KR101654136B1 - Method for preparing mesoporous carbon catalyst composite - Google Patents
Method for preparing mesoporous carbon catalyst composite Download PDFInfo
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- KR101654136B1 KR101654136B1 KR1020150060442A KR20150060442A KR101654136B1 KR 101654136 B1 KR101654136 B1 KR 101654136B1 KR 1020150060442 A KR1020150060442 A KR 1020150060442A KR 20150060442 A KR20150060442 A KR 20150060442A KR 101654136 B1 KR101654136 B1 KR 101654136B1
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9008—Organic or organo-metallic compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The present invention relates to a porous carbon catalyst composite comprising a nitrogen-containing porous carbon composite and an ion of a transition metal coordinatively bonded to nitrogen (N), and a process for producing the same. The porous carbon catalyst composite of the present invention can substitute for platinum, has excellent oxygen reduction activity, and can shorten the production time of the catalyst by using the self-assembling property of the block copolymer in the formation of the porous structure of the catalyst, Can be simplified.
Description
The present invention relates to a porous carbon catalyst composite and a method for producing the same, and more particularly, to a porous carbon catalyst composite and a porous carbon catalyst composite which can replace platinum and have excellent oxygen reduction reaction activity.
Fuel cells, which convert chemical energy generated by oxidation of fuel directly into electric energy, are attracting attention as next generation energy sources. Especially, in the automobile related fields, researches for commercialization are actively carried out because of advantages such as fuel consumption reduction, emission gas reduction, .
In order to increase the rate of redox reaction, the fuel cell should use platinum, a noble metal catalyst, for the anode and cathode of the fuel cell. However, platinum is not only high in price but also has a limited amount of reserves. As an example of a hydrogen fuel cell vehicle, the average amount of platinum used in a fuel cell vehicle is 50 g per unit, and when producing 70 million cars a year, 3,500 tons of platinum is required. However, the current production of platinum is only 180 tons per year, and the estimated amount of platinum is about 36,000 tons, making it difficult to cope with mass production of hydrogen fuel cell vehicles. In terms of price, the platinum price is 65,000 won per g, and the raw material cost of 50 g of platinum is more than 3.25 million won. Furthermore, since platinum is complexed, pyrolyzed, and the like to be processed into ultrafine particles of 2 to 3 nm, the production cost of the platinum catalyst is greatly increased. To solve this problem, it is necessary to develop an oxygen reduction catalyst that can replace platinum.
Korean Patent Laid-Open Publication No. 10-2007-0105701 entitled " Cathode catalyst for fuel cell, membrane-electrode assembly and fuel cell system for fuel cell comprising the same ", is a non-noble metal catalyst material for replacing a platinum catalyst, -ON. ≪ / RTI > However, the Co-Fe-O-N catalyst has a problem that the catalyst activity is significantly lower than that of platinum.
Therefore, it is necessary to develop a new catalyst having excellent oxygen reduction activity and improved durability as an oxygen reduction catalyst that can replace platinum. In addition, the conventional method of producing a porous catalyst using a preliminarily synthesized porous mold requires time-consuming and complicated processes, and therefore, it is necessary to develop a method of manufacturing a porous catalyst that can shorten the manufacturing time and simplify the process.
An object of the present invention is to provide a porous carbon catalyst composite which can replace platinum and is excellent in oxygen reduction reaction activity.
It is another object of the present invention to provide a method for producing a porous carbon catalyst composite which can shorten the production time of the catalyst and simplify the process by using the self-assembling property of the block copolymer to form a porous structure.
According to an aspect of the present invention,
A porous carbon composite material containing nitrogen; And an ion of a transition metal coordinatively bonded to the nitrogen (N).
The transition metal may be at least one selected from Fe, Co, Cr, Ni, Cu, Zn, and Mn.
The porous carbon catalyst composite includes a plurality of pores, and the plurality of pores may have a cylindrical shape or a spherical shape, and may be aligned in a predetermined direction.
The nitrogen may be covalently bonded to 1 to 3 carbons of the porous carbon composite.
The average diameter of the pores may be between 2 and 100 nm.
According to another aspect of the present invention,
There is provided an electrode material comprising the porous carbon catalyst composite.
According to another aspect of the present invention,
There is provided a fuel cell including the electrode material as an anode.
According to another aspect of the present invention,
Preparing a mixed solution comprising a block copolymer including a hydrophobic polymer block and a hydrophilic polymer block, a carbon precursor, a silica precursor, and a metal chelate compound and a solvent (step a); (B) preparing a complex in which the carbon precursor, the silica precursor and the metal chelate compound are positioned on the hydrophilic polymer block by self-assembling the block copolymer by removing the solvent of the mixed solution; (C) preparing a porous carbon composite material comprising a porous carbon material containing nitrogen, ions of transition metal, and silica by heat treating the composite to form pores; And removing the silica from the porous carbon composite to thereby prepare a porous carbon catalyst composite comprising a porous carbon material and ions of a transition metal (step d).
The metal chelate compound may be at least one selected from 1,10-phenanthroline iron (II), porphyrin iron (II) and phthalocyanine iron (II).
The metal chelate compound may be 1,10-phenanthroline iron (II).
Step b may evaporate the solvent to evaporation induced self-assembly (EISA) the block copolymer.
The evaporation-induced self-assembly may be performed at 30 < 0 > C to 70 < 0 > C.
The heat treatment temperature may be 600 ° C to 1200 ° C.
The heat treatment may be performed in a gas atmosphere of any one of argon, nitrogen, helium, and neon.
Removal of the silica in step d may be carried out using a basic solution or an acidic solution.
The carbon precursor may be at least one selected from the group consisting of resol, furfuryl alcohol, furfuryl amine, sucrose, glucose and dopamine.
The block copolymer may be a multi-block copolymer.
The block copolymer may be at least one selected from a diblock copolymer and a triblock copolymer.
The triblock copolymer may be any one selected from the group consisting of a polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer, a polyethylene oxide-polystyrene-polyethylene oxide block copolymer, and a polyethylene oxide-polyisoprene-polyethylene oxide block copolymer.
The silica precursor may be at least one selected from tetraethylorthosilicate, n-octacetyltrimethoxysilane, and sodium silicate.
The solvent may be at least one selected from the group consisting of ethanol, aqueous hydrogen chloride solution, tetrahydrofuran, and dimethylformamide.
The porous carbon catalyst composite of the present invention can substitute for platinum and has an excellent effect of oxygen reduction reaction.
In addition, when the porous structure of the catalyst is formed, the self-assembling property of the block copolymer is used to shorten the production time of the catalyst and to simplify the process.
1 is a schematic view showing a process and structure of a porous carbon catalyst composite of the present invention.
2 is a flow chart of a method for producing the porous carbon catalyst composite of the present invention.
Fig. 3 shows the UV-vis absorption spectrum of the mixed solution prepared according to Production Example 1. Fig.
4 is a graph for confirming the structural characteristics of the porous carbon catalyst composite of the present invention.
5 is an SEM image and TEM image of the porous carbon catalyst composite of the present invention.
6 shows the N1s spectrum of Example 1 measured by X-ray photoelectron spectroscopy (XPS).
7 is a graph for confirming the oxygen reduction reaction activity of the porous carbon catalyst composite of the present invention.
8 shows the polarization curve of the oxygen reduction reaction of the anode prepared according to Example 2 and Comparative Example 4. Fig.
Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention.
However, the following description does not limit the present invention to specific embodiments. In the following description of the present invention, detailed description of related arts will be omitted if it is determined that the gist of the present invention may be blurred .
The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises ",or" having ", and the like, specify that the presence of stated features, integers, steps, operations, elements, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.
Hereinafter, the porous carbon catalyst composite of the present invention will be described in detail.
1 is a schematic view showing a process and structure of a porous carbon catalyst composite of the present invention.
Referring to FIG. 1, the porous carbon catalyst composite of the present invention may include a porous carbon composite material containing nitrogen and ions of a transition metal coordinated to nitrogen (N).
The transition metal may be coordinatively coupled with the nitrogen to form a catalyst point. The catalytic site may have an oxidation-reduction reaction activity, thereby improving the oxidation-reduction activity.
The transition metal may be Fe, Co, Cr, Ni, Cu, Zn, Mn, or the like.
The nitrogen may be covalently bonded to 1 to 3 carbons of the porous carbon composite.
The porous carbon catalyst composite may include a plurality of pores. The plurality of pores may have a cylindrical shape or a spherical shape, and may be aligned in a predetermined direction. The regularity of the pores can improve the redox reaction activity. The average diameter of the pores may be 2 to 100 nm, preferably 2 to 50 nm, more preferably 2 to 30 nm. The pore is a passage through which the reactant can be supplied to the catalyst point, and the oxidation / reduction reaction activity of the porous carbon catalyst composite can be improved due to the porous structure.
2 is a flow chart of a method for producing the porous carbon catalyst composite of the present invention.
The method for producing the porous carbon catalyst composite of the present invention will be described with reference to FIG.
First, a mixed solution containing a block copolymer including a hydrophobic polymer block and a hydrophilic polymer block, a carbon precursor, a silica precursor, a metal chelate compound and a solvent is prepared (step a).
The metal chelate compound may be 1,10-phenanthroline iron (II), porphyrin iron (II), phthalocyanine iron (II) or the like, preferably 1,10-phenanthroline iron .
The carbon precursor may be a resol, furfuryl alcohol, furfuryl amine, sucrose, glucose, or dopamine. Preferably, the carbon precursor is a resorcinol, .
The block copolymer may be a multiblock copolymer, and may be a double block copolymer or a triblock copolymer, but may preferably be a triblock copolymer.
The triblock copolymer may be a polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer, a polyethylene oxide-polystyrene-polyethylene oxide block copolymer, a polyethylene oxide-polyisoprene-polyethylene oxide block copolymer, Oxide-polypropylene oxide-polyethylene oxide block copolymer.
However, the present invention is not limited thereto. Any block copolymer including a hydrophilic block and a hydrophobic block and having self-assembling properties may be used, and a polyethylene oxide-polyisoprene block copolymer or a polyethylene oxide-polystyrene block copolymer may be used as the double block copolymer.
The silica precursor may be tetraethylorthosilicate, n-octacetyltrimethoxysilane, sodium silicate, or the like, preferably tetraethylorthosilicate.
The solvent of the mixed solution may be ethanol, an aqueous solution of hydrogen chloride, tetrahydrofuran, dimethylformamide or the like, preferably ethanol and a hydrogen chloride aqueous solution.
Next, the solvent of the mixed solution is removed to self-assemble the block copolymer to prepare a complex in which the carbon precursor, the silica precursor and the metal chelate compound are located in the hydrophilic polymer block (step b).
The block copolymer is a polymer composed of a hydrophilic block and a hydrophobic block. When the solvent is removed, the block copolymer is precipitated and self-assembled, resulting in a pattern. At this time, the solvent is removed through evaporation, and the evaporation-induced self-assembly (EISA) of the block copolymer can be performed when the solvent is evaporated. The evaporation-induced self-assembly may be performed at 30 ° C to 70 ° C, preferably at 35 ° C to 65 ° C, more preferably at 40 ° C to 60 ° C.
Next, the composite is heat-treated to form pores to prepare a porous carbon composite material containing a porous carbon material containing nitrogen, ions of transition metal and silica (step c).
The metal chelate compound of the hydrophilic block of the block copolymer forms a catalyst point due to the heat treatment, and the carbon precursor and the silica precursor form a carbon-silica complex to form a pore wall of the porous carbon catalyst composite. The hydrophobic block of the block copolymer is pyrolyzed to become pores of the porous carbon catalyst composite.
The heat treatment temperature may be 600 ° C to 1200 ° C, preferably 700 to 1100 ° C, and more preferably 800 to 1000 ° C. In addition, the heat treatment is preferably performed in an inert gas atmosphere such as argon, nitrogen, helium, or neon.
Finally, the silica is removed from the porous carbon composite material to prepare a porous carbon catalyst composite containing a porous carbon material and ions of a transition metal (step d).
The silica may be etched into a basic solution or an acidic solution. The basic solution may be a solution of sodium hydroxide, calcium hydroxide, potassium hydroxide or the like, and the acidic solution may be hydrofluoric acid.
[Example]
Hereinafter, preferred embodiments of the present invention will be described. However, this is for illustrative purposes only, and thus the scope of the present invention is not limited thereto.
Manufacturing example 1: Preparation of mixed solution
0.64 g of Pluronic F127 (Aldrich) was dissolved in 2.23 ml of ethanol and 0.22 ml of 0.2 M HCl to prepare a polymer solution. Next, 93 mg of FeCl 2 -4H 2 O and 253 mg of 1,10-phenanthroline were mixed with 16.9 ml of ethanol and 1.67 ml of 0.2M HCl to prepare a Fe (phen) 3 Cl 2 complex solution. 0.292 g of resole, 0.892 ml of tetraethylorthosilicate (Aldrich) and 7 g of the Fe (phen) 3 Cl 2 complex solution were added to the polymer solution to prepare a mixed solution.
Manufacturing example 2: self-assembled Block copolymer Produce
The mixed solution prepared according to Preparation Example 1 was stirred for 1 hour, and then the solution was poured into a dish. The solvent was evaporated at 50 占 폚 and then placed in an oven at 100 占 폚 for 24 hours to prepare a self-assembled block copolymer.
Example 1: Preparation of porous carbon catalyst composite
The self-assembled block copolymer prepared according to Preparation Example 2 was heat-treated at 900 ° C for 2 hours in an argon atmosphere. Next, silica was etched with a 2 M NaOH solution to prepare a porous carbon catalyst composite. The chemical structures of the catalyst points that can be included in the porous carbon catalyst composite prepared according to Example 1 are shown in Formulas (1) to (3).
[Chemical Formula 1]
(2)
(3)
Example 2: Preparation of anode
The porous carbon catalyst composite prepared according to Example 1 was immersed in 2-propanol (Junsei chemical) to prepare a slurry, and 5% by weight of Nafion solution (Aldrich, low-fat alcohol and water containing 15 to 20% ) Was added dropwise to the slurry. The weight ratio of naphion to the porous carbon catalyst composite was 0.6. The porous carbon catalyst composite ink was prepared by dispersing by sonication for 1 hour to prepare a porous carbon catalyst composite ink. Then, 10 μl of the porous carbon catalyst composite ink was coated on the glassy carbon polished with 45 nm alumina particles (Alfa-Aesar) catal / cm < 2 > dropwise to prepare a positive electrode.
Comparative Example 1: Preparation of pore-free catalyst composite
A pore-free catalyst composite was prepared in the same manner as in Example 1, except that Pluronic F127 (Aldrich) was not used in the mixed solution of Preparation Example 1.
Comparative Example 2: Preparation of porous carbon catalyst composite without iron ion
A porous carbon catalyst composite without iron ion was prepared in the same manner as in Example 1, except that FeCl 2 -4H 2 O was not used in the mixed solution of Preparation Example 1.
Comparative Example 3: Preparation of a cathode comprising a catalyst composite without pores
A positive electrode was prepared in the same manner as in Example 2, except that the porous carbon catalyst composite prepared according to Example 1 was replaced with the porous catalyst composite prepared in Comparative Example 1.
Comparative Example 4: Preparation of a cathode comprising a porous carbon catalyst composite without iron ions
A cathode was prepared in the same manner as in Example 2, except that the porous carbon catalyst composite prepared according to Example 1 was replaced by the catalyst complex free of iron ions prepared in Comparative Example 2.
Comparative Example 5: Preparation of a positive electrode containing platinum catalyst
The anode was prepared by dropping 50 μg catal / cm 2 of a platinum catalyst (Pt /
[Test Example]
Test Example 1: Iron Chelate (Fe 2+ (phen) 3 )of Confirm
Fig. 3 shows the UV-vis absorption spectrum of the mixed solution prepared according to Production Example 1. Fig.
Referring to FIG. 3, the maximum peak appeared near the wavelength of 510 nm. This means that the iron chelate (Fe 2+ (phen) 3 ) and the iron chelate are not separated by the block copolymer, resole and hydrolyzed silica precursor.
Therefore, it was found that the porous catalyst of the present invention is very advantageous for forming the catalyst point in the subsequent carbonization process due to the iron chelate.
Test Example 2: Identification of structural characteristics
4 (a) shows the X-ray diffraction spectrum of the catalyst composite prepared according to Production Example 2 (m-FePhen-as-syn), Example 1 (m-FePhen-C) and Comparative Example 1 (SAXS) pattern. FIG. 4 (b) shows the results of N 2 adsorption measurement of the catalyst composite prepared according to Example 1 and Comparative Example 1. FIG. 5 (a) and 5 (b) are SEM images of Example 1, and FIGS. 5 (c) and 5 (d) are TEM images of Example 1. FIG.
Referring to (a) of Figure 4, the peak of Preparation 2 (m-FePhen-as- syn) represents a cylinder arrangement structure of hexagonal crystal (P6mm). The peak of the porous carbon catalyst composite of Example 1 (m-FePhen-C) obtained by heat-treating the catalyst composite of Production Example 2 at 900 ° C was shifted to a high vector position due to shrinkage of the structure. However, the position of the peak was preserved, and it was found that the arrangement of the structure was not destroyed. On the other hand, no indication related to the arrangement was shown in Comparative Example 1 (b-FePhen-C).
Thus, it was found that Pluronic F127 plays a role as a structure directing agent.
4 (b), the mesoporous structure of the catalyst composite of Example 1 was measured with a pore size distribution measured by nitrogen absorption measurement of Example 1 (m-FePhen-C) . The most significant pore peak showed a clear peak at 9.3 nm. Brunauer-Emmett-Teller (Brunauer-Emmett-Teller) surface area calculated by the method of Example 1 in the case were very large compared to 192m 2 / g of Comparative Example 1 to 1437 m 2 / g. Example 1 is judged to have a very large surface area by a micropore formed by removing mesopores and silica formed by decomposition of a block copolymer. On the contrary, Comparative Example 1 is judged to have a low surface area due to a wide irregular pore distribution and low porosity.
Accordingly, it was found that the porous carbon catalyst composite of Example 1 (m-FePhen-C) had regular porous structure, large pore size, and large surface area favorable for the oxygen reduction reaction.
5 (a) and 5 (b), the porous carbon catalyst composite of Example 1 showed that columnar mesopores were arranged very regularly in hexagonal form.
Referring to FIGS. 5 (c) and 5 (d), solid particles of several tens of nanometers are also observed because the iron ions (Fe 2 + ) are partially replaced with metal or oxide forms and sintered into large particles . The approximate average pore diameter is 9.1 nm, which is similar to the pore size of 9.3 nm in FIG. 4 (b).
Thus, the regular porous structure of Example 1 (m-FePhen-C) was confirmed.
Test Example 3: nitrogen functional ( functional ) Confirmation of
6 shows the N1s spectrum of Example 1 measured by X-ray photoelectron spectroscopy (XPS).
Referring to FIG. 6, four peaks of pyridinic N (398.2 eV, 44.8%), pyrrolic N (399.5 eV, 4.7%), quaternary N (401.2 eV, 44.1% . pyridinic N and pyrrolic N means nitrogen located at the edge of the basal plane of the carbon, accounting for 51.2% of the nitrogen functionality.
Therefore, it is judged that the iron ion can bond with the nitrogen at the above position and form a catalyst point.
Test Example 4: Determination of oxygen reduction activity of porous carbon catalyst composite
7 (a) shows the oxygen reduction polarization curve of the anode prepared according to Example 2 and Comparative Examples 3 to 5. FIG. 7 (b) shows the oxygen reduction polarization curve of Example 2 at various angular velocities. 7 (c) shows a Koutecky-Levich plot of Example 2, and FIG. 7 (d) shows the electron transfer number of Example 2 at each potential will be.
7 (a), Example 2 (m-FePhen-C) and Comparative Example 3 (b-FePhen-C) had active sites formed from the same precursor, The oxygen reduction activity was very low as compared with the oxygen reduction activity of Example 2. This means that the reaction kinetics is lowered by the mass transport resistance of the catalyst particles. The half-wave potential of Comparative Example 3 was lower by 154 mV than the half-wave potential of Example 2, and the curve reached the diffusion limited current at 0.5 V only. Comparative Example 4 (m-Phen-C) used the same nitrogen precursor as in Example 2 and had a porous structure but had no iron ion and had very low onset potential and did not reach the diffusion limiting current I could confirm. Therefore, it was found that the preference for the direct reduction pathway in which four electrons are transferred from the catalyst surface is low.
The Koutecky-Levich plot can be expressed as
[Formula 1]
In the
The path of the oxygen reduction reaction mediated by the generation of H 2 O 2 has an electron transition number of 2 and the direct path to H 2 O has an electron transition number of 4. Referring to FIGS. 7 (b), 7 (c), 7 (d) and 1, the relationship between the inverse current density and the inverse square of the angular velocity of the
Therefore, it was found that the catalyst composite of the present invention having catalytic sites containing both porous and iron ions exhibits high oxygen reduction activity.
Test Example 5: Catalytic Identification of oxygen reduction reaction activity
8 (a) shows the oxygen reduction reaction polarization curve of Example 2, and Fig. 8 (b) shows the oxygen reduction reaction polarization curve of Comparative Example 4. Fig.
Gewirth and his colleagues found that cyanide anion (CN - ) poisoned the core metal of a macrocycle containing nitrogen using primitive and pyrolysed phthalocyanine molecules under basic conditions . That is, it can be judged that the cyanide anion (CN - ) inhibits the action of the metal catalyst coordinated nitrogen catalyst site.
Referring to (a) and (b) of Figure 8, CN - ions not 0.1 M of KOH solution and CN - when tested in (KOH in 10 mM of KCN, 0.1 M) ion solution of Example 2 (m -FePhen-C) showed a 69 mV shift in the on-state potential and the half-wave potential with a negative value when the CN - ion was present. However, the limiting current value did not change, which means that the decrease in the activity of the oxygen reduction reaction is due to the poisoning of the catalyst rather than the environmental factors such as the solubility of the O 2 or the viscosity of the solution. On the other hand, Comparative Example 4 (m-Phen-C) exhibited almost the same oxygen reduction activity in 0.1 M KOH solution and CN - ion solution.
Therefore, it can be confirmed that the catalyst point similar to the macrocycle in which the iron ion is coordinated to the oxygen reduction activity exhibited by Example 2 is a major contributor.
The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.
Claims (20)
(B) preparing a complex in which the carbon precursor, the silica precursor and the metal chelate compound are positioned on the hydrophilic polymer block by self-assembling the block copolymer by removing the solvent of the mixed solution;
(C) preparing a porous carbon composite material comprising a porous carbon material containing nitrogen, ions of transition metal, and silica by heat treating the composite to form pores; And
Removing the silica from the porous carbon composite material to prepare a porous carbon catalyst composite comprising a porous carbon material and ions of a transition metal (step d);
Wherein the porous carbon catalyst composite is produced by a method comprising the steps of:
The porous carbon catalyst composite
A porous carbon composite material containing nitrogen; And
And an ion of a transition metal coordinatively bonded to the nitrogen (N)
Wherein the porous carbon catalyst composite comprises a plurality of pores,
Wherein the plurality of pores are in the form of a cylinder and are aligned in a predetermined direction
A method for producing a porous carbon catalyst composite.
Wherein the transition metal is at least one selected from Fe, Co, Cr, Ni, Cu, Zn, and Mn.
Wherein the nitrogen is covalently bonded to 1 to 3 carbons of the porous carbon composite material.
Wherein the metal chelate compound is at least one selected from the group consisting of 1,10-phenanthroline iron (II), porphyrin iron (II), and phthalocyanine iron (II).
Wherein the metal chelate compound is 1,10-phenanthroline iron (II).
Wherein step b) evaporates the solvent to evaporation induced self-assembly (EISA) the block copolymer.
Wherein the evaporation-induced self-assembly is carried out at 30 ° C to 70 ° C.
Wherein the heat treatment temperature is 600 ° C to 1200 ° C.
Wherein the heat treatment is performed in a gas atmosphere of any one of argon, nitrogen, helium, and neon.
Wherein the removal of the silica in step d is carried out using a basic solution or an acidic solution.
Wherein the carbon precursor is at least one selected from the group consisting of resol, furfuryl alcohol, furfuryl amine, sucrose, glucose and dopamine. Carbon catalyst composite.
Wherein the block copolymer is a multiblock copolymer.
Wherein the block copolymer is at least one selected from a diblock copolymer and a triblock copolymer.
Wherein the triblock copolymer is any one selected from the group consisting of a polyethylene oxide-polypropylene oxide-polyethylene oxide block copolymer, a polyethylene oxide-polystyrene-polyethylene oxide block copolymer and a polyethylene oxide-polyisoprene-polyethylene oxide block copolymer A method for producing a porous carbon catalyst composite.
Wherein the silica precursor is at least one selected from the group consisting of tetraethylorthosilicate, n-octacosyltrimethoxysilane, and sodium silicate.
Wherein the solvent is at least one selected from the group consisting of ethanol, aqueous hydrogen chloride solution, tetrahydrofuran, and dimethylformamide.
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| WO2020096331A1 (en) * | 2018-11-07 | 2020-05-14 | 주식회사 엘지화학 | Lithium secondary battery |
| CN111744527A (en) * | 2020-06-24 | 2020-10-09 | 中国石油大学(华东) | High-performance carbon-based electrocatalytic oxygen reduction material based on mesoporous silica molecular sieve and preparation method thereof |
| KR20220045724A (en) * | 2020-10-06 | 2022-04-13 | 한국과학기술원 | A porous molybdenum carbide/carbon composite, a method for manufacturing the same, a catalyst for hydrogen generation reaction comprising the porous molybdenum carbide/carbon composite |
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| KR102466853B1 (en) | 2020-10-06 | 2022-11-16 | 한국과학기술원 | A porous molybdenum carbide/carbon composite, a method for manufacturing the same, a catalyst for hydrogen generation reaction comprising the porous molybdenum carbide/carbon composite |
| KR20220139688A (en) * | 2021-04-08 | 2022-10-17 | 울산과학기술원 | Method for manufacturing carbon fiber coating metal catalyst and carbon fiber for manufacturing electrode prduced thereby |
| KR102636169B1 (en) * | 2021-04-08 | 2024-02-16 | 울산과학기술원 | Method for manufacturing carbon fiber coating metal catalyst and carbon fiber for manufacturing electrode prduced thereby |
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