KR101680100B1 - Noble Metal Catalyst Containing Transition Metal Oxide and Carbon Material and Preparation Method Thereof - Google Patents

Noble Metal Catalyst Containing Transition Metal Oxide and Carbon Material and Preparation Method Thereof Download PDF

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KR101680100B1
KR101680100B1 KR1020150070862A KR20150070862A KR101680100B1 KR 101680100 B1 KR101680100 B1 KR 101680100B1 KR 1020150070862 A KR1020150070862 A KR 1020150070862A KR 20150070862 A KR20150070862 A KR 20150070862A KR 101680100 B1 KR101680100 B1 KR 101680100B1
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oxide
metal oxide
noble metal
transition metal
catalyst
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Korean (ko)
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유동진
라마누잠칸난
장혜리
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전북대학교 산학협력단
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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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/10—Magnesium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • 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)
    • 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
    • B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
    • B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues

Abstract

The present invention relates to a noble metal electrocatalyst for a fuel cell comprising a transition metal oxide, secondary metal oxide and a carbonaceous material, and a method for preparing the same. Particularly, the method for preparing a noble metal electrocatalyst comprises the steps of: forming a primary transition metal oxide; forming a secondary metal oxide; forming a carbonaceous material which is reduced graphene oxide; and forming a noble metal catalyst comprising a carbonaceous material-transition metal oxide. The noble metal electrocatalyst according to the present invention has excellent activity and provides a high-energy catalyst capable of producing an excessive amount of oxygen.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a noble metal electrocatalyst containing a transition metal oxide and a carbon material,

The present invention relates to a noble metal electrocatalyst comprising a transition metal oxide, a secondary metal oxide and a carbonaceous material, and a process for producing the same. More particularly, transition metal oxide and secondary metal oxide as transition metal oxide, transition metal oxide, and one or more noble metal electrocatalysts comprising a carbon material for oxidation reaction of the hydrated and solvated molecules, It is located on the surface.

The electrocatalyst composition of the present invention comprises a step of preparing a first transition metal oxide, a step of preparing a secondary metal oxide, a step of producing a carbon material, which is a reduced graphene oxide, a step of preparing a noble metal catalyst containing a carbon material- .

The present invention can be used in the production of electrode materials that can be used in fuel cells. The present invention relates to carbon and transition metal oxides as cocatalysts and also relates to the field of catalytic oxidation and alcoholic oxidation reactions of alcohols and thus can be used in the production of electrode materials which can be used in fuel cells.

The invention also relates to a catalyst comprising a carbon support having a composition consisting of a catalyst consisting of one or more nanostructured transition metal oxides and a nano-noble metal catalyst.

The precursor may be used for preparing a carbon support used for the production of metal oxides, the secondary metal oxide may be combined with the primary metal oxide, or the secondary metal oxide may be coated on the primary metal oxide / carbon support and the nanostructured precious metal may be carbon / Metal oxide support. The present invention further relates to a one component / two part metal oxide catalyst as a cocatalyst, comprising a carbon support. The present invention also relates to the field of electrocatalytic oxidation of hydroxyl groups contained in hydrocarbons by catalytic oxidation of oxygen-enriched solvated water.

As a background of the present invention, studies for using catalysts involved in various types of reactions have included carbon-based support catalysts for fuel cell electrodes, particularly for anode catalysts with low cost and robust materials. Over the past few years, many reports have been published in the field of oxidation of water over transition metal oxide catalysts. This is promising compared to fossil fuels, and is a potential and clean economic energy source. On the other hand, research on direct alcohol fuel cell (DAFC) has increased explosively and miniaturized cells have been commercialized.

Catalysts play an important role, during which platinum-based catalysts have been used. Thus, the cost of the battery has increased, which has been a major drawback to commercialization. So researchers are focusing on cheap catalysts with multifunctional properties. Graphene and metal oxides supporting noble metal catalysts have been studied for alcohol electrooxidation reactions.

It has been reported by Kannan et al. That manganite-based electrocatalysts that support palladium nanoparticles exhibit improved electrooxidation performance and are more stable against electrooxicity. [Kannan R, Karunakaran K, Vasanthkumar S. PdNi-decorated manganite nanocatalyst for electrooxidation of ethylene glycol in alkaline media. Ionics 2012; 18: 803809, Kannan R, Kim AE, Yoo DJ. Synthesis and characterization and electrocatalytic studies of palladium manganese oxyhydroxide nanocomposite toward direct ethylene glycol fuel cell. Chin Sci Bull 2014; 59: 34133419].

In addition, Huang et al. Showed improved electrocatalytic activity of Pt / MnO 2 / GNS through the synergy of metal oxides when compared to Pt / GO. [Huang H, Chen Q, He M, Sun X, Wang X. A ternary Pt / MnO 2 / graphene nanoohybrid with an ultra high electrocatalytic activity towards methanol oxidation. J Power Sources 2013; 189-195)

The Pd / MnO 2 -rGO was prepared by the Liu group through a three step process, which demonstrated that the prepared catalyst exhibited a high methanol electrochemical oxidation capability. In addition, MnO 2 in the catalyst absorbs OH - ions, thereby oxidizing toxic intermediates. [Liu R, Zhou H, Yao Y, Huang Z, Fu C, Kauang Y. Preparation of Pd / MnO 2 -reduced graphene oxide nanocomposite for methanol electro-oxidation in alkaline media. Electrochem Commun 2013; 26: 63-66]. Electrolysis of water on oxidized manganese electrodes has been studied, and metal oxides have been reported to help produce oxygen gas at low potentials in alkaline electrolytes. [Deab MSE, Awad MI, Mohammad AM, Ohsaka T. Enhanced water electrolysis: electrocatalytic generation of oxygen gas at manganese oxide nanorods modified electrodes, Electrochem Commum 2009; 9: 2082-2087]

Gorline et al. Have shown that MnOx is an excellent OER catalyst, and furthermore, it has been reported that the addition of a trace amount of gold catalyst significantly increases the OER current. [Y. Gorlin, C. J. Chung, J. D. Benck, D. Nordlund, L. Seitz, T. C. Weng, D. Sokaras, B. M. Clemens, T. F. Jaramillo, J Am Chem Soc 136 2014 4920-4626].

The Suib group has tested enhanced oxidation of water on various oxidized manganese such as amorphous oxide manganese, cryptomerane type tunnel oxide manganese, layered oxidized manganese and stratified burnisite. [A. Iyer, J. D. Pilar, C. K. King'ondu, E. Kissel, H. F. Garces, H. Huang, A. M. El-Sawy, P. K. Dutta, S. L. Suib, J Phys Chem C 16 (2012) 6474-6483]. These amorphous oxide nanogranites show excellent oxidation reaction of water in both chemical and photochemical processes. The disordered structure of oxidized manganese and mixed valence leads to improved response.

Bulk metal oxides have been of interest for many years, with several investigations documenting the relative activity of polydispersed compositions and disordered structural forms, as heterogeneous water oxidation catalysts.

The problem of interpreting the causes of catalytic activity of disordered materials, particularly metal oxides, is partly explored in a wide range of possible forms that can be found or exist for each material. Minerals of manganese oxide and / or manganese hydroxide naturally occur in 30 different crystal structures. Some of these oxidized nanosphere polymorphs have been tested for the oxidation reaction activity of water. Both nanoparticles of α-MnO 2 , β-MnO 2 and Mn 2 O 3 have been reported to promote oxidation of water when used in mineral oxide systems.

The δ-MnO 2 particles electrodeposited on the electrode were found to only oxidize water under strongly alkaline conditions. As mentioned previously, other polymorphic nanocrystals such as? -MnO 2 are active catalysts.

A study on the oxidation reaction of photochemical water by polymorph crystals of manganese oxide was studied by Robinson et al. J.M., J. G. Gardner, Z. Zhang, D. Masrongiovanni, E. Garfunkel, J. Li, M. Greenblett, GC Dismukes, J Am Chem Soc 135 (2013) 3494-3501] . They found that disordered manganese oxides exhibit better catalytic oxidation of water than square manganese oxides. Mn 2 O 3 and Mn 3 O 4 have a better ability to oxidize water than α-MnO 2 and β-MnO 2 because Mn-O at the edge sharing the octahedral structure is weak Due to the fact that it is catalytically more reactive due to its flexible linkage. On the other hand, MnO 2 with short and strong Mn-O bonds is more stable and promotes the generation of oxygen at high oxidation potentials. Korean Patent Registration No. 10-0728611 (an electrode catalyst for a fuel cell and a production method therefor) according to the present invention relates to an electroconductive polymer coating all or a part of the surface of a carbon-based carrier; Transition metal active ingredient particles distributed on the surface of the electroconductive polymer; And an electrode catalyst for a fuel cell comprising a chloride, a nitride, or a sulfur oxide of a transition metal distributed in the electroconductive polymer, or a transition metal active component atom. Korean Patent Laid-Open Publication No. 10-2012-0089858 (a catalyst having a metal oxide doping for a fuel cell) comprises a support, at least one catalytically active metal of the platinum group or an alloy containing at least one metal of the platinum group, And at least one oxide of at least one metal selected from Si, W, Mo, Zn, Ta, Nb, V, Cr and Zr. However, these prior arts have different technical constructions from those of the present invention.

As a study on the use of catalysts involved in various types of reactions, carbon-based support catalysts for anode catalysts of low cost and robust materials have been of great interest. Recently, there have been many reports on the oxidation reaction of water on transition metal oxide catalysts. This is an energy source that is more environmentally friendly and more economical than fossil fuels and potentially has potential. On the other hand, as the research on direct alcohol fuel cell (DAFC) has been explosively increased and the miniaturized cell has been commercialized, the catalyst plays a very important role. Since the cost of the battery is increased due to the use of the platinum catalyst, It has become a main drawback.

The present invention relates to a method for producing a composite oxide comprising the steps of preparing a primary metal oxide which is a transition metal oxide, a step of producing a secondary metal oxide, a step of producing a carbon material which is a reduced graphene oxide, And a manufacturing step.

The active catalysts bound to the carbon and metal oxide nanostructures of the present invention are particularly useful for the oxidation of hydroxyl groups contained in hydrocarbons such as methanol, ethanol and isopropanol which are useful for quantitative energy and hydrogen evolution. In this reaction process, the catalyst oxidizes the organic compounds and further affects the additional oxidation of the secondary products produced in the reaction process . Also, the transition metal oxide complex composed of carbon supporting the noble metal catalyst shows excellent catalytic activity to generate oxygen from a solvent containing hydroxyl group, and the energy catalyst produces excess oxygen.

The present invention can provide a catalyst design comprising a graphene support containing single or dual metal oxides and transition metal compositions and catalytic oxidation of water in a solvated system.

1 is a high-resolution transmission electron microscope image of a carbon compound.
2 is a high-resolution transmission electron microscope image of a composite catalyst prepared from the reduced graphene-manganese oxide-titanium oxide of Example 3 as a carbon / transition metal oxide.
FIG. 3 is a high-resolution transmission electron microscope image of a graphene oxide-manganese oxide-titanium oxide composite catalyst reduced to palladium nanoparticles of Example 4 as a noble metal / metal oxide / carbon composite catalyst.
4 is powder x-ray diffraction analysis of a noble metal / metal oxide / carbon composite catalyst.
Powder x-ray diffraction analysis of the reduced graphene oxide-manganese oxide-titanium oxide composite catalyst on the palladium nanoparticles of Example 4 shows a peak at m-position and a peak at titanium oxide, And a peak of reduced graphene oxide. It also shows the peak of palladium nanoparticles in the graph at position c.
5 is a cyclic voltammetric curve of a noble metal / metal oxide / carbon composite catalyst electrode containing hydroxyl group including solvated compound. Is a cyclic voltammetric curve for a reduced graphene oxide-manganese oxide-titanium oxide composite catalyst for the palladium nanoparticles of Example 4.
FIG. 6 is a cyclic voltammogram of a noble metal / metal oxide / carbon composite catalyst electrode having hydroxyl groups including solvated compounds in various potential windows. Is a cyclic voltammetric curve for a reduced graphene oxide-manganese oxide-titanium oxide composite catalyst for the palladium nanoparticles of Example 4.
7 is a cyclic voltammetric curve of a noble metal / metal oxide / carbon composite catalyst electrode of hydroxyl group including a solvated compound in a high / wide potential window. Is a cyclic voltammetric curve for a reduced graphene oxide-manganese oxide-titanium oxide composite catalyst for the palladium nanoparticles of Example 4.

The present invention relates to a process for producing a primary transition metal oxide, a process for producing a secondary metal oxide, a process for preparing a carbon material which is a reduced graphene oxide, and a process for preparing a noble metal catalyst containing a carbon material- .

The present invention provides a catalyst and a method for preparing a catalyst composition useful in various electrochemical oxidation reactions including oxygen and hydrogen generation by an electrooxidation reaction of a hydroxyl-containing hydroxyl group. Such catalysts include graphenes composed of a carbon or graphene oxide or a single transition metal compound or a double oxide, among the carbon materials present in nature, on the support, in particular the carbon support. The catalyst comprises a noble metal catalyst located on the carbon / transition metal oxide.

The catalyst composition of the present invention may comprise one or more of a primary transition metal oxide and a secondary transition metal oxide and optionally a primary transition metal oxide or a secondary transition metal oxide or both, Lt; / RTI > The active catalyst is composed of a primary transition metal oxide or a secondary metal oxide on carbon and acts as a support material as a whole. These composites mainly act as supports and serve as cocatalysts in electrocatalytic reactions.

The carbon support is activated, and the noble metal nanoparticles are composed of at least 1 to 5% by weight of the total catalyst, the content of the primary transition metal oxide is 10 to 15% as a whole higher than that of the secondary metal oxide by 5 to 9% The content of 70-80% may be higher than both the metal oxide and the metal nanoparticles.

The present invention relates to a catalyst comprising a carbon support that forms a transition metal oxide composition comprising a metal oxide and / or a metal oxide located on carbon. In the catalyst composition derived from the precursor composition of such a transition metal compound, the primary metal oxide is selected from a combination of at least one of the elements cobalt, vanadium, chromium, and manganese.

Primary catalyst / carbon-based composites derived from precursors of transition metals and oxidized carbon derivatives are selected from cobalt, vanadium, chromium, manganese and magnesium elements and combinations of these metals.

The secondary metal oxide of the catalyst / carbon support derived from the precursor composition of the transition metal and the oxidized carbon derivative is selected from manganese, cobalt, vanadium, chromium, titanium and magnesium elements and combinations of these metals.

Carbon supports are synthesized by oxidation reaction of carbon powders using a strong oxidizing agent such as permanganic acid, sodium or potassium salt of chromic acid and iron oxide. Chromic acid, which uses about 20 to 50 times (ml) The ratio of carbon to salt is 1: 3, 1: 4, 1: 5 times the weight of acid types such as nitric acid, sulfuric acid and / or perchloric acid. Furthermore, the oxidation reaction takes place at an elevated temperature between 40 ° C and 100 ° C. This reaction is controlled by strong and fast oxidants, including permanganate, peroxides and ferric chloride.

The metal oxide on the carbon material (carbon support) is composed of single or double metal oxides having the general molecular formula of AxBy. Wherein the compound A is composed of any one or a combination of cobalt, vanadium, chromium, manganese, and magnesium, and the molar ratio (x) thereof is in the range of 0.1 to 0.9. Similarly, the second metal compound B is composed of any one selected from the group consisting of cobalt, vanadium, chromium, manganese and magnesium, or a combination thereof and has x = 0.1 to 0.9 and y = 0.9 to 0.1 molar ratio with respect to the base metal, (Y) ranges from 0.1 M to (Y) to 0.9 mol, and the molar ratio of the total composition (A + B) is 1.0.

The metal oxide is prepared by a process comprising hydrothermal reaction at a temperature between 100 [deg.] C and 200 [deg.] C. The calcination temperature of the final composite material was calcined at a high temperature between 200 and 600 ° C. The drying temperature of the carbonaceous material is from 20 ° C to 60 ° C.

This process involves contacting the carbon support with a metal oxide source and a carbon phase by a method of combining one or more solvents. Moreover, the noble metal catalyst can be produced by in situ generation on a metal oxide / carbon support using 5 to 10 ml of a reducing agent (0.1 M) containing a mixed solution of sodium borohydride, hydrazine, ethylene glycol, ascorbic acid and hydroquinone Respectively.

The electrode was measured by cyclic voltammetry and the catalyst was coated on a stable electrode using 0.1-1 v / v% of a commercialized binder such as polyvinyl difluoride, liquid paraffin and Nafion solution. The noble metal of the nano structure may be selected from elements including platinum, palladium, gold or ruthenium.

The present invention relates to a process for the preparation of noble metal catalysts comprising primary and secondary transition metal oxide / carbon composites, wherein the enhanced oxidation of hydroxylated and solvated molecules by the catalytic electrode. It is also possible to use a catalyst prepared according to an improved oxidation reaction of a hydroxylated and solvated molecule on a nano-structured noble metal on a transition metal oxide / oxide / oxidized carbon catalyst material, And the oxidation reaction at the rock stage.

≪ Example 1 > Preparation of primary transition metal manganese oxide hydroxides

Manganese oxide hydroxide was prepared by the hydrothermal reaction as follows. 40 ml of hydrogen peroxide and 5 ml of nitric acid were added dropwise to a solution of hydrogen peroxide (3.25 g in 100 ml). After the solution was completely added to the solution, the obtained gel was reacted at 60-80 占 폚 for 12 hours. The product was washed several times with distilled water and separated by centrifugation. Lt; RTI ID = 0.0 > 105 C < / RTI >

≪ Example 2 > Of the secondary metal oxide of manganese oxide / titanium oxide Produce

≪ Example 2-1 > Manganese oxide

1 g of the above-prepared manganese oxide / titanium oxide was dispersed in a mixture of 15 ml of water and 15 ml of ethanol.

Was added dropwise to a foil covered with 1 ml of titanium isopropoxide and 500 mg of elemental aluminum and sonicated. After 30 minutes, the entire contents were transferred to a Teflon lined autoclave and subjected to hydrothermal reaction at 180 占 폚. After 12 hours the reaction was terminated and cooled, the product was washed with excess water and dried using a microwave oven at 30 second intervals for 10 minutes.

<Example 2-2> Titanium oxide

1 g of the thus prepared manganese oxide hydroxide was mixed with 15 ml of water and 15 ml of ethanol solution and stirred for 30 seconds. 1 ml of titanium propoxide and 500 mg of urea were added dropwise to the foil covered with aluminum. Lt; RTI ID = 0.0 &gt; 105 C &lt; / RTI &gt; overnight. And then calcined in an air atmosphere of 400 DEG C for 2 hours.

&Lt; Example 3 > Reduced graphene oxide-manganese oxide-titanium oxide (carbon material)

800 g of the manganese oxide hydroxide prepared above and 200 mg of graphene oxide were dispersed in 15 ml of ethanol and 15 ml of water. One milliliter of titanium isopropoxide and 500 mg of urea were immediately added dropwise to the aluminum foil and sonicated. After 5 minutes, the entire contents were transferred to an autoclave covered with Teflon and subjected to hydrothermal reaction at 180 ° C. After 12 minutes, the reaction was terminated and cooled. The product was washed with excess water and dried in a hot oven at &lt; RTI ID = 0.0 &gt; 105 C &lt; / RTI & And calcined at 400 DEG C for 2 hours in an inert atmosphere.

Reduced Graphene oxide - Manganese oxide - Titanium oxide was prepared.

&Lt; Example 4 > Preparation of reduced graphene oxide-manganese oxide-titanium oxide (noble metal catalyst containing carbon material / transition metal oxide) for palladium nanoparticles

Preparation of reduced graphene oxide-manganese oxide-titanium oxide for palladium nanoparticles was carried out by reduction at room temperature to about 10 mg of RGO / MnTiOx (OH), 2 mg of palladium chloride and 10 mg of ashes The ascorbic acid was mixed using a mortar for 2 minutes. The final composite product was dried for 2 hours in a hot oven at 80 ° C.

INDUSTRIAL APPLICABILITY The transition metal oxide composite composed of carbon supporting a noble metal catalyst has excellent catalytic activity for producing oxygen from a solvent containing a hydroxyl group, and thus is industrially applicable.

Claims (11)

The present invention relates to a noble metal electrocatalyst comprising a reduced graphene oxide as a carbon support in an amount of 75 to 80% by weight of the total constitution, and further comprising a noble metal electrocatalyst comprising a transition metal oxide, manganese oxide, titanium oxide as a secondary metal oxide, delete delete delete The noble metal catalyst according to claim 1, wherein the nano-structured noble metal is selected from platinum, palladium, gold and ruthenium, The method according to claim 1, wherein the metal oxide on the carbon support is a monovalent or divalent metal oxide having a molecular formula of AxBy, the compound A is composed of manganese, the compound B is composed of titanium, 0.1 to 0.9 mol and y = 0.9 to 0.1 mol, and the molar ratio of (A + B) of the total composition is 1.0,  A step of preparing a manganese oxide as a primary transition metal oxide, a step of producing titanium as a secondary metal oxide, a step of producing a carbon material as a reduced graphene oxide, and a step of preparing a carbon material - a step of preparing a noble metal electrocatalyst comprising a transition metal oxide-metal oxide 8. The process of claim 7 wherein the noble metal electrocatalyst is characterized in that the catalyst prepared on the nano-structured noble metal on the carbonaceous material of the primary transition metal oxide and the secondary metal oxide is hydroxylated and causes an enhanced oxidation reaction of the solvated molecule For preparing precious metal electrocatalyst delete delete delete
KR1020150070862A 2015-05-21 2015-05-21 Noble Metal Catalyst Containing Transition Metal Oxide and Carbon Material and Preparation Method Thereof KR101680100B1 (en)

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100728611B1 (en) 2005-11-25 2007-06-14 주식회사 진우엔지니어링 Catalyst for fuel cell electrode and method of preparing the same

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100728611B1 (en) 2005-11-25 2007-06-14 주식회사 진우엔지니어링 Catalyst for fuel cell electrode and method of preparing the same

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* Cited by examiner, † Cited by third party
Title
- Electrochemistry Communications 26 (2013) 63-66
- Phys. Chem. Chem. Phys., 2013, 15, 20333-20344

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