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WO2007072665A1 - Électrode d’oxydoréduction pour pile à combustible directe - Google Patents

Électrode d’oxydoréduction pour pile à combustible directe Download PDF

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Publication number
WO2007072665A1
WO2007072665A1 PCT/JP2006/323925 JP2006323925W WO2007072665A1 WO 2007072665 A1 WO2007072665 A1 WO 2007072665A1 JP 2006323925 W JP2006323925 W JP 2006323925W WO 2007072665 A1 WO2007072665 A1 WO 2007072665A1
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WO
WIPO (PCT)
Prior art keywords
electrode
oxygen reduction
potential
current
curve
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2006/323925
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English (en)
Japanese (ja)
Inventor
Ken-Ichiro Ota
Nobuyuki Kamiya
Shigenori Mitsushima
Yan Liu
Akimitsu Ishihara
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Yokohama National University NUC
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Yokohama National University NUC
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Publication date
Application filed by Yokohama National University NUC filed Critical Yokohama National University NUC
Priority to JP2007551024A priority Critical patent/JP5055557B2/ja
Publication of WO2007072665A1 publication Critical patent/WO2007072665A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • 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
    • H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00—Fuel cells; Manufacture thereof
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
    • H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
    • H01M8/1013—Other direct alcohol fuel cells [DAFC]
    • 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

Definitions

  • the present invention relates to an oxygen reduction electrode used in a direct fuel cell that directly oxidizes liquid fuel such as an alcohol aqueous solution.
  • Direct fuel cells that use liquid fuel such as methanol as a direct fuel do not require a hydrogen gas cylinder and have a simple structure. Therefore, they are being applied to portable applications, mobile power supplies, and distributed power supplies. Yes.
  • a direct fuel cell has a structure in which a proton conductive polymer electrolyte membrane is sandwiched between a negative electrode and a positive electrode, a methanol aqueous solution serving as fuel is supplied to the negative electrode, and air is supplied to the positive electrode. Then, fuel is oxidized at the negative electrode, and oxygen is reduced at the positive electrode, and the electric energy is taken out to the outside.
  • Patent Document 1 Japanese Patent Laid-Open No. 11 144745
  • Patent Document 2 Japanese Patent Laid-Open No. 2002-184427
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-257453
  • Non-specific literature l Yan Liu et.al., Zirconium uxides for PRFC Cathodes, Electrochemical and solid-state Letter, 8 (8), A400— A402 (2005)
  • an object of the present invention is to provide an oxygen reduction electrode for a direct fuel cell which is excellent in oxygen reduction catalytic ability even when a liquid fuel is used.
  • the oxygen reduction electrode for a direct fuel cell of the present invention is used as a positive electrode of a direct fuel cell that oxidizes a liquid fuel composed of an aqueous solution of an organic compound at the negative electrode, and ZrO (0.25 ⁇ xl 2.0) xl
  • an oxygen reduction electrode for a direct fuel cell excellent in oxygen reduction catalytic ability can be obtained even when liquid fuel is used.
  • the oxygen reduction electrode of the present invention is used as a positive electrode of a direct fuel cell in which a liquid fuel comprising an aqueous solution of an organic compound is oxidized at the negative electrode.
  • a direct fuel cell an electrolyte membrane is sandwiched between a positive electrode and a negative electrode, the liquid fuel is supplied from the outside of the negative electrode, and oxygen is contained from the outside of the positive electrode.
  • a gas (usually air) is supplied to extract electrical energy from the outside!
  • the negative electrode and the positive electrode are usually formed by applying an electrode active material as a catalyst on the surface of a porous electrode substrate.
  • organic compound what contains a carbon atom and a hydrogen atom in chemical structures, such as alcohol and ether, can be used, for example.
  • organic compound include methanol, ethanol, glycol, acetal, dimethyl ether, etc., but the activity energy of the acid-acid reaction is particularly small. It is effective in improving the energy conversion efficiency.
  • the electrode active material of the oxygen reduction electrode of the present invention is ZrO (0.25 ⁇ xl ⁇ 2.0), CoO (0.2 ⁇ x2 ⁇ 1.3
  • a metal oxide having at least one composition ratio is provided.
  • the electrode active material in the present invention is in a state where oxygen of the metal oxide is insufficient when surface analysis is performed with XPS (X-ray photoelectron spectroscopy analyzer).
  • an electrode active material force electrode containing at least one metal oxide is formed.
  • the reason why the coefficients xl to x5 are defined in the above range is that if each coefficient is less than the above range, the metal component becomes excessive, and the metal component becomes active and becomes unstable. It is. In addition, if each coefficient exceeds the above range (for example, when xl becomes equal to the upper limit of 2.0), it becomes a complete acid state, oxygen adsorption does not occur, and it does not act as an oxygen reduction catalyst. .
  • the metal oxide can be obtained, for example, by sputtering a metal or metal oxide target on a carbon electrode substrate.
  • spray reaction method using solution containing metal salt can also be used.
  • the formation of metal oxides with insufficient oxygen can be achieved by controlling the gas pressure in the sputtering atmosphere when depositing by sputtering, by controlling the annealing atmosphere in the case of heat treatment, and by controlling the atmosphere in the case of the spray reaction method. It can be carried out.
  • the electrode active material does not dissolve and is stable even when used in the presence of an aqueous solution of an organic compound.
  • FIGS. 1 and 2 schematically show current-potential curves of electrodes.
  • Fig. 1 shows the curve when the electrode according to the present invention is used
  • Fig. 2 shows the curve when the Pt electrode is used.
  • curve L is in an acidic solution without liquid fuel (alcoholic aqueous solution).
  • E eq is the theoretical o equilibrium potential, showing a balance between the rate of oxygen reduction and evolution.
  • the equilibrium potential is the potential at which the oxygen electrode reaction is in equilibrium, and the electrode reaction formula: 1Z20 + 2H ++
  • the equilibrium potential is the state in which the live reaction is balanced. When the potential is lower than the equilibrium potential, oxygen reduction occurs preferentially.
  • Curved fl is a current-potential curve in liquid fuel (alcoholic aqueous solution).
  • E eq is the theoretical equilibrium potential of the liquid fuel.
  • the oxidation and reduction reaction of the fuel is in a balanced state.
  • the acid-oxidation reaction of the fuel proceeds. Since the electrode of the present invention is inactive to the fuel acid, the current value associated with the fuel acid decreases.
  • Curve L shows the voltage tl when the liquid fuel supplied to the negative electrode of the fuel cell permeates the positive electrode.
  • curve L is a combination of curve L and curve L.
  • the electrode of the present invention has a small oxidation current of fuel.
  • curve L is almost the same as curve L, and the catalytic reaction is reduced by the permeated fuel.
  • curve L is in an acidic solution containing no liquid fuel (alcohol aqueous solution).
  • Curve L shows the electric power t2 when the liquid fuel supplied to the negative electrode of the fuel cell permeates the positive electrode.
  • Curve L is a combination of curve L and curve L.
  • Pt electrode is t2 02 f2
  • Curve L showing the reaction of only oxygen reduction, which is greatly affected by the oxidation current associated with fuel oxidation
  • the reason for setting the current density in the range of 10 ⁇ AZcm 2 to 15 ⁇ AZcm 2 is that the oxygen reduction reaction is dominant in this range of current, and the oxygen reduction is measured by measuring the current in this region. This is because the selectivity of the reaction can be evaluated.
  • the performance of the oxygen reduction electrode is reduced.
  • the air electrode acts by supplying oxygen as a reactant to the portion where the catalyst and the electrolyte are in contact.
  • a polymer having a sulfonic acid group is used as an electrolyte in a water-containing state. Therefore, the catalytic ability of the oxygen reduction electrode can be evaluated by substituting the electrolyte with sulfuric acid and simulating the above-described state of the air electrode.
  • the oxygen reduction catalyst is inactive with respect to the acid-oxidation reaction of the liquid fuel (eg, alcohol such as methanol) of the fuel cell, and oxygen reduction. Since it has sufficient catalytic activity for the reaction, it can contribute to the improvement of the performance (power generation efficiency, etc.) of the direct fuel cell.
  • the liquid fuel eg, alcohol such as methanol
  • a cylindrical glassy carbon having a diameter of 5.2 mm was used as a base material, and a ZrO thin film was formed on the bottom surface by sputtering as an electrode material.
  • Sputtering conditions are as follows: He partial pressure is 1 X 10 _3 Pa or less
  • the thickness of the obtained thin film was measured with a quartz vibration type film thickness meter, and found to be 30 nm.
  • O / Zr was 1.81. This means that the thin film produced is ZrO lacking oxygen compared to ZrO.
  • Electrolyte 1 was used. Prepare an aqueous solution containing 0.1 mol / L HSO alone as the electrolyte.
  • Electrolyte 2 was used. Each of the electrolytes 1 and 2 was filled in an electrolytic cell using a reversible hydrogen electrode as a reference electrode, a platinum electrode with platinum black as a counter electrode, and the oxygen reduction electrode as a working electrode. The electrode reaction was evaluated by scanning the potential at 5 mV / s in an oxygen atmosphere at 30 ° C.
  • the electrode reaction in the electrolyte 1 mimics the state in which liquid fuel (methanol) permeates the positive electrode (air electrode) of the fuel cell.
  • the electrode reaction in the electrolyte 2 simulates a state in which liquid fuel (methanol) does not permeate the positive electrode (air electrode) of the fuel cell.
  • Fig. 3 shows a current-potential curve when the oxygen reduction electrode is used (the electrolyte 1 shows a broken line in the figure, and the electrolyte 2 shows a solid line.
  • the electrolytes 1 and 2 were used, the current-potential curves were almost the same, and even when the electrolyte 1 was used, the current indicating the acidity of CH OH was strong. From this,
  • the electrode of this example has very poor catalytic activity for CH OH.
  • the negative current on the vertical axis in Fig. 3 indicates the rate of the oxygen reduction reaction.
  • An electrode that can obtain a large oxygen reduction current when the potential on the horizontal axis is high is more active.
  • the curve obtained by synthesizing the curve using electrolyte 2 is the actual curve. Force representing an electrode reaction in a fuel cell Because the acid current of methanol is small, the electrode of Example 1 does not decrease the oxygen reduction potential (that is, the performance of the oxygen reduction electrode does not decrease;) Wow.
  • Co 0 and CoO can also be mixed, so that not only the highest oxidation number of Co 0 but also oxygen-deficient acids
  • FIG. 5 shows a current-potential curve when the oxygen reduction electrode is used.
  • the current-potential curves when using electrolytes 1 and 2 are almost the same, and even when electrolyte 1 is used, CH OH
  • Example 2 Exactly the same as Example 1 except that SnO having a stoichiometric composition was used as a sputtering target.
  • an oxygen reduction electrode having a catalyst thickness of 30 nm was prepared. This electrode was also considered to contain oxygen-deficient oxides.
  • the electrode of this example is CH OH
  • FIG. 8 shows a current-potential curve when the oxygen reduction electrode is used.
  • the current-potential curves when using electrolytes 1 and 2 are almost the same, and even when electrolyte 1 is used, CH OH
  • Example 2 Exactly the same as Example 1 except that a sputter having a stoichiometric composition was used as a sputtering target.
  • FIG. 10 shows a current-potential curve when the oxygen reduction electrode is used.
  • the current-potential curves when using electrolytes 1 and 2 are almost the same, and even when electrolyte 1 is used, CH OH
  • a Pt electrode having a catalyst thickness of 30 nm was prepared in the same manner as in Example 1 except that Pt was used as the sputtering target.
  • FIG. 11 shows a current-potential curve when the above Pt electrode is used (only in this figure, electrolyte 1 shows a thin line in the figure, and electrolyte 2 shows a thick line in the figure.) 0 Using electrolyte 1 When the potential was less than 0.62 V, the acid current was detected when the force was 0.62 V or more, which is the current value indicating the acid current. On the other hand, when electrolyte 2 was used, no oxidation current occurred. Therefore As already explained in Fig.
  • the curve obtained by synthesizing the curve using electrolyte 2 represents the electrode reaction in the actual fuel cell, and the oxygen reduction potential of the Pt electrode decreases due to the oxidation current of methanol ( That is, it can be seen that the performance of the oxygen reduction electrode is reduced).
  • Table 1 shows E and E (unit V) at current densities of ⁇ lO .u A / cm 2 and 5 / z AZcm 2 from the current-potential curves of FIGS. In the table, “With MeOH” so
  • Table 2 shows ⁇ / ⁇ calculated from Table 1.
  • the electrode of each example having an E / E force or more is a fuel.
  • the oxygen reduction reaction has a high selectivity due to the low oxidation reaction of the sample, and therefore exhibits excellent oxygen reduction catalytic activity. That is, the electrode of each example has high oxygen reduction selectivity even when used in the condition where the fuel coexists.
  • the dispersion is stirred and suspended with ultrasonic waves, 30 L is taken from this solution, and dropped onto a circular part of a glassy carbon electrode (diameter: 5.2 mm) so that the catalyst in the solution is uniformly dispersed and dried. It was.
  • a naphthion (registered trademark) solution was further dropped on the catalyst, and heat treatment was performed at 120 ° C. in a nitrogen atmosphere to solidify the naphthion (registered trademark) to obtain an electrode.
  • the obtained electrode was immersed in a sulfuric acid solution of O.lmol / dm 3 and the oxygen reduction catalytic ability was evaluated at 30 ° C. and atmospheric pressure.
  • a reversible hydrogen electrode in the same concentration sulfuric acid solution was used as a reference electrode. The current density is displayed per geometric area.
  • FIG. 12 shows a current-potential curve when the above electrode is used and electrolyte 1 (without methanol) is used. Compared to the curve in Fig. 3, it was found that the oxygen reduction catalytic ability with a small reduction current was inferior.
  • FIG. 1 is a diagram schematically showing a current-potential curve of an electrode of the present invention.
  • FIG. 2 is a diagram schematically showing a current-potential curve of a Pt electrode.
  • FIG. 3 is a diagram showing a current-potential curve when an oxygen reduction electrode according to an embodiment of the present invention is used.
  • FIG. 4 is a diagram showing an XRD diffraction chart of the oxygen reduction electrode according to the embodiment of the present invention.
  • FIG. 5 is another diagram showing a current-potential curve when the oxygen reduction electrode according to the embodiment of the present invention is used.
  • FIG. 6 is still another diagram showing a current-potential curve when the oxygen reduction electrode according to the embodiment of the present invention is used.
  • FIG. 7 is still another view showing an XRD diffraction chart of the oxygen reduction electrode according to the embodiment of the present invention.
  • FIG. 8 is another diagram showing a current-potential curve when the oxygen reduction electrode according to the embodiment of the present invention is used.
  • FIG. 9 is another diagram showing an XRD diffraction chart of the oxygen reduction electrode according to the embodiment of the present invention.
  • FIG. 10 is another diagram showing a current-potential curve when the oxygen reduction electrode according to the embodiment of the present invention is used.
  • FIG. 1 l is a diagram showing a current-potential curve when a Pt electrode is used for V.
  • FIG. 12 Another graph showing the current-potential curve when oxygen is insufficient and the ZrO electrode is used V
  • FIG. 1 A first figure.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Materials Engineering (AREA)
  • Inert Electrodes (AREA)
  • Fuel Cell (AREA)

Abstract

La présente invention concerne une électrode d’oxydoréduction présentant une excellente capacité catalytique d’oxydoréduction dans une pile à combustible directe, un combustible liquide composé d’une solution aqueuse d’un composé organique étant oxydé au niveau de l’électrode négative. L’invention concerne spécialement une électrode d’oxydoréduction pour piles à combustible directes, contenant un oxyde de métal présentant au moins un élément de composition sélectionné parmi le groupe composé de ZrOx1 (0,25 < x1 < 2,0), CoOx2 (0,2 < x2 < 1,3), NbOx3 (0,3 < x3 < 2,5), TiOx4 (0,25 < x4 < 2,0) et SnOx5 (0,25 < x5 < 2,0) comme matériau actif d’électrode. L’électrode d’oxydoréduction satisfait à la relation suivante : 0,9 ≤ (EO/ES) ≤ 1, Es étant le potentiel d’électrode dans une solution d'acide sulfurique à 0,1 mol, et E0 étant le potentiel d’électrode dans une solution aqueuse contenant 0,1 mol/L d’acide sulfurique et 0,1 mil/L du composé organique à une densité de courant allant de -10 μA/cm2 à -5 μA/cm2.
PCT/JP2006/323925 2005-12-19 2006-11-30 Électrode d’oxydoréduction pour pile à combustible directe Ceased WO2007072665A1 (fr)

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Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2009017011A1 (fr) * 2007-07-31 2009-02-05 Showa Denko K.K. Catalyseur d'électrode en oxyde de métal, utilisation de celui-ci et procédé servant à produire un catalyseur d'électrode en oxyde de métal
WO2012096022A1 (fr) 2011-01-14 2012-07-19 昭和電工株式会社 Procédé de production de catalyseur d'électrode de pile à combustible, catalyseur d'électrode de pile à combustible et son application
WO2012096023A1 (fr) 2011-01-14 2012-07-19 昭和電工株式会社 Procédé de fabrication d'un catalyseur d'électrode de pile à combustible, catalyseur d'électrode de pile à combustible et son application
WO2012114778A1 (fr) 2011-02-21 2012-08-30 昭和電工株式会社 Procédé de fabrication d'un catalyseur d'électrode pour pile à combustible
WO2013021688A1 (fr) 2011-08-09 2013-02-14 昭和電工株式会社 Procédé de production de catalyseur d'électrode pour piles à combustible, catalyseur d'électrode pour piles à combustible et utilisation de celui-ci
WO2013021681A1 (fr) 2011-08-09 2013-02-14 昭和電工株式会社 Procédé de fabrication de catalyseur pour pile à combustible liquide directe, catalyseur fabriqué par celui-ci et application de celui-ci
US9136541B2 (en) 2010-02-10 2015-09-15 Showa Denko K.K. Process for producing fuel cell electrode catalyst, process for producing transition metal oxycarbonitride, fuel cell electrode catalyst and uses thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10658676B2 (en) 2016-12-22 2020-05-19 Showa Denko K.K. Oxygen reduction catalyst

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JPH078797A (ja) * 1994-03-10 1995-01-13 Agency Of Ind Science & Technol 金超微粒子固定化チタン系金属酸化物からなる酸化触媒、還元触媒、可燃性ガスセンサ素子および電極用触媒
WO2006019128A1 (fr) * 2004-08-19 2006-02-23 Japan Science And Technology Agency Catalyseur à électrode d’oxyde de métal

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH078797A (ja) * 1994-03-10 1995-01-13 Agency Of Ind Science & Technol 金超微粒子固定化チタン系金属酸化物からなる酸化触媒、還元触媒、可燃性ガスセンサ素子および電極用触媒
WO2006019128A1 (fr) * 2004-08-19 2006-02-23 Japan Science And Technology Agency Catalyseur à électrode d’oxyde de métal

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5254975B2 (ja) * 2007-07-31 2013-08-07 昭和電工株式会社 金属酸化物電極触媒およびその用途、ならびに金属酸化物電極触媒の製造方法
US8182950B2 (en) 2007-07-31 2012-05-22 Showa Denko K.K. Metal oxide electrocatalyst, use thereof, and process for producing metal oxide electrocatalysts
WO2009017011A1 (fr) * 2007-07-31 2009-02-05 Showa Denko K.K. Catalyseur d'électrode en oxyde de métal, utilisation de celui-ci et procédé servant à produire un catalyseur d'électrode en oxyde de métal
US9136541B2 (en) 2010-02-10 2015-09-15 Showa Denko K.K. Process for producing fuel cell electrode catalyst, process for producing transition metal oxycarbonitride, fuel cell electrode catalyst and uses thereof
US9118083B2 (en) 2011-01-14 2015-08-25 Showa Denko K.K Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst, and uses thereof
WO2012096023A1 (fr) 2011-01-14 2012-07-19 昭和電工株式会社 Procédé de fabrication d'un catalyseur d'électrode de pile à combustible, catalyseur d'électrode de pile à combustible et son application
WO2012096022A1 (fr) 2011-01-14 2012-07-19 昭和電工株式会社 Procédé de production de catalyseur d'électrode de pile à combustible, catalyseur d'électrode de pile à combustible et son application
US9350025B2 (en) 2011-01-14 2016-05-24 Showa Denko K.K. Method for producing fuel cell electrode catalyst, fuel cell electrode catalyst, and uses thereof
WO2012114778A1 (fr) 2011-02-21 2012-08-30 昭和電工株式会社 Procédé de fabrication d'un catalyseur d'électrode pour pile à combustible
US10026968B2 (en) 2011-02-21 2018-07-17 Showa Denko K.K. Method for producing fuel cell electrode catalyst
WO2013021688A1 (fr) 2011-08-09 2013-02-14 昭和電工株式会社 Procédé de production de catalyseur d'électrode pour piles à combustible, catalyseur d'électrode pour piles à combustible et utilisation de celui-ci
WO2013021681A1 (fr) 2011-08-09 2013-02-14 昭和電工株式会社 Procédé de fabrication de catalyseur pour pile à combustible liquide directe, catalyseur fabriqué par celui-ci et application de celui-ci
KR20140053284A (ko) 2011-08-09 2014-05-07 쇼와 덴코 가부시키가이샤 직접 액체형 연료 전지용 촉매의 제조 방법 및 상기 방법에 의해 제조된 촉매 및 그 용도
US9379390B2 (en) 2011-08-09 2016-06-28 Showa Denko K.K. Process for producing catalyst for direct-liquid fuel cell, catalyst produced by the process and uses thereof
US10044045B2 (en) 2011-08-09 2018-08-07 Showa Denko K.K. Process for producing a fuel cell electrode catalyst, fuel cell electrode catalyst and use thereof

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