WO2012057226A1 - パラジウム-金合金を有する還元用触媒 - Google Patents
パラジウム-金合金を有する還元用触媒 Download PDFInfo
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- WO2012057226A1 WO2012057226A1 PCT/JP2011/074715 JP2011074715W WO2012057226A1 WO 2012057226 A1 WO2012057226 A1 WO 2012057226A1 JP 2011074715 W JP2011074715 W JP 2011074715W WO 2012057226 A1 WO2012057226 A1 WO 2012057226A1
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- catalyst
- palladium
- gold
- carbon
- alloying
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/44—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers
- C07C209/48—Preparation of compounds containing amino groups bound to a carbon skeleton by reduction of carboxylic acids or esters thereof in presence of ammonia or amines, or by reduction of nitriles, carboxylic acid amides, imines or imino-ethers by reduction of nitriles
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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
- B01J23/48—Silver or gold
- B01J23/52—Gold
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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
- H01M4/92—Metals of platinum group
- H01M4/921—Alloys or mixtures with metallic elements
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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
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M2008/1095—Fuel cells with polymeric electrolytes
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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
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group 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
Definitions
- the present invention relates to a reduction catalyst having a palladium-gold alloy.
- a supported palladium catalyst in which palladium or an alloy of palladium and another metal is supported on a support such as alumina or carbon is a heterogeneous solid catalyst, such as hydrogenation of olefin, acetylene, nitro group, ketone, aldehyde, nitrile, etc.
- a heterogeneous solid catalyst such as hydrogenation of olefin, acetylene, nitro group, ketone, aldehyde, nitrile, etc.
- a supported palladium catalyst for example, a Pd—C catalyst and a Pd—Al 2 O 3 catalyst are disclosed, and these catalysts can be used for a hydrogenation reaction under heating and under pressure (non-conversion).
- Patent Document 1 a Pd—C catalyst and a Pd—Al 2 O 3 catalyst are disclosed, and these catalysts can be used for a hydrogenation reaction under heating and under pressure (non-conversion).
- an object of the present invention is to provide a supported palladium catalyst which is excellent in reducing ability and exhibits a high conversion rate and preferably excellent selectivity when used in a hydrogenation reaction.
- the present inventors have focused on the degree of alloying as an index for estimating the structure of the alloy at the micro level, and have completed the present invention.
- the present invention solves the above-mentioned problems by comprising a conductive carbon and a palladium-gold alloy supported on the carbon, and the alloying degree of the alloy is 50 to 100%.
- a catalyst for use is provided.
- the reduction catalyst of the present invention is an oxygen reduction catalyst in one embodiment, and a hydrogenation catalyst in another embodiment.
- the oxygen reduction catalyst is a cathode electrode catalyst for a solid polymer electrolyte fuel cell.
- the present invention further provides a cathode electrode for a solid polymer electrolyte fuel cell using the cathode electrode catalyst.
- the present invention further provides a method for reducing oxygen, comprising contacting oxygen with the reduction catalyst of the present invention.
- the present invention further provides a method for hydrogenating an organic compound having a reducing functional group, which comprises bringing the organic compound having a reducing functional group into contact with the reduction catalyst of the present invention.
- the reducing functional group include a carbon-carbon double bond-containing group (for example, alkenyl group), a carbon-carbon triple bond-containing group (for example, alkynyl group), a nitro group, a carbonyl group, and a cyano group. .
- the present invention further provides use of the reduction catalyst of the present invention as an oxygen reduction catalyst.
- the present invention further provides the use of the reduction catalyst of the present invention as a hydrogenation catalyst.
- the reduction catalyst of the present invention is excellent in reducing ability and is useful, for example, as an oxygen reduction catalyst, and further as a cathode electrode catalyst for a solid polymer electrolyte fuel cell.
- the cathode electrode of the present invention using the cathode electrode catalyst is useful for a solid polymer electrolyte fuel cell expected as a stationary battery as a household power supply facility and a mobile battery as an automobile power supply.
- the reduction catalyst of the present invention is also useful as a hydrogenation catalyst exhibiting a high conversion rate.
- the hydrogenation catalyst is used, for example, in a reaction in which hydrogen is added to an aliphatic nitrile compound to convert it to a primary amine. Excellent selectivity.
- Reduction catalyst 1-1 Formation of Palladium-Gold Alloy-Supported Carbon
- the conductive carbon support for example, acetylene black and furnace black carbon powders are suitable.
- the molar ratio of palladium to gold is preferably 9.5: 0.5 to 7: 3.
- the palladium-gold alloy-supported carbon can be formed as follows. -Disperse the conductive carbon powder uniformly in pure water. -A mixed solution of palladium salt and gold salt is used as a raw material for the alloy to be supported. Using sodium chloropalladate, palladium chloride, palladium nitrate, etc. as the palladium salt, and using chloroauric acid, sodium chloroaurate, etc. as the gold salt, the total weight of the supported alloy is preferably 10-40% by weight of the catalyst weight, More preferably, it is weighed so as to be 20 to 30% by weight. -Palladium ions and gold ions are adsorbed on a conductive carbon support by a chemical adsorption method. Next, the metal ions supported on these conductive carbons are chemically reduced. As the reducing agent, hydrazine, formaldehyde, sodium formate, formic acid or the like can be used.
- the reducing agent hydrazine, formaldehyde, sodium formate
- particles made of a palladium-gold alloy can be formed on the conductive carbon support.
- the degree of alloying of the palladium-gold alloy is usually 50 to 100%, preferably 70 to 100%, more preferably 80 to 100%. Even more preferably, it is 90 to 100%. If the degree of alloying is less than the lower limit, the resulting catalyst may be inferior in reducing ability.
- the degree of alloying of a palladium-gold alloy is measured as follows from X-ray diffraction (XRD) data, specifically, from the peak top position of the (220) plane and the measured values of the spacing d. It is an indicator.
- the palladium-gold alloy catalyst can discriminate its crystal structure by using a diffraction pattern in X-ray diffraction, and the deviation from the plane distance d calculated from the intrinsic diffraction angle 2 ⁇ of palladium or gold alone.
- the size is calculated for each of the interplanar spacing d of the alloy state obtained by the preparation and the interplanar spacing d of the ideal alloy state, and the ratio of the magnitudes of these deviations is determined according to Vegard's law.
- a value prorated by the mole fraction of gold is used as an index of the degree of alloying of the entire catalyst.
- the degree of alloying was defined as follows from the theoretical value and actual measurement value of d. That is, as shown in the following formula, the degree of alloying of each metal was calculated, and the sum of the respective metals in consideration of the molar fraction of each metal was defined as the degree of alloying of the palladium-gold alloy.
- the Pd mole fraction is calculated by the formula: (Pd ratio) / 100
- the Au mole fraction is calculated by the formula: 1-Pd mole fraction.
- Alloying degree of composition metal (%) (
- d is a value calculated from the above Bragg conditional formula based on the result of XRD measurement.
- the peak on the (220) plane in XRD is observed as a single peak, it is calculated from the peak position.
- the peak on the (220) plane in XRD is observed as two peaks, the peak on the high angle side corresponds to palladium, and the peak on the low angle side corresponds to gold.
- the alloying degree of the composition metal is calculated as shown in Table 3, and the alloying degree of the palladium-gold alloy is 96.02%.
- the degree of alloying of the palladium-gold alloy is 12.85%.
- the degree of alloying can be adjusted as follows. That is, in “1-1. Formation of palladium-gold alloy-supported carbon”, the degree of alloying can be adjusted by adjusting the pH when the reducing agent is added.
- the pH is preferably 9.0 to 13.0, more preferably 10.0 to 13.0, and even more preferably 11.0 to 13.0. When the pH is within the above range, it is easy to adjust the alloying degree of the obtained palladium-gold alloy within the range of 50 to 100%.
- a known pH adjusting agent can be used without particular limitation for adjusting the pH. Examples of the pH adjuster include potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate and the like.
- the reduction reaction in which the catalyst of the present invention can be used is not particularly limited.
- oxygen reduction reaction oxygen reduction reaction
- benzyl ether, benzyl ester A hydrogenolysis reaction such as a benzyloxycarbonyl group can be mentioned.
- the catalyst of the present invention is an oxygen reduction catalyst used in an oxygen reduction reaction
- examples thereof include a cathode electrode catalyst for a solid polymer electrolyte fuel cell.
- the hydrogenation is, for example, a reaction in which hydrogen is added to an aliphatic nitrile compound to convert it to a primary amine.
- the aliphatic nitrile compound include an aliphatic nitrile compound represented by the general formula: R 1 —CN
- examples of the primary amine include, for example, a formula represented by the general formula: R 1 —CH 2 —NH 2 .
- primary amines In the formula, R 1 represents an unsubstituted or substituted alkyl group.
- R 1 examples include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a t-butyl group, a pentyl group, a hexyl group, an octyl group, and the like.
- a part or all of the hydrogen atoms of the alkyl group are halogen atoms such as fluorine atom, bromine atom, chlorine atom, hydroxyl group, amino group, carbonyl group, oxo group (ie, ⁇ O), alkoxy group, thiol
- halogen atoms such as fluorine atom, bromine atom, chlorine atom, hydroxyl group, amino group, carbonyl group, oxo group (ie, ⁇ O), alkoxy group, thiol
- Examples include a group substituted with a group, such as a chloromethyl group, a bromoethyl group, and a 3,3,3-trifluoropropyl group.
- the catalytic hydrogenation reaction from nitrile to amine proceeds with various metal catalysts (Co, Ni, Rh, Pd, Pt, etc.).
- metal catalysts Co, Ni, Rh, Pd, Pt, etc.
- the ratio of these amines varies greatly depending on the reaction conditions such as the catalyst, temperature, pressure and solvent, and selection of the catalyst and the reaction conditions is important when mainly obtaining primary amines. For example, a reaction at a high temperature promotes condensation accompanied by elimination of ammonia, so that secondary and tertiary amines are advantageously formed.
- the equilibrium to the step where the imine intermediate reacts with the primary amine to produce the secondary amine is suppressed, resulting in a decrease in the production of secondary and tertiary amines.
- the primary amine can be mainly produced by performing the reaction in an acidic solvent or an acylating solvent such as acetic anhydride. This is considered to be because an ammonium salt is formed between the acid and the generated primary amine, and the addition of the amine to the imine intermediate is suppressed.
- the hydrogenation catalyst of the present invention can remarkably improve the selectivity of primary amine synthesis in the reaction of adding hydrogen to an aliphatic nitrile compound to convert it to an amine.
- Electrode for solid polymer electrolyte fuel cell In order to prepare an anode electrode and a cathode electrode, a catalyst layer is prepared on a gas diffusion layer, and both catalyst layers are opposed to an ion exchange membrane of a polymer electrolyte. Then, an ion exchange membrane-electrode assembly (MEA) is formed by pressure molding. Both electrodes are formed by the following preparation method.
- conductive carbon and a dispersant are kneaded, a Teflon (registered trademark) aqueous solution is added to maintain water repellency, and the one applied to the conductive carbon sheet is dried.
- the catalyst and pure water are kneaded, and a Nafion solution or the like is added according to other conventional methods. After further kneading, the catalyst layer is coated on the gas diffusion layer.
- the electrode sheet is prepared.
- the theoretical amount ratio of palladium to gold was 9: 1 in terms of molar ratio, and the loading ratio by ICP analysis was 25% by weight of palladium and 5.2% by weight of gold based on the catalyst weight.
- the samples A to D were evaluated for oxygen reduction activity by a rotating disk electrode.
- an electrochemical measurement system HZ-3000 (Hokuto Denko) was used.
- the rotating electrode device is composed of a rotating electrode manufactured by Hokuto Denko, the same control device, and the same electrolysis cell.
- the electrode was prepared by applying a catalyst to the glassy carbon disk electrode attached to the rotating electrode by the following procedure.
- a 30% by weight palladium-supported carbon catalyst referred to as sample E was also used.
- a solution in which 10 mg of the catalyst, 5 ml of pure water and 20 ⁇ l of 5 wt% Nafion solution (Aldrich) were added was prepared in advance, and ultrasonic dispersion was performed for 15 minutes. 2. 10 ⁇ l of the above solution was dropped onto glassy carbon. 3. Dried overnight at room temperature.
- the evaluation conditions are as follows. 1. 0.1M perchloric acid was used for the electrolyte, a silver / silver chloride electrode was used for the reference electrode, and a platinum mesh with platinum black was used for the counter electrode. 2. After the electrolyte was degassed with argon gas for 30 minutes or more, the rotating electrode was immersed, and the electrode was pretreated with a reversible hydrogen potential of 85 mV to 1085 mV and a scanning speed of 50 mV / sec. 3. Thereafter, a current-potential curve at a rotational speed of 1600 rpm was measured at a scanning potential of 135 mV to 1085 mV as a reversible hydrogen potential and a scanning speed of 10 mV / sec. 4).
- the electrolyte was saturated with oxygen gas for 15 minutes or longer, and the current-potential curve at a rotational speed of 1600 rpm was measured with a reversible hydrogen potential of 135 mV to 1085 mV and a scanning speed of 10 mV / sec.
- FIG. 4 shows a current-potential curve of each catalyst at a rotational speed of 1600 rpm.
- the current value at each potential in the graph of FIG. 4 is obtained by subtracting the current value obtained at evaluation condition item 3 from the current value obtained at evaluation condition item 4 at each potential.
- the current value obtained in the evaluation condition item 4 includes, in addition to the oxygen reduction current, a current for reducing metal catalyst particles, that is, palladium-gold alloy particles or oxides on the surface of the palladium particles. Therefore, in order to evaluate the true oxygen reduction current, it is necessary to remove the current that reduces the oxide on the surface of the metal catalyst particles. As a method for this, as described above, a true oxygen reduction current was obtained by subtracting the current value obtained in the evaluation condition item 3 from the current value obtained in the evaluation condition item 4.
- the oxygen reduction current at 0.85 V at the reversible hydrogen potential was used as a standard.
- the value of the oxygen reduction current is shown in Table 6 for each catalyst.
- FIG. 5 illustrates the results shown in Table 6 and is a graph showing the relationship between the degree of alloying and the oxygen reduction current. The larger the absolute value of the oxygen reduction current, the better.
- palladium-gold alloy-supported carbon catalysts (samples A and B) having a high degree of alloying of 96.02% or 85.41% exhibited a higher oxygen reduction potential than palladium-supported carbon catalysts. And excellent in oxygen reducing ability (FIG. 5).
- palladium-gold alloy-supported carbon catalysts (samples C and D) having a low alloying value of 64.18% or 12.85% have a lower oxygen reduction potential and higher oxygen reduction ability than palladium-supported carbon catalysts. Inferior.
- a palladium-gold alloy-supported carbon catalyst with a low degree of alloying it is considered that gold particles having a low oxygen reducing ability are present in the vicinity of the palladium particles without being alloyed, thereby inhibiting the oxygen reduction reaction by palladium. The possibility is suggested.
- a palladium-gold alloy-supported carbon catalyst having a high degree of alloying it is considered that the electronic state of palladium is changed by alloying, and as a result, oxygen reduction ability superior to that of palladium alone is exhibited. It is thought that.
- Valeronitrile (3.4 g) was used as a model substrate.
- the substrate and 50 ml of the solvent were put into the reaction vessel and suspended.
- the obtained reaction solution was separated and extracted with pure water and hexane (when acetic acid was used as a solvent, the solution was neutralized with a caustic soda solution and then separated and extracted).
- an appropriate amount of nitrobenzene as an internal standard substance was added to the upper layer (hexane layer) and sampled.
- the sampling sample was analyzed by gas chromatography (GC).
- GC gas chromatography
- Table 8 shows the combination of the catalyst and solvent used, and the measurement results of the conversion and selectivity.
- the conversion is the weight ratio between the consumed substrate and the substrate before the reaction
- the selectivity is the molar ratio of the obtained amines 1-3.
Abstract
Description
本発明は、更に、本発明の還元用触媒に酸素を接触させることを含む、酸素を還元する方法を提供する。
本発明は、更に、本発明の還元用触媒に還元性官能基を有する有機化合物を接触させることを含む、還元性官能基を有する有機化合物を水素化する方法を提供する。還元性官能基としては、例えば、炭素-炭素二重結合含有基(例えば、アルケニル基)、炭素-炭素三重結合含有基(例えば、アルキニル基)、ニトロ基、カルボニル基、シアノ基等が挙げられる。該有機化合物としては、例えば、オレフィン、アセチレン、ニトロ化合物、ケトン、アルデヒド、ニトリル等が挙げられる。
本発明は、更に、本発明の還元用触媒の、酸素還元用触媒としての使用を提供する。
本発明は、更に、本発明の還元用触媒の、水素化用触媒としての使用を提供する。
(1)還元用触媒
1-1.パラジウム-金合金担持カーボンの形成
導電性カーボン担体としては、例えば、アセチレンブラック系及びファーネスブラック系のカーボン粉末が適する。担持させるパラジウム-金合金において、パラジウムと金とのモル比は、好ましくは9.5:0.5~7:3である。
・導電性カーボン粉末を純水に均一に分散させる。
・担持させる合金の原料としてはパラジウム塩と金塩との混合溶液を用いる。パラジウム塩として塩化パラジウム酸ナトリウム、塩化パラジウム、硝酸パラジウム等を用い、金塩として塩化金酸、塩化金酸ナトリウム等を用い、担持させる合金の総重量が触媒重量の好ましくは10~40重量%、より好ましくは20~30重量%となるように秤量する。
・化学吸着法により導電性カーボン担体にパラジウムイオンおよび金イオンを吸着させる。
・次に、これら導電性カーボン上に担持された金属イオンを化学的に還元する。還元剤にはヒドラジン、ホルムアルデヒド、ギ酸ナトリウム、ギ酸等を用いる事ができる。
・本発明の還元用触媒において、パラジウム-金合金の合金化度は、通常、50~100%であり、好ましくは70~100%であり、より好ましくは80~100%であり、更により好ましくは90~100%である。該合金化度が上記下限値未満であると、得られる触媒は還元能に劣る場合がある。
2dsinθ = nλ
(ただし、n=1, λ=1.540598Å)
に当てはめて得たものである。
合金化度(%) = Σ(組成金属のモル分率)i・(組成金属の合金化度)i
= [Pdモル分率]・[Pdの合金化度]+[Auモル分率]・[Auの合金化度]
組成金属の合金化度(%)
=(|d(実測)-d(基準データ)|/{d(理論)-d(基準データ)})×100
本発明の触媒を用いることのできる還元反応は特に限定されず、例えば、酸素還元反応;オレフィン、アセチレン、ニトロ基、ケトン、アルデヒド、ニトリル等の水素化反応;ベンジルエーテル、ベンジルエステル、ベンジルオキシカルボニル基等の水素化分解反応が挙げられる。
本発明の触媒が酸素還元反応に用いられる酸素還元用触媒である場合、その例としては固体高分子電解質型燃料電池用カソード電極触媒が挙げられる。
本発明の触媒が水素化反応に用いられる水素化用触媒である場合、該水素化としては、例えば、脂肪族ニトリル化合物に水素を付加して第一級アミンに転換する反応が挙げられる。脂肪族ニトリル化合物としては、例えば、一般式:R1-CNで表される脂肪族ニトリル化合物が挙げられ、第一級アミンとしては、例えば、一般式:R1-CH2-NH2で表される第一級アミンが挙げられる。式中、R1は非置換または置換のアルキル基を表す。上記R1としては、例えば、メチル基、エチル基、プロピル基、イソプロピル基、ブチル基、t-ブチル基、ペンチル基、ヘキシル基、オクチル基等の炭素原子数1~20、好ましくは3~10のアルキル基;該アルキル基の水素原子の一部または全部をフッ素原子、臭素原子、塩素原子等のハロゲン原子、水酸基、アミノ基、カルボニル基、オキソ基(即ち、=O)、アルコキシ基、チオール基等で置換した基、例えば、クロロメチル基、ブロモエチル基、3,3,3-トリフルオロプロピル基等が挙げられる。
アノード電極及びカソード電極を調製するためには、ガス拡散層の上に触媒層を調製し、高分子電解質のイオン交換膜に両触媒層を対面させ、加圧成型によりイオン交換膜-電極接合体(MEA)が形成される。両電極は以下の調製法により成形される。
純水2.5Lを用い、触媒担体となるアセチレンブラック44 gを分散させ、得られた分散液を95℃まで加熱し、均一の触媒担体懸濁液を調製した。別に純水500mlを準備し、塩化パラジウム酸ナトリウムをパラジウム換算で15.8gと塩化金酸を金換算で3.3g溶解し、パラジウム塩および金塩の混合溶液を調製した。次に前記触媒担体懸濁液にパラジウム塩および金塩の混合溶液を滴下して新たに懸濁液を得た。この新たに得た懸濁液を室温まで降温した。さらに、純水500mlを用い、ホルムアルデヒドと水酸化カリウムを溶解させて還元剤溶液を得、この還元剤溶液を上記で室温まで降温した懸濁液へ60分かけて滴下した。滴下後50℃まで加熱し、還元を行った。
こうして、触媒担体であるアセチレンブラックの表面にパラジウムおよび金の粒子を担持した。
反応液を冷却後、固形物をろ過し洗浄した。
その後、乾燥を約70℃の大気中で行い、その後粉砕し、担体であるアセチレンブラック上にパラジウム-金合金を担持した触媒を得た。
なお、上記還元剤溶液のpHを13.0、11.0、10.0および8.0に調整してそれぞれサンプルA~Dを得た。
尚、同モル比が8:2、7:3である場合についても調製した。
上記(1)で得られたサンプルA~Dについて、XRD測定を行い、XRDパターンを得た。これらのXRDパターンにおける(220)面のピークを観察したところ、サンプルA~Cについては単一のピークであったのに対し、サンプルDについては二つのピークであった。サンプルDでは、高角度側のピークをパラジウムに、低角度側のピークを金に対応させた。(220)面のピーク位置から合金化度を算出した。結果を表5に示す。
パラジウム-金合金担持カーボン触媒の酸素還元能を評価するため、上記サンプルA~Dについて回転ディスク電極による酸素還元活性の評価を行った。評価装置には電気化学測定システム(HZ-3000)(北斗電工)を用いた。回転電極装置は北斗電工製の回転電極、同制御装置、同電解セルにより構成される。電極調製は、回転電極に装着されたグラッシーカーボンディスク電極に以下の手順で触媒を塗布することにより行った。なお、比較用の触媒として、30重量%パラジウム担持カーボン触媒(サンプルEとする)も用いた。
2.上記溶液をグラッシーカーボン上へ10μl滴下した。
3.一晩室温にて乾燥させた。
1.電解液に0.1M過塩素酸を用い、参照電極に銀/塩化銀電極、対極には白金黒付白金メッシュを使用した。
2.電解液をアルゴンガスで30分以上脱気した後、回転電極を浸し、走査電位を可逆水素電位で85mV~1085 mV、走査速度を50 mV/secとして電極の前処理を行なった。
3.その後、走査電位を可逆水素電位で135mV~1085mV、走査速度を10mV/secとして、回転数1600rpmにおける電流-電位曲線を測定した。
4.電解液を酸素ガスで15分以上飽和し、走査電位を可逆水素電位で135mV~1085mV、走査速度を10mV/secとして、回転数1600rpmにおける電流-電位曲線を測定した。
評価条件項目4で得られる電流値は、酸素還元電流に加え、金属触媒粒子、すなわち、パラジウム-金合金粒子またはパラジウム粒子の表面の酸化物を還元する電流を含む。よって、真の酸素還元電流を評価するためには、金属触媒粒子表面の酸化物を還元する電流を除くことが必要である。そのための方法として、上記のとおり、評価条件項目4で得られた電流値から評価条件項目3で得られた電流値を引くことにより、真の酸素還元電流とした。
表7に示す反応条件下、吉草酸ニトリルの水添反応を実施した。
Claims (9)
- 導電性カーボンと、該カーボンに担持されたパラジウム-金合金とを有してなり、該合金の合金化度が50~100%である還元用触媒。
- 酸素還元用触媒である請求項1に係る触媒。
- 固体高分子電解質型燃料電池用カソード電極触媒である請求項2に係る触媒。
- 水素化用触媒である請求項1に係る触媒。
- 前記水素化が脂肪族ニトリル化合物に水素を付加して第一級アミンに転換する反応である請求項4に係る触媒。
- 前記合金の量が該触媒重量に対して10~40重量%である請求項1に係る触媒。
- 請求項3に係る触媒を用いた固体高分子電解質型燃料電池用カソード電極。
- 請求項1に記載の還元用触媒に酸素を接触させることを含む、酸素を還元する方法。
- 請求項1に記載の還元用触媒に還元性官能基を有する有機化合物を接触させることを含む、還元性官能基を有する有機化合物を水素化する方法。
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WO2023167199A1 (ja) * | 2022-03-01 | 2023-09-07 | 三井金属鉱業株式会社 | 電極触媒及びその製造方法並びに燃料電池 |
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