrene-based copolymer particles to obtain a catalyst including a catalyst layer including a catalyst metal supported on the particles and a carbon shell formed on the catalyst layer.

Unlike the conventional method for producing a platinum catalyst, the present invention does not use a block copolymer as a starting material, but uses a monomer and cross-links it to form particles, so that various monomers can be selected. The monomer is styrene (Styrene), 4-vinylbiphenyl (4-vinylbiphenyl), 2-vinyl pyridine (2-vinyl pyridine), N-ethyl-2-vinylcarbazole (N-ethyl-2-vinylcarbazole), It may include at least one selected from the group consisting of benzyl methacrylate, benzyl acrylate, and combinations thereof.

The first crosslinking agent may include at least one selected from the group consisting of divinylbenzene, vinylbenzyl azide, and combinations thereof. In particular, the thickness of the carbon shell to be formed later may be adjusted according to the content of vinylbenzyl azide in the first crosslinking agent.

The starting material is 75 mol% to 90 mol% of styrene, 5 mol% to 10 mol% of divinylbenzene, and 5 mol% of vinylbenzyl azide among 100 mol% of the sum of styrene, divinylbenzene and vinylbenzyl azide to 20 mol%.

The surfactant is polyvinylpyrrolidone, sodium dodecyl sulfate, cetrimonium bromide, dodecyltrimethylammonium bromide, polyvinyl alcohol, and It may include at least one selected from the group consisting of combinations thereof.

3 is a reference diagram illustrating a state when the starting material is stirred for a predetermined time. According to this, the starting material is a monomer, a first cross-linking agent including divinylbenzene (DVB) and vinylbenzyl azide (VBA) is surrounded by a surfactant and is present in the form of micelles.

In the present invention, polystyrene-based copolymer particles are prepared by adding an initiator to the starting material in the state shown in FIG. 3 and irradiating ultraviolet rays to cause a crosslinking reaction.

The initiator is not particularly limited and a photoinitiator such as potassium persulfate may be used.

Next, the polystyrene-based copolymer particles may be hyper crosslinked.

The hyper crosslinking may be a Friedel-Craft reaction. This is crosslinking with adjacent moieties, thus allowing the particle to retain its internal morphology and shape while undergoing the carbonization step.

The hyper crosslinking may be performed by immersing the polystyrene-based copolymer particles in a mixture of a crosslinking catalyst, a second crosslinking agent, and a crosslinking solvent at a temperature of 30°C to 90°C for 12 hours to 48 hours. The immersion time may vary depending on the type of material.

The cross-linking catalyst may include at least one selected from the group consisting of FeCl ₃ , FeCl ₃ .6H ₂ O, AlCl ₃ , CoCl ₃ , ZnCl ₃ , CrCl ₄ and combinations thereof.

The second crosslinking agent may include at least one selected from the group consisting of formaldehyde dimethyl acetal, trichloromethane, carbon tetrachloride, and combinations thereof.

The crosslinking solvent is 1,2-dichloroethane (1,2 dichloroethane; DCE), 1,2-dichloropropane (1,2-dichloropropane; DCP), 1,4-dichlorobenzene (1,4-dichlorobenzene; DCB) ) and may include at least one selected from the group consisting of combinations thereof.

After dispersing the hyper-crosslinked block copolymer particles in ethanol, a precursor containing the metal atoms is poured into the solution to deposit metal atoms on the particles, stirred at a temperature of 60° C. to 100° C., and the ethanol is evaporated. After drying, the product may be dried at a temperature of 40°C to 60°C.

The precursor including the metal atom may include FeCl ₃ , CoCl ₂ , NiCl ₂ , and the like.

Thereafter, the dried resultant may be carbonized to obtain metal atom/carbonized polystyrene-based copolymer particles. The carbonization may be performed for 1 hour to 3 hours at a temperature range of 600° C. to 1100° C. under a nitrogen atmosphere.

The metal atom/carbonized polystyrene-based copolymer particles are added to a solution containing ethanol and a platinum precursor, dried, and then the obtained powder is thermally reduced in an inert atmosphere to obtain the catalyst composite described above.

The thermal reduction may be performed for 10 minutes to 2 hours in a temperature range of 300° C. to 700° C. under H ₂ /N ₂ atmosphere.

Hereinafter, the present invention will be described in detail with reference to the following Examples and Comparative Examples. However, the technical spirit of the present invention is not limited or limited thereto.

Example 1

Prepare the starting material by mixing styrene (0.913 ml), divinylbenzene (46 μl), vinylbenzyl azide (100 μl) and polyvinylpyrrolidone (300 mg/100 ml deionized water) and stirring for about 15 minutes. did. Potassium persulfate (60 mg/4 ml deionized water) was added dropwise to the starting material, followed by nitrogen bubbling (N ₂ bubbling) for about 30 minutes, followed by reaction at about 70° C. and about 24 hours in a nitrogen atmosphere. and emulsion polymerization of the starting material. 4 is a scanning electron microscope analysis result of the emulsion polymerization result. The average particle diameter (D50) of the above result was about 85.8±7.3 nm. The resultant was irradiated with ultraviolet rays (254 nm) and stirred for about 12 hours to pre-crosslink. Thereafter, the excess surfactant was removed by repeated centrifugation at 13,000 rpm for 2.5 hours, and dried under vacuum for about 12 hours to obtain polystyrene-based copolymer particles.

The polystyrene-based copolymer particles (400 mg) were dispersed in dichloroethane. Then FeCl ₃ (2 g) was added to the solution, and formaldehyde dimethyl acetal (4 mL) was slowly poured into the solution. The solution was stirred at about 50° C. for about 2 hours, then the temperature was raised to 80° C. and crosslinked for about 22 hours. To remove excess FeCl ₃ , the solution was washed with a mixture containing 90% by weight of ethanol and 10% by weight of hydrochloric acid, filtered and dried for about 12 hours.

The hyper-crosslinked product was dispersed in 20 ml of ethanol. Thus, FeCl ₃ (48 mg) was poured into the above solution to deposit iron (Fe) atoms. The solution was continuously stirred at 80°C. The solution was continuously stirred at 80 °C. After evaporation of the ethanol, the product was dried under vacuum at 50° C. overnight. Thereafter, the powder was carbonized at about 900° C. under a nitrogen flow at a ramping rate of 10° C./min for 2 hours to obtain iron atom/carbonized polystyrene-based copolymer particles. 5A is a scanning electron microscope analysis result of the carbonized product. The average particle diameter (D50) of the above result was about 77.5±3.3 nm. The present invention can maintain a spherical shape because the emulsion-polymerized product is hyper-crosslinked and then carbonized. On the other hand, Figure 5b is a scanning electron microscope analysis results of the emulsion-polymerized product was carbonized without hyper-crosslinking. If carbonization is performed without hyper-crosslinking, it can be seen that the spherical shape cannot be maintained and decomposed by heat treatment of about 900°C or higher.

H ₂ PtCl ₆ was dissolved in ethanol, and then the iron atom/carbonized polystyrene-based copolymer particles were added to the solution. The mixture was dried and the obtained black powder was reduced at 500° C. for 1 hour under a H ₂ /N ₂ flow rate (20: 180 sccm). Finally, the FePt/cPS particle catalyst was obtained as a black powder. The platinum content of the catalyst was adjusted to 1% by weight. 6 is a scanning electron microscope result of the FePt / cPS particle catalyst obtained through the example. The average particle diameter (D50) of the above catalyst was about 77.5±3.3 nm.

An electrochemical half-cell test was performed using the above catalyst.

Specifically, the electrochemical half-cell test was performed in a three-elec-trode cell with a CHI 760E potentiostat at 25°C. The working electrode was a rotating ring disk electrode of glassy carbon (Pine, area: 0.247 cm ² ). The counter electrode was a coiled platinum wire, and the reference electrode was Ag/AgCl saturated with 3 M NaCl. All potentials of the half-cell tests obtained by evolution and hydrogen oxidation in aH ₂ -saturated 0.1 M HClO ₄ solution using a Pt rotating disk electrode were reported for a reversible hydrogen electrode (RHE). . The catalyst powder was mixed in deionized water, IPA and 5 wt % Nafion® and sonicated in an ultrasonic bath for 20 minutes. The catalyst ink was loaded onto the working electrode and dried. The catalyst was activated by repeating 50 cycles of CV from 0.05 V _RHE to 1.0 V _RHE in Ar-saturated 0.1 M HClO ₄ solution at 100 mV s ⁻¹ . Linear sweep voltammetry (LSV) results were collected between 0.05 V _RHE and 1.1 V _RHE for the positive scan direction in O ₂ -saturated 0.1 M HClO ₄ solution at 10 mV s ⁻¹ and 1600 rpm. . ORR mass and specific activity were estimated using the Koutecky-Levich equation at 0.9 V _RHE from the LSV curve after iR correction. Durability was tested by performing accelerated degradation tests (ADThalf cell, hc) between 0.6 V _RHE and 1.0 V _RHE for 5,000 and 10,000 cycles in O2-saturated 0.1 M HClO ₄ at 100 mV s ⁻¹ . The results are shown in FIGS. 7A and 7B. In addition, the results of measuring the mass activity and durability of the catalyst obtained in Examples are shown in Table 1 below.

Mass activity @ 0.9 V _RHE (A mg ^{- 1} _Pt ) 100 nm Initial 5.81 After 5K cycles 5.31 After 10K cycles 3.98

Referring to this, it can be confirmed that a catalyst structure showing high characteristics was made even though the amount of platinum was very small as 1% by weight. In particular, high performance and excellent durability of 5A mg ^{- 1} _Pt or more were confirmed, and high mass activity was observed even after 10,000 cycles.

A full-cell test was performed using the above catalyst. In addition, a commercially available platinum catalyst (Commercial Pt/C) was set as a comparative example and tested together. The results are shown in FIGS. 8A and 8B. In addition, the results of measuring their mass activity are shown in Table 2 below.

Item Example (1wt% Pt loaded 0.01 mg _Pt cm ^-2 ) Comparative Example (commercial Pt/C, 20wt% Pt loaded 0.2 mg _Pt cm ^-2 ) Mass activity [A mg ^{- 1} _Pt ] 1.7 0.1~0.2

Referring to this, the catalyst according to the present invention showed high full-cell performance and durability despite a significantly reduced amount of platinum (1/20 level compared to a commercial catalyst). Commercial Pt/C showed a 30% decrease in performance after 30,000 cycles.

Examples 2 to 4

Meanwhile, in order to examine the effect of the content of the first crosslinking agent on the thickness of the carbon shell, a catalyst was prepared in the same manner as in Example 1, but the composition of the starting material was adjusted as shown in Table 3 below to prepare a catalyst.

division vinylbenzyl azide styrene divinylbenzene Example 2 5 mol% 90 mol% 5 mol% Example 3 10 mol% 85 mol% 5 mol% Example 4 20 mol% 75 mol% 5 mol%

9A to 9C are scanning electron microscope analysis results for the catalysts obtained in Examples 2 to 4, respectively. Referring to this, it can be seen that as the content of vinylbenzyl azide increases, the thickness of the carbon shell increases. Through this, it was confirmed that vinylbenzyl azide plays an important role in the formation of the carbon shell.

As described above, although the embodiments have been described with reference to the limited embodiments and drawings, various modifications and variations are possible by those skilled in the art from the above description. For example, even if the described techniques are performed in an order different from the described method, and/or the described components are combined or combined in a different form from the described method, or replaced or substituted by other components or equivalents Appropriate results can be achieved. Therefore, other implementations, other embodiments, and equivalents to the claims are also within the scope of the following claims.

10: carbonized polystyrene-based copolymer particles 20: catalyst layer 30: carbon shell

Claims (16)

Carbonized polystyrene-based copolymer particles;
a catalyst layer comprising a catalyst metal supported on the particles; and
A catalyst composite comprising a; carbon shell formed on the catalyst layer. According to claim 1,
The particle is a catalyst composite having a spherical shape. According to claim 1,
The particles have an average particle diameter (D50) of 50 nm to 1 μm. According to claim 1,
The catalyst metal is platinum; and
A catalyst composite comprising at least one selected from the group consisting of iron, nickel, cobalt, and combinations thereof. According to claim 1,
The carbon shell is a catalyst composite having a thickness of 5 nm or less. preparing polystyrene-based copolymer particles by adding an initiator to a starting material including a monomer, a first crosslinking agent, and a surfactant and crosslinking through ultraviolet irradiation;
hyper-crosslinking the polystyrene-based copolymer particles;
Doping a metal atom to the resultant, followed by carbonization to obtain a metal atom/carbonized polystyrene-based copolymer particles; and
Polystyrene-based copolymer particles carbonized by dissolving the metal atoms/carbonized polystyrene-based copolymer particles in a mixture containing a platinum precursor and thermal reduction, a catalyst layer including a catalyst metal supported on the particles, and formed on the catalyst layer A method for producing a catalyst composite comprising a; obtaining a catalyst comprising a carbon shell. 7. The method of claim 6,
The monomer is styrene (Styrene), 4-vinylbiphenyl (4-vinylbiphenyl), 2-vinyl pyridine (2-vinyl pyridine), N-ethyl-2-vinylcarbazole (N-ethyl-2-vinylcarbazole), A method for preparing a catalyst composite comprising at least one selected from the group consisting of benzyl methacrylate, benzyl acrylate, and combinations thereof. 7. The method of claim 6,
The first crosslinking agent is a method for producing a catalyst complex comprising at least one selected from the group consisting of divinylbenzene (Divinylbenzene), vinyl benzyl azide (Vinylbenzyl azide), and combinations thereof. 7. The method of claim 6,
The monomer comprises styrene,
The first crosslinking agent includes divinylbenzene and vinylbenzyl azide,
In 100 mol% of styrene, divinylbenzene and vinylbenzyl azide combined
A method for producing a catalyst composite comprising 75 mol% to 90 mol% of styrene, 5 mol% to 10 mol% of divinylbenzene, and 5 mol% to 20 mol% of vinylbenzyl azide. 7. The method of claim 6,
The surfactant is polyvinylpyrrolidone, sodium dodecyl sulfate, cetrimonium bromide, dodecyltrimethylammonium bromide, polyvinyl alcohol, and A method for producing a catalyst composite comprising at least one selected from the group consisting of combinations thereof. 7. The method of claim 6,
The hyper-crosslinking is a method of producing a catalyst composite by immersing the polystyrene-based copolymer particles in a mixture of a crosslinking catalyst, a second crosslinking agent and a solvent at a temperature of 30°C to 90°C for 12 hours to 48 hours. 12. The method of claim 11,
The cross-linking catalyst is FeCl ₃ , FeCl ₃ ·6H ₂ O, AlCl ₃ , CoCl ₃ , ZnCl ₃ , CrCl ₄ and a method for producing a catalyst complex comprising at least one selected from the group consisting of combinations thereof. 12. The method of claim 11,
The second crosslinking agent is formaldehyde dimethyl acetal (Formaldehyde dimethyl acetal), trichloromethane (Trichloromethane) and carbon tetrachloride (Carbon tetrachloride) and a method for preparing a catalyst complex comprising at least one selected from the group consisting of combinations thereof . 7. The method of claim 6,
The metal atom is a method for producing a catalyst composite comprising at least one selected from the group consisting of iron, nickel, cobalt, and combinations thereof. 7. The method of claim 6,
The carbonization is a method for producing a catalyst composite that is carried out for 1 hour to 3 hours at a temperature range of 600 ℃ to 1100 ℃ under a nitrogen atmosphere. 7. The method of claim 6,
The thermal reduction is, H ₂ /N ₂ Method for producing a catalyst composite that is performed for 10 minutes to 2 hours in a temperature range of 300 ℃ to 700 ℃ under an atmosphere.

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