JP2002210365A - CATALYST FOR CLEANING NOx AND ITS PRODUCTION METHOD - Google Patents
CATALYST FOR CLEANING NOx AND ITS PRODUCTION METHODInfo
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- JP2002210365A JP2002210365A JP2001010206A JP2001010206A JP2002210365A JP 2002210365 A JP2002210365 A JP 2002210365A JP 2001010206 A JP2001010206 A JP 2001010206A JP 2001010206 A JP2001010206 A JP 2001010206A JP 2002210365 A JP2002210365 A JP 2002210365A
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- conductive material
- electron
- ion
- cerium
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Abstract
Description
【０００１】[0001]
【発明の属する技術分野】本発明は、自動車や小型発電
装置などに使用される内燃機関、ファンヒータやストー
ブなどの暖房機、および焼却炉などから排出される排気
ガスからＮＯxを浄化するための、燃焼排気ガス用のＮ
Ｏx浄化用触媒に関するものである。The present invention relates to the internal combustion engines used in automobiles and small power generator, heater such as a fan heater and stoves, and the like for purifying NO x from the exhaust gas discharged from the incinerator Of N for combustion exhaust gas
The present invention relates to an O x purification catalyst.
【０００２】[0002]
【従来の技術】従来の自動車などの内燃機関に使用され
る排気ガスのＮＯx浄化は、三元触媒の使用に代表され
るように、排気ガス中に含まれるＮＯやＮＯ2などの窒
素酸化物を窒素へ還元する反応と排気ガス中の炭化水素
（以下ＨＣと省略）やＣＯなどの還元性物質を酸化させ
る反応を同一の触媒上で行ない、高効率に浄化を行なう
方法が実用化されている。 The NO x purification BACKGROUND OF THE INVENTION exhaust gas used in an internal combustion engine, such as a conventional automobile, as typified by the use of three-way catalysts, NOx such as NO and NO 2 in the exhaust gas A method has been put into practical use in which a reaction for reducing substances to nitrogen and a reaction for oxidizing reducing substances such as hydrocarbons (hereinafter abbreviated as HC) and CO in exhaust gas are performed on the same catalyst, thereby purifying with high efficiency. ing.
【０００３】例えば、図４に、文献「新しい触媒化学
（第２版）」（三共出版（株）１９９７年発行）の１３
１〜１３３頁に記載されているガソリンエンジン用三元
触媒に関する空気と燃料の重量比（空燃比）とＮＯx、
ＨＣおよびＣＯの浄化（転化）率との関係を示す。空燃
比１４．７近傍であれば前記３成分すべての転化率が８
０％以上となるので、常にこの空燃比になるようにエン
ジンの燃焼状態が制御される。このとき、三元触媒に供
給される排気ガス中のＮＯxと還元剤は化学的にほぼ等
量となる。また前記文献に記載されているように、三元
触媒には触媒活性の高い貴金属が使用されており、なか
でもＮＯx還元能の高いＲｈとＨＣやＣＯの酸化能の高
いＰｔ、Ｐｄから構成されるＰｔ−Ｐｄ−Ｒｈ系触媒が
広く用いられている。[0003] For example, FIG. 4 shows a document “New Catalyst Chemistry (Second Edition)” (published by Sankyo Publishing Co., Ltd., 1997).
The weight ratio of air to fuel (air-fuel ratio) and NO x for the three-way catalyst for gasoline engines described on pages 1 to 133,
The relationship between HC and CO purification (conversion) rates is shown. If the air-fuel ratio is around 14.7, the conversion of all three components is 8
Since it is 0% or more, the combustion state of the engine is controlled so as to always maintain this air-fuel ratio. At this time, NO x with a reducing agent in the exhaust gas supplied to the three-way catalyst becomes chemically substantially equal amounts. In addition, as described in the literature, the three-way catalyst has been used a high noble metal catalytic activity, among them NO x high reducing ability Rh and HC and CO with high oxidation ability Pt, composed of Pd Pt-Pd-Rh-based catalysts are widely used.
【０００４】図５は、従来の三元触媒の機能を模式的に
表記した図である。図において、６は触媒活性を有する
微細金属粒子（貴金属微粒子）、７はその微細金属粒子
を担持する基材である。この基材には金属担持量の増大
と耐熱性の観点から、表面積の大きいアルミナが使用さ
れる。図５においては、同一の金属表面に解離吸着した
ＮＯxおよび還元剤（ＨＣまたはＣＯ）が酸化還元反応
を起こし、Ｎ2、ＣＯ2およびＨ2Ｏに変換される。FIG. 5 is a diagram schematically showing the function of a conventional three-way catalyst. In the figure, reference numeral 6 denotes fine metal particles having catalytic activity (noble metal fine particles), and reference numeral 7 denotes a base material supporting the fine metal particles. Alumina having a large surface area is used for this substrate from the viewpoints of increasing the amount of metal carried and heat resistance. In FIG. 5, NO x and a reducing agent (HC or CO) dissociated and adsorbed on the same metal surface cause an oxidation-reduction reaction and are converted into N 2 , CO 2 and H 2 O.
【０００５】[0005]
【発明が解決しようとする課題】前述のように、従来の
三元触媒では貴金属微粒子をアルミナのように耐熱性が
高く表面積の大きい基材に担持する構造のものが広く使
用されている。ところで、貴金属はその資源量が有限で
あり高価であるために使用量の低減が求められている。
その方策として貴金属の利用効率を高めるために粒子径
をより小さくして貴金属の重量あたりの表面積を高めて
貴金属表面の反応サイト数を増やすことにより反応効率
を増やすなどの方法が用いられている。しかし、貴金属
種によっては粒子径を小さくしても、排ガス浄化時に触
媒が加熱されるために粒径成長が起こることがある。そ
の結果、貴金属の表面積が小さくなって触媒反応が起こ
りにくくなり、反応効率が低下してしまうため、耐久性
が低いという問題点があった。As described above, conventional three-way catalysts having a structure in which noble metal fine particles are supported on a substrate having high heat resistance and a large surface area, such as alumina, are widely used. By the way, since noble metals have a limited amount of resources and are expensive, it is required to reduce the amount used.
As a measure therefor, a method of increasing the reaction efficiency by increasing the surface area per weight of the noble metal by increasing the surface area per weight of the noble metal and increasing the number of reaction sites on the surface of the noble metal has been used in order to increase the use efficiency of the noble metal. However, depending on the kind of the noble metal, even if the particle diameter is reduced, the catalyst may be heated at the time of purifying the exhaust gas, so that the particle diameter may grow. As a result, the surface area of the noble metal is reduced, so that the catalytic reaction is less likely to occur, and the reaction efficiency is reduced. Therefore, there is a problem that the durability is low.
【０００６】前述の問題点の対策としては、触媒活性を
有する微細金属粒子の添加量を増やすことが最も有効で
あるが、触媒活性を有する微細金属粒子に使われる主た
る材料が貴金属であるため、資源量や価格の観点で添加
量を増やすことは困難であるという問題点があった。As a countermeasure against the above-mentioned problem, it is most effective to increase the amount of fine metal particles having catalytic activity. However, since the main material used for fine metal particles having catalytic activity is a noble metal, There was a problem that it was difficult to increase the amount of addition from the viewpoint of resource amount and price.
【０００７】そこで、本発明は、排気ガス中のＮＯx浄
化において、より少ない触媒活性金属量で高効率に浄化
する触媒を提供することを目的とする。[0007] Therefore, the present invention provides a the NO x purification in the exhaust gas, and to provide a catalyst for purifying a high efficiency with less catalytically active metal content.
【０００８】[0008]
【課題を解決するための手段】本発明の第１の構成に係
るＮＯx浄化用触媒は、電子伝導性物質粒子表面の一部
にイオン伝導性物質が配置され、かつ触媒活性を有する
複数個の微細金属粒子が、前記イオン伝導性物質表面と
電子伝導性物質粒子表面との両方に接触して配置され、
前記イオン伝導性物質および電子伝導性物質を介してそ
れぞれイオンおよび電子が移動することにより、前記微
細金属粒子におけるＮＯxの還元反応と還元剤の酸化反
応とを電気化学的に行なうものである。 The NO x purification catalyst according to the first configuration of the present invention, in order to solve the problem] is disposed ion conductive material in a part of the electron conducting material particle surface, and a plurality of catalytically active Fine metal particles are arranged in contact with both the ion conductive material surface and the electron conductive material particle surface,
The ion and the electron move through the ion-conductive substance and the electron-conductive substance, respectively, to electrochemically perform a reduction reaction of NO x and an oxidation reaction of a reducing agent in the fine metal particles.
【０００９】本発明の第２の構成に係るＮＯx浄化用触
媒は、電子伝導性物質が金属であるものである。[0009] the NO x purification catalyst according to the second configuration of the present invention is an electron conductive material is a metal.
【００１０】本発明の第３の構成に係るＮＯx浄化用触
媒は、電子伝導性物質が金属酸化物であるものである。A third of the NO x purifying catalyst according to the configuration of the present invention is an electron conductive material is a metal oxide.
【００１１】本発明の第４の構成に係るＮＯx浄化用触
媒は、イオン伝導性物質が化学式Ｃｅ1-xＡxＯy（ｘは
０．５から０．１までの数値、ｙは１．７５から２まで
の数値、ＡはＹｂ、Ｙ、Ｇｄ、Ｓｍ、ＮｄまたはＬａで
ある。）で示される複合酸化物であるものである。[0011] the NO x purification catalyst according to the fourth aspect of the present invention, the numerical value of the ion conductive material from the formula Ce 1-x A x O y (x is 0.5 to 0.1, y is 1 .75 to 2, where A is Yb, Y, Gd, Sm, Nd or La).
【００１２】本発明の第５の構成に係るＮＯx浄化用触
媒は、微細金属粒子が、白金、パラジウム、ロジウム、
オスミウム、ルテニウム、イリジウムのうち少なくとも
１種の元素よりなるものである。[0012] The 5 NO x purifying catalyst according to the configuration of the present invention, fine metal particles, platinum, palladium, rhodium,
It is composed of at least one element of osmium, ruthenium, and iridium.
【００１３】本発明の第１の方法に係るＮＯx浄化用触
媒の製造方法は、第１ないし第５の何れかの構成に係る
ＮＯx浄化用触媒の製造方法であって、電子伝導性物質
粒子を分散させた有機酸水溶液中にイオン伝導性物質の
水溶性前駆体を混合し、生成した沈殿物を焼成すること
により、電子伝導性物質粒子表面の一部にイオン伝導性
物質を配置するものである。[0013] The method of manufacturing the NO x purification catalyst according to the first method of the present invention is a manufacturing method of the NO x purifying catalyst according to any one of the first to fifth, electron-conductive material A water-soluble precursor of an ion-conductive substance is mixed in an organic acid aqueous solution in which particles are dispersed, and the resulting precipitate is calcined to dispose the ion-conductive substance on a part of the surface of the electron-conductive substance particles. Things.
【００１４】本発明の第２の方法に係るＮＯx浄化用触
媒の製造方法は、第１ないし第５の何れかの構成に係る
ＮＯx浄化用触媒の製造方法であって、有機酸水溶液に
イオン伝導性物質の水溶性前駆体と電子伝導性物質の水
溶性前駆体とを混合し、生成した沈殿物を焼成すること
により、電子伝導性物質粒子表面の一部にイオン伝導性
物質を配置するものである。[0014] manufacturing method of the NO x purifying catalyst according to the second method of the present invention is a manufacturing method of the NO x purifying catalyst according to any one of the first to fifth, in an aqueous solution of an organic acid A water-soluble precursor of an ion-conductive substance and a water-soluble precursor of an electron-conductive substance are mixed, and the resulting precipitate is calcined to place the ion-conductive substance on a part of the surface of the electron-conductive substance particles. Is what you do.
【００１５】本発明の第３の方法に係るＮＯx浄化用触
媒の製造方法は、有機酸水溶液がシュウ酸またはクエン
酸の水溶液であるものである。The third manufacturing method of the NO x purifying catalyst according to the method of the present invention an aqueous solution of an organic acid is an aqueous solution of oxalic acid or citric acid.
【００１６】本発明の第４の方法に係るＮＯx浄化用触
媒の製造方法は、イオン伝導性物質の水溶性前駆体が硝
酸化合物であものである。In the method for producing a NO x purification catalyst according to a fourth method of the present invention, the water-soluble precursor of the ion-conductive substance is a nitric acid compound.
【００１７】本発明の第５の方法に係るＮＯx浄化用触
媒の製造方法は、第１ないし第５の何れかの構成に係る
ＮＯx浄化用触媒の製造方法であって、表面の一部にイ
オン伝導性物質を配置した電子伝導性物質粒子を、触媒
活性を有する金属の前駆体溶液に浸漬し、前記イオン伝
導性物質および電子伝導性物質粒子の表面を、前記触媒
活性を有する金属の前駆体で被覆したのち、焼成を行な
うことにより、イオン伝導性物質および電子伝導性物質
粒子の表面に触媒活性を有する微細金属粒子を配置する
ものである。The manufacturing method of the fifth the NO x purification catalyst according to the method of the present invention is a manufacturing method of the NO x purifying catalyst according to any one of the first to fifth, part of the surface The electron conductive material particles in which the ion conductive material is arranged are immersed in a precursor solution of a metal having catalytic activity, and the surfaces of the ion conductive material and the electron conductive material particles are coated with the metal having the catalytic activity. After coating with the precursor, baking is performed to arrange fine metal particles having catalytic activity on the surfaces of the ion conductive substance and the electron conductive substance particles.
【００１８】なお、複数の触媒活性な微細金属粒子を用
いて酸化反応および還元反応を電気化学的に行なう触媒
システムについては、本件出願人が出願しており、特開
平１０−２７００５５号公報に開示されている。また、
この「電気化学触媒」を用いて燃料電池の一酸化炭素被
毒に対する耐久性を高める方法が、本件出願人による特
開平１０−２７００５６号公報に開示されている。本発
明では、この「電気化学触媒」を燃焼排気ガス用途で使
用するＮＯx浄化用触媒に応用し、主に従来の三元触媒
を代替する触媒として新たに開発した。A catalyst system for electrochemically performing an oxidation reaction and a reduction reaction using a plurality of fine metal particles having catalytic activity has been filed by the present applicant and disclosed in Japanese Patent Application Laid-Open No. Hei 10-270055. Have been. Also,
A method of increasing the durability of a fuel cell against carbon monoxide poisoning by using the “electrochemical catalyst” is disclosed in Japanese Patent Application Laid-Open No. Hei 10-270056 by the present applicant. In the present invention, it is applied to the NO x purification catalyst using this "electrochemical catalyst" in the combustion exhaust gas applications, newly developed as a catalyst to replace the mostly conventional three-way catalyst.
【００１９】[0019]
【発明の実施の形態】図１は、本発明の一実施の形態に
よるＮＯx浄化用触媒の構造を模式的に示す断面図であ
る。図１において、１は電子伝導性物質粒子、２はイオ
ン伝導性物質であり、電子伝導性物質粒子１表面の一部
にイオン伝導性物質２が配置されている。３ａ，３ｂ，
４は電子伝導性物質粒子１表面およびイオン伝導性物質
２表面に配置された触媒活性を有する微細金属粒子であ
り、３ａおよび３ｂは電子伝導性物質粒子１表面とイオ
ン伝導性物質２表面の両方に接触して配置された微細金
属粒子ＡおよびＢである。４は電子伝導性物質粒子１表
面とイオン伝導性物質２表面の一方のみに接触して配置
されている微細金属粒子である。図１では、分かりやす
いように、電子伝導性物質粒子１およびイオン伝導性物
質２に比べて、微細金属粒子３ａ，３ｂ，４の拡大率を
大きくして示している。イオン伝導性物質２中の矢印
は、電荷担体として酸素イオンを用いた場合のイオンの
流れる方向を、また電子伝導性物質粒子１中の矢印は、
電子の流れる方向を、それぞれ示している。Figure 1 DETAILED DESCRIPTION OF THE INVENTION is a cross-sectional view schematically showing the structure of the NO x purifying catalyst according to an embodiment of the present invention. In FIG. 1, reference numeral 1 denotes electron conductive material particles, 2 denotes an ion conductive material, and an ion conductive material 2 is disposed on a part of the surface of the electron conductive material particles 1. 3a, 3b,
Reference numeral 4 denotes fine metal particles having catalytic activity disposed on the surface of the electron conductive material particle 1 and the surface of the ion conductive material 2, and 3a and 3b denote both the surface of the electron conductive material particle 1 and the surface of the ion conductive material 2. And fine metal particles A and B arranged in contact with the metal particles. Reference numeral 4 denotes fine metal particles arranged in contact with only one of the surfaces of the electron conductive material particles 1 and the ion conductive material 2. In FIG. 1, the enlargement ratio of the fine metal particles 3 a, 3 b, and 4 is larger than those of the electron conductive material particles 1 and the ion conductive material 2 for easy understanding. The arrow in the ion conductive material 2 indicates the direction in which ions flow when oxygen ions are used as charge carriers, and the arrow in the electron conductive material particle 1 indicates
The directions in which electrons flow are shown.
【００２０】なお、図１では、電子伝導性物質粒子１表
面およびイオン伝導性物質２表面に、微細金属粒子３
ａ，３ｂおよび微細金属粒子４の両方が配置されている
場合を示しているが、微細金属粒子３ａ，３ｂがあれ
ば、微細金属粒子４はなくてもよい。In FIG. 1, fine metal particles 3 are provided on the surfaces of the electron conductive material particles 1 and the ion conductive material 2.
Although the case where both a and 3b and the fine metal particles 4 are arranged is shown, the fine metal particles 4 need not be provided as long as the fine metal particles 3a and 3b are present.
【００２１】また、図１では、電子伝導性物質粒子１表
面の一部にイオン伝導性物質２が配置され、さらに微細
金属粒子３ａ，３ｂ，４が配置されたＮＯx浄化用触媒
粒子を１個示しているが、実際にはこのような粒子が複
数個集まって二次粒子を形成していることもある。Further, in FIG. 1, ion conductive material 2 is disposed on a part of the electron conducting material particle 1 a surface, finer metal particles 3a, 3b, 4 and the NO x purification catalyst particles disposed one However, in practice, a plurality of such particles may collectively form secondary particles.
【００２２】排気ガス中に含まれるＮＯxと還元剤とし
て含まれるＨＣやＣＯは、微細金属粒子３ａ，３ｂまた
は４の表面に吸着される。このとき、ＮＯxと還元剤が
同一の金属粒子表面に吸着した場合には、従来の三元触
媒と同様に単一微細金属粒子での酸化還元反応がおこ
り、Ｈ2ＯとＣＯ2とＮ2に分解される。しかし本発明に
おいては、ＮＯxと還元剤が異なる微細金属粒子３ａ，
３ｂ表面に吸着した場合においても、微細金属粒子３
ａ，３ｂ間が電子伝導性物質１およびイオン伝導性物質
２により電気的に接続されていることにより電気化学的
酸化還元反応が起こる。すなわち、微細金属粒子３ａ上
に吸着したＮＯxはＮ2と酸素イオンに分解され、酸素イ
オンはイオン伝導性物質２内を通過して別の微細金属粒
子３ｂに移動する。この微細金属粒子Ｂ３ｂの表面上
で、酸素イオンは粒子表面上に吸着したＨＣを酸化し、
ＣＯ2とＨ2Ｏが生成する。その際に発生する余剰電子
は、電子伝導性物質１中を通過して微細金属粒子３ａに
移動し、粒子３ａ上での酸素イオンの生成に使用され
る。NO x contained in the exhaust gas and HC and CO contained as the reducing agent are adsorbed on the surface of the fine metal particles 3a, 3b or 4. At this time, when NO x and the reducing agent are adsorbed on the same metal particle surface, an oxidation-reduction reaction occurs in a single fine metal particle as in a conventional three-way catalyst, and H 2 O, CO 2 and N 2 Decomposed into two . However, in the present invention, NO x with a reducing agent is different fine metal particles 3a,
3b, the fine metal particles 3
Since the a and 3b are electrically connected by the electron conductive substance 1 and the ion conductive substance 2, an electrochemical oxidation-reduction reaction occurs. That, NO x adsorbed on the fine metal particles 3a is decomposed into N 2 and oxygen ions, oxygen ions move to another fine metal particles 3b through the ion conductive material 2. On the surface of the fine metal particles B3b, oxygen ions oxidize HC adsorbed on the particle surface,
CO 2 and H 2 O are produced. The surplus electrons generated at that time pass through the electron conductive material 1, move to the fine metal particles 3a, and are used to generate oxygen ions on the particles 3a.
【００２３】このように、本発明においては、同一微細
金属粒子上でのＮＯxと還元剤（ＨＣまたはＣＯ）の酸
化還元反応に加え、ＮＯxの還元反応とＨＣまたはＣＯ
の酸化反応を異なる微細金属粒子３ａ，３ｂの表面で起
こすことが可能であるため、従来の三元触媒のようにＮ
ＯxとＨＣまたはＣＯとが同一微細金属粒子上に接触す
る必要はない。すなわち、微細金属粒子３ａおよび３ｂ
の何れか一方の表面上にＮＯxが、他方の表面上にＨＣ
またはＣＯが接触すれば浄化反応が進行することになる
ため、ＮＯxおよび還元剤が微細金属粒子３ａ，３ｂ，
４表面に接触して酸化還元反応を起こす確率が高くな
る。その結果、微細金属粒子の表面積を拡げた場合と同
様の効果を、より少ない触媒活性を有する金属粒子量で
得ることができ、ＮＯx浄化効率が従来よりも向上す
る。As described above, in the present invention, in addition to the oxidation-reduction reaction of NO x and a reducing agent (HC or CO) on the same fine metal particles, the reduction reaction of NO x and HC or CO
Can be caused on the surfaces of the different fine metal particles 3a and 3b, so that N
And O x and HC or CO is not necessary to contact with the same fine metal particles. That is, the fine metal particles 3a and 3b
HC either on one surface of the NO x is, on the other surface
Alternatively, the purification reaction proceeds when CO comes in contact with the catalyst, so that the NO x and the reducing agent contain fine metal particles 3a, 3b,
4 The probability of causing an oxidation-reduction reaction by contacting the surface is increased. As a result, the same effect as in the case of expanding the surface area of the fine metal particles, can be obtained in quantity metallic particles having less catalytic activity, NO x purification efficiency is improved than before.
【００２４】また前述のように、触媒表面上にＮＯxが
接触して還元される確率が高くなることにより、ＮＯx
とＨＣまたはＣＯとの酸化還元反応速度も向上する。そ
の結果、排気ガスを大量に流した場合でもＮＯxを浄化
することが可能となる。Further, as described above, the probability that NO x comes into contact with the catalyst surface to be reduced increases, so that NO x
And the rate of redox reaction between HC and CO are also improved. As a result, it becomes possible to purify NO x even when large quantities flowing exhaust gas.
【００２５】図２は、本発明における微細金属粒子３
ａ，３ｂを電子伝導性物質粒子１表面とイオン伝導性物
質２表面の両方に接触して配置したＮＯx浄化用触媒に
関し、関係する物質の電気化学素反応を示す電位図であ
る。なお、図２の電位は、可逆水素電位を基準にした値
で表記している。文献「電気化学便覧」に記載されてい
るように、ＮＯおよびＮＯ2の還元電位は、それぞれ式
（１）および式（２）で表され、カーボン、Ｈ2および
一酸化炭素の酸化電位は式（３）、式（４）および式
（５）で表記される。なお、ＨＣはメタン、プロパンな
ど種々の炭化水素の総称であるが、カーボンの電位とほ
ぼ同等であることが既に知られている。FIG. 2 shows fine metal particles 3 according to the present invention.
FIG. 4 is a potential diagram showing an electrochemical element reaction of a related substance with respect to a NO x purification catalyst in which a and 3b are arranged in contact with both the surface of the electron conductive substance particle 1 and the surface of the ion conductive substance 2. Note that the potential in FIG. 2 is represented by a value based on the reversible hydrogen potential. As described in the literature “Electrochemical Handbook”, the reduction potentials of NO and NO 2 are represented by the formulas (1) and (2), respectively, and the oxidation potentials of carbon, H 2 and carbon monoxide are represented by the formulas Expressions (3), (4) and (5) are used. Note that HC is a general term for various hydrocarbons such as methane and propane, but it is already known that HC is almost equivalent to the potential of carbon.
【００２６】 式（１）ＮＯ＋４Ｈ+＋４ｅ-→Ｎ2＋２Ｈ2Ｏ Ｅ＝１．４９５Ｖ 式（２）ＮＯ2＋８Ｈ+＋８ｅ-→Ｎ2＋４Ｈ2Ｏ Ｅ＝１．３６３Ｖ 式（３）Ｃ＋２Ｈ2０→ＣＯ2＋４Ｈ+＋４ｅ- Ｅ＝０．２０７Ｖ 式（４）Ｈ2→２Ｈ+＋２ｅ- Ｅ＝０．０００Ｖ 式（５）ＣＯ＋Ｈ2０→ＣＯ2＋２Ｈ+＋２ｅ- Ｅ＝−０．１０３ＶFormula (1) NO + 4H + + 4e − → N 2 + 2H 2 O E = 1.495V Formula (2) NO 2 + 8H + + 8e − → N 2 + 4H 2 O E = 1.363V Formula (3) C + 2H 20 → CO 2 + 4H + + 4e - E = 0.207V formula (4) H 2 → 2H + + 2e - E = 0.000V formula (5) CO + H 2 0 → CO 2 + 2H + + 2e - E = -0.103V
【００２７】式（１）〜式（５）では水素イオンを介在
させた場合の電気化学素反応およびその電位について記
載したが、酸素イオンを介在させた場合でも、生成物や
電位は基本的に同一となる。Formulas (1) to (5) describe the electrochemical element reaction and its potential when hydrogen ions are interposed. However, even when oxygen ions are interposed, the products and potentials are basically the same. Will be the same.
【００２８】式（１）および式（２）は、ＮＯxからＮ2
を生成させる還元反応であり、式（３）、式（４）およ
び式（５）は還元剤の酸化反応である。還元反応と酸化
反応を比較すると、その電位差は１Ｖ以上であり、これ
らの間には起電力が生じることになる。この起電力はイ
オンおよび電子を移動させる駆動力となる。したがっ
て、本発明においては、微細金属粒子３ａおよび３ｂの
表面上にそれぞれＮＯxおよびＨＣが接触しさえすれ
ば、電気化学反応による酸化還元反応が起こり、ＮＯx
浄化が進行する。Equations (1) and (2) are calculated from NO x to N 2
, And equations (3), (4) and (5) are oxidation reactions of the reducing agent. Comparing the reduction reaction and the oxidation reaction, the potential difference is 1 V or more, and an electromotive force is generated between them. This electromotive force becomes a driving force for moving ions and electrons. Therefore, in the present invention, as long as NO x and HC are brought into contact with the surfaces of the fine metal particles 3a and 3b, respectively, an oxidation-reduction reaction by an electrochemical reaction occurs, and NO x
Purification proceeds.
【００２９】電子伝導性物質１としては、金属や金属酸
化物など電子抵抗が低い物質であれば使用可能である。
具体的には、金、銀、銅、コバルト、鉄、ニッケル、ル
テニウム、スズ、インジウム、アンチモン、亜鉛などの
電子伝導性を有する金属、あるいは、酸化銀、酸化ニッ
ケル、酸化インジウム、酸化スズ、酸化アンチモン、酸
化亜鉛などの金属酸化物を少なくとも１種以上含む物
質、およびこれらの複合体などが使用可能である。As the electron conductive substance 1, any substance having a low electronic resistance such as a metal or a metal oxide can be used.
Specifically, a metal having electronic conductivity such as gold, silver, copper, cobalt, iron, nickel, ruthenium, tin, indium, antimony, and zinc, or silver oxide, nickel oxide, indium oxide, tin oxide, and oxide Substances containing at least one kind of metal oxide such as antimony and zinc oxide, and composites thereof can be used.
【００３０】電子伝導性物質粒子１の平均粒子径は１０
μｍ以下であることが好ましく、平均粒子径が１０μｍ
を越えると重量あたりの表面積が小さくなるため、イオ
ン伝導性物質の担持量が低下するので好ましくない。The average particle diameter of the electron conductive material particles 1 is 10
μm or less, the average particle diameter is 10 μm
Exceeding the surface area is not preferred because the surface area per weight becomes small and the amount of the ion-conductive substance carried is reduced.
【００３１】イオン伝導性物質２としては、酸素イオン
または水素イオンを伝導する物質であれば使用可能であ
る。特に、イオン伝導性物質２として複合酸化物を使用
した場合には、高温での材料安定性が高くなり、高速運
転時に起こる触媒の急速昇温にも耐えることが可能とな
り、触媒の耐久性が増す。As the ion conductive substance 2, any substance that conducts oxygen ions or hydrogen ions can be used. In particular, when a composite oxide is used as the ion-conductive substance 2, the material stability at high temperatures is increased, and it is possible to withstand the rapid temperature rise of the catalyst that occurs during high-speed operation. Increase.
【００３２】具体的には、例えば、下記の式（Ｉ）で示
されるペロブスカイト型酸化物、式（II）で示される複
合酸化物などを使用することができる。Specifically, for example, perovskite oxides represented by the following formula (I), composite oxides represented by the formula (II), and the like can be used.
【００３３】式（Ｉ）：Ｌａ1-xＳｒxＧａ1-yＭｇyＯ3
（ｘは０．０５から０．３までの数値、ｙは０．１から
０．３までの数値である。） 式（II）：Ｃｅ1-xＡxＯy（ｘは０．５から０．１まで
の数値、ｙは１．７５から２までの数値、ＡはＹｂ、
Ｙ、Ｇｄ、Ｓｍ、ＮｄまたはＬａである。） 特に、式（II）で示される物質の中でセリウム（Ｃｅ）
とサマリウム（Ｓｍ）の複合酸化物は、４００℃程度の
低温で高い酸素イオン伝導性を有する物質であり、ま
た、ある程度の電子伝導性も併有しており、材料として
は最も望ましい。また、式（Ｉ）で示される物質は、Ｈ
2Ｏが共存すると、水素イオン伝導性物質となる。Formula (I): La 1-x Sr x Ga 1-y Mg y O 3
(X is a numerical value from 0.05 to 0.3, y is a numerical value from 0.1 to 0.3.) Formula (II): Ce 1-x A x O y (x is from 0.5 to 0.3) A value to 0.1, y is a value from 1.75 to 2, A is Yb,
Y, Gd, Sm, Nd or La. In particular, among the substances represented by the formula (II), cerium (Ce)
A composite oxide of samarium (Sm) and samarium (Sm) is a substance having high oxygen ion conductivity at a low temperature of about 400 ° C. and also has a certain degree of electron conductivity, and is the most desirable material. Further, the substance represented by the formula (I) is H
When 2 O coexists, it becomes a hydrogen ion conductive substance.
【００３４】イオン伝導性物質２の粒径は５μｍ以下で
あることが好ましく、５μｍを越えるとイオン伝導の抵
抗が大きくなるため、電気化学反応の効率が低下するの
で好ましくない。The particle size of the ion conductive material 2 is preferably 5 μm or less, and if it exceeds 5 μm, the resistance of ion conduction increases, which is not preferable because the efficiency of the electrochemical reaction decreases.
【００３５】触媒活性を有する微細金属粒子３ａ，３
ｂ，４としては、ＮＯxを解離吸着するものが好ましく
用いられる。具体的には、材料の安定性の観点などか
ら、白金（Ｐｔ）、パラジウム（Ｐｄ）、ロジウム（Ｒ
ｈ）、オスミウム（Ｏｓ）、ルテニウム（Ｒｕ）、イリ
ジウム（Ｉｒ）、およびこれらの混合物、または合金の
微細粒子が用いられる。Fine metal particles 3a, 3 having catalytic activity
b, a 4, what is preferably used for dissociative adsorption of NO x. Specifically, from the viewpoint of material stability and the like, platinum (Pt), palladium (Pd), rhodium (R
h), fine particles of osmium (Os), ruthenium (Ru), iridium (Ir), and mixtures or alloys thereof.
【００３６】微細金属粒子３ａ，３ｂ，４の平均粒子径
は１ｎｍ〜１００ｎｍであることが好ましく、１ｎｍ〜
５０ｎｍであることがより好ましい。平均粒子径が１ｎ
ｍ未満では粒子として担持できない傾向があり、１００
ｎｍを越えると金属重量に対する表面積が小さくなるた
め、触媒の活性が低下する傾向がある。The average particle diameter of the fine metal particles 3a, 3b, 4 is preferably 1 nm to 100 nm, more preferably 1 nm to 100 nm.
More preferably, it is 50 nm. Average particle size is 1n
If it is less than 100 m, there is a tendency that it cannot be supported as particles.
If it exceeds nm, the surface area with respect to the weight of the metal becomes small, so that the activity of the catalyst tends to decrease.
【００３７】電子伝導性物質粒子１表面の一部へのイオ
ン伝導性物質２の配置は、電子伝導性物質粒子を分散さ
せた有機酸水溶液中にイオン伝導性物質の水溶性前駆体
を混合し、生成した沈殿物を焼成することにより、ある
いは、有機酸水溶液にイオン伝導性物質の水溶性前駆体
と電子伝導性物質の水溶性前駆体とを混合し、生成した
沈殿物を焼成することにより、実現される。The ion conductive substance 2 is arranged on a part of the surface of the electron conductive substance particles 1 by mixing a water-soluble precursor of the ion conductive substance with an organic acid aqueous solution in which the electron conductive substance particles are dispersed. , By baking the generated precipitate, or by mixing a water-soluble precursor of an ion conductive material and a water-soluble precursor of an electron conductive material in an organic acid aqueous solution, and baking the generated precipitate. Is realized.
【００３８】イオン伝導性物質２の焼成温度は、焼成物
のＸ線回折による結晶構造評価において、複合酸化物結
晶の回折ピークが得られる所定の焼成温度以上であれば
よいが、温度が高すぎると結晶粒径が増大し、表面積が
小さくなってしまう。すなわち、５００℃以上であれば
よいが、１７００℃以下で焼成することが望ましく、８
００℃程度での焼成が特に望ましい。The sintering temperature of the ion-conductive substance 2 may be higher than a predetermined sintering temperature at which a diffraction peak of the composite oxide crystal is obtained in the evaluation of the crystal structure of the fired product by X-ray diffraction, but the temperature is too high. As a result, the crystal grain size increases, and the surface area decreases. That is, it is sufficient that the temperature be 500 ° C. or higher, but it is desirable to perform firing at 1700 ° C. or lower.
Firing at about 00 ° C. is particularly desirable.
【００３９】また、有機酸水溶液としてシュウ酸または
クエン酸の水溶液を用いることにより、焼成物中の不純
物含有量を抑えることが可能となり、イオン伝導性物質
２のイオン伝導性能が増し、触媒活性を高めることが可
能となる。Further, by using an aqueous solution of oxalic acid or citric acid as the organic acid aqueous solution, the content of impurities in the calcined product can be suppressed, the ionic conductivity of the ion-conductive substance 2 increases, and the catalytic activity increases. It is possible to increase.
【００４０】また、イオン伝導性物質の水溶性前駆体と
して硝酸化合物を用いた場合には、焼成物中の不純物含
有量を抑えることが可能となり、イオン伝導性物質２の
イオン伝導性能が増し、触媒活性を高めることが可能と
なる。When a nitric acid compound is used as the water-soluble precursor of the ion-conductive substance, the content of impurities in the calcined product can be suppressed, and the ion-conductivity of the ion-conductive substance 2 is increased. It is possible to increase the catalytic activity.
【００４１】表面の一部にイオン伝導性物質を配置した
電子伝導性物質粒子表面への微細金属粒子の配置は、表
面の一部にイオン伝導性物質を配置した電子伝導性物質
粒子を、触媒活性を有する金属の前駆体溶液に浸漬し、
イオン伝導性物質および電子伝導性物質粒子の表面を、
触媒活性を有する金属の前駆体で被覆したのち、焼成を
行なうことにより、実現される。この方法により、電気
伝導性物質表面に、より細かい微細金属粒子を担持させ
ることができ、ＮＯx転化率を向上させることができ
る。The placement of the fine metal particles on the surface of the electron conductive material having an ion conductive material disposed on a part of the surface is performed by using the electron conductive material particles having the ion conductive material disposed on a part of the surface with a catalyst. Immersed in a precursor solution of an active metal,
The surface of the ion conductive material and the electron conductive material particles,
It is realized by coating with a precursor of a metal having catalytic activity and then performing calcination. By this method, finer fine metal particles can be supported on the surface of the electrically conductive material, and the NO x conversion can be improved.
【００４２】微細金属粒子担持電気伝導性物質の焼成温
度は２５０〜７００℃、焼成時間は０．５〜６時間とす
ることが好ましい。焼成温度が２５０℃未満または焼成
時間が０．５時間未満では、バインダー材が焼結され
ず、触媒が脆く、剥離しやすくなる傾向があり、焼成温
度が７００℃をこえる場合または焼成時間が６時間をこ
える場合、触媒が変質する傾向がある。The firing temperature of the conductive material supporting fine metal particles is preferably 250 to 700 ° C., and the firing time is preferably 0.5 to 6 hours. If the sintering temperature is less than 250 ° C. or the sintering time is less than 0.5 hours, the binder material is not sintered, and the catalyst tends to be brittle and easily peeled off. If the time is exceeded, the catalyst tends to deteriorate.
【００４３】[0043]
【実施例】以下、実施例を示し本発明を説明するが、本
発明はこれらにより限定されるものではない。The present invention will be described below with reference to examples, but the present invention is not limited to these examples.
【００４４】実施例１．イオン伝導性物質の水溶性前駆
体として硝酸セリウム水和物と硝酸サマリウム水和物と
をセリウム：サマリウムの元素モル比８：２で混合して
水中に均一に溶解させ、イオン伝導性物質の前駆体水溶
液を作製した。次に、シュウ酸無水物を溶解させた水溶
液中に、酸化亜鉛・酸化アンチモン粒子混合体水性ゾル
（日産化学（株）製・商品名セルナックス）を分散さ
せ、均一分散液を作製した。この均一分散液に前記のイ
オン伝導性物質の前駆体水溶液を滴下し、水に不溶のシ
ュウ酸セリウムおよびシュウ酸サマリウム混合体を生成
・析出させた。この析出の際に、電子伝導性物質粒子で
ある前記の酸化亜鉛・酸化アンチモン粒子がシュウ酸セ
リウム・シュウ酸サマリウムの混合体に包合される。そ
の後溶液を静置して析出物を沈殿させた後、濾過を行
い、さらに濾別した固体を再度水中に分散展開して洗浄
を行った後に静置して濾過を行い、沈殿物を濾別した。
この固体を１５０℃で２時間加熱した後、８００℃で３
時間焼成し、酸化亜鉛粒子と酸化アンチモン粒子の表面
の一部にセリウムサマリウム複合酸化物（Ｃｅ0.8Ｓｍ
0.2Ｏ1.9）を付着配置した粒子（セリウムサマリウム複
合酸化物付きの酸化亜鉛粒子および酸化アンチモン粒
子）を得た。Embodiment 1 Cerium nitrate hydrate and samarium nitrate hydrate are mixed as a water-soluble precursor of an ion-conductive substance at an elemental molar ratio of cerium: samarium of 8: 2 and uniformly dissolved in water to form a precursor of the ion-conductive substance. An aqueous body solution was prepared. Next, an aqueous sol of a mixture of zinc oxide and antimony oxide particles (trade name: Cellnax, manufactured by Nissan Chemical Industries, Ltd.) was dispersed in an aqueous solution in which oxalic anhydride was dissolved to prepare a uniform dispersion. The precursor aqueous solution of the ion-conductive substance was dropped into the uniform dispersion to produce and precipitate a water-insoluble cerium oxalate and samarium oxalate mixture. At the time of this deposition, the zinc oxide / antimony oxide particles, which are electron conductive material particles, are encapsulated in a mixture of cerium oxalate / samarium oxalate. After that, the solution was allowed to stand to precipitate a precipitate, followed by filtration, and the filtered solid was dispersed and developed again in water, washed, and then allowed to stand, filtered, and the precipitate was separated by filtration. did.
After heating this solid at 150 ° C for 2 hours,
After calcination for a period of time, the cerium-samarium composite oxide (Ce 0.8 Sm
0.2 O 1.9 ) were obtained to obtain particles (zinc oxide particles and antimony oxide particles with a cerium-samarium composite oxide).
【００４５】このセリウムサマリウム複合酸化物付きの
酸化亜鉛粒子および酸化アンチモン粒子を水中に分散さ
せ、触媒活性を有する金属の前駆体水溶液としてジニト
ロアンミン白金硝酸を溶解させた水溶液を所定量添加し
て充分撹拌した。この分散溶液のｐHが８になるまでア
ンモニア水を添加した後、濾過を行い、分離した固体を
１２０℃で３時間、２５０℃で３時間の焼成処理を行
い、セリウムサマリウム複合酸化物付きの酸化亜鉛粒子
および酸化アンチモン粒子の表面にさらに白金微細粒子
を付着配置したＮＯx浄化用触媒粉末を得た。The zinc oxide particles and antimony oxide particles with the cerium-samarium composite oxide are dispersed in water, and a predetermined amount of an aqueous solution in which dinitroammineplatinic nitric acid is dissolved is added as a precursor aqueous solution of a metal having catalytic activity. Stirred. After adding ammonia water until the pH of the dispersion solution becomes 8, filtration is performed, and the separated solid is subjected to a calcination treatment at 120 ° C. for 3 hours and at 250 ° C. for 3 hours to obtain an oxidation with a cerium-samarium composite oxide. NO x purification catalyst powder was obtained in which platinum fine particles were further attached to the surfaces of zinc particles and antimony oxide particles.
【００４６】このＮＯx浄化用触媒粉末の断面を拡大率
１００万倍の透過型電子顕微鏡で観察したところ、酸化
亜鉛粒子または酸化アンチモン粒子の表面にセリウムサ
マリウム複合酸化物が配置され、酸化亜鉛粒子または酸
化アンチモン粒子の表面およびセリウムサマリウム複合
酸化物の表面に白金微細粒子が配置されているのが確認
され、酸化亜鉛粒子または酸化アンチモン粒子の表面と
セリウムサマリウム複合酸化物の表面との両方に接触し
て配置されている白金微細粒子も確認された。When a cross section of the NO x purification catalyst powder was observed with a transmission electron microscope at a magnification of 1,000,000, a cerium-samarium composite oxide was arranged on the surface of the zinc oxide particles or the antimony oxide particles, and the zinc oxide particles were Alternatively, it was confirmed that platinum fine particles were arranged on the surface of the antimony oxide particles and the surface of the cerium samarium composite oxide, and both the surfaces of the zinc oxide particles or the antimony oxide particles and the surface of the cerium samarium composite oxide were contacted. Also, platinum fine particles arranged in a manner as described above were confirmed.
【００４７】実施例２〜６．実施例１と同様の方法で、
硝酸サマリウム水和物の代わりに、硝酸イッテルビウム
水和物、硝酸イットリウム水和物、硝酸ガドリニウム水
和物、硝酸ネオジウム水和物、硝酸ランタン水和物をそ
れぞれ用い、酸化亜鉛粒子と酸化アンチモン粒子に、そ
れぞれセリウムイッテルビウム複合酸化物、セリウムイ
ットリウム複合酸化物、セリウムガドリニウム複合酸化
物、セリウムネオジウム複合酸化物、セリウムランタン
複合酸化物を付着配置したセリウム含有複合酸化物付き
の酸化亜鉛粒子および酸化アンチモン粒子を得た。Embodiments 2-6. In the same manner as in Example 1,
Instead of samarium nitrate hydrate, ytterbium nitrate hydrate, yttrium nitrate hydrate, gadolinium nitrate hydrate, neodymium nitrate hydrate, and lanthanum nitrate hydrate are used to form zinc oxide particles and antimony oxide particles, respectively. Cerium-ytterbium composite oxide, cerium-yttrium composite oxide, cerium-gadolinium composite oxide, cerium-neodymium composite oxide, cerium-lanthanum composite oxide, and zinc oxide and antimony oxide particles with cerium-containing composite oxide. Obtained.
【００４８】これらのセリウム含有複合酸化物付きの酸
化亜鉛粒子および酸化アンチモン粒子を水中に分散さ
せ、ジニトロアンミン白金硝酸を溶解させた水溶液を所
定量添加して充分撹拌した。この分散溶液のｐHが８に
なるまでアンモニア水を添加した後、濾過を行い、分離
した固体を１２０℃で３時間加熱した後、２５０℃で３
時間の焼成処理を行い、セリウム含有複合酸化物付きの
酸化亜鉛粒子および酸化アンチモン粒子に、さらに白金
微細粒子を付着配置したＮＯx浄化用触媒粉末を得た。The zinc oxide particles and the antimony oxide particles with the cerium-containing composite oxide were dispersed in water, and a predetermined amount of an aqueous solution in which dinitroammineplatinic nitric acid was dissolved was added and stirred sufficiently. Ammonia water was added until the pH of the dispersion became 8. Then, filtration was performed, and the separated solid was heated at 120 ° C. for 3 hours.
Baked processing time, the zinc oxide particles and antimony oxide particles with the cerium-containing composite oxide, to give the the NO x purification catalyst powder was further adhered arranged platinum fine particles.
【００４９】これらのＮＯx浄化用触媒粉末の断面を拡
大率１００万倍の透過型電子顕微鏡で観察したところ、
酸化亜鉛粒子または酸化アンチモン粒子の表面にセリウ
ム含有複合酸化物が配置され、酸化亜鉛粒子または酸化
アンチモン粒子の表面およびセリウム含有複合酸化物の
表面に白金微細粒子が配置されているのが確認され、酸
化亜鉛粒子または酸化アンチモン粒子の表面とセリウム
含有複合酸化物の表面との両方に接触して配置されてい
る白金微細粒子も確認された。When the cross section of these NO x purification catalyst powders was observed with a transmission electron microscope at a magnification of 1,000,000 times,
The cerium-containing composite oxide is arranged on the surface of the zinc oxide particles or the antimony oxide particles, and it is confirmed that the platinum fine particles are arranged on the surfaces of the zinc oxide particles or the antimony oxide particles and the surface of the cerium-containing composite oxide. Platinum fine particles which were arranged in contact with both the surfaces of the zinc oxide or antimony oxide particles and the surface of the cerium-containing composite oxide were also confirmed.
【００５０】実施例７〜１２．実施例１〜６で得たセリ
ウム含有複合酸化物付きの酸化亜鉛粒子および酸化アン
チモン粒子について、実施例１〜６と同様の方法で、ジ
ニトロアンミン白金硝酸の代わりにジニトロアンミンパ
ラジウム硝酸を用いてパラジウム微細粒子を付着させ、
セリウム含有複合酸化物付きの酸化亜鉛粒子および酸化
アンチモン粒子に、さらにパラジウム微細粒子を付着配
置したＮＯx浄化用触媒粉末を得た。Embodiments 7 to 12 With respect to the zinc oxide particles and antimony oxide particles with the cerium-containing composite oxide obtained in Examples 1 to 6, in the same manner as in Examples 1 to 6, palladium was replaced with dinitroamminepalladium nitrate instead of dinitroammineplatinum nitrate. Attach fine particles,
The zinc oxide particles and antimony oxide particles with the cerium-containing composite oxide, to give the the NO x purification catalyst powder was further adhered disposed palladium fine particles.
【００５１】これらのＮＯx浄化用触媒粉末の断面を拡
大率１００万倍の透過型電子顕微鏡で観察したところ、
酸化亜鉛粒子または酸化アンチモン粒子の表面にセリウ
ム含有複合酸化物が配置され、酸化亜鉛粒子または酸化
アンチモン粒子の表面およびセリウム含有複合酸化物の
表面にパラジウム微細粒子が配置されているのが確認さ
れ、酸化亜鉛粒子または酸化アンチモン粒子の表面とセ
リウム含有複合酸化物の表面との両方に接触して配置さ
れているパラジウム微細粒子も確認された。When the cross section of these NO x purification catalyst powders was observed with a transmission electron microscope at a magnification of 1,000,000 times,
The cerium-containing composite oxide is disposed on the surface of the zinc oxide particles or the antimony oxide particles, and it is confirmed that the palladium fine particles are disposed on the surfaces of the zinc oxide particles or the antimony oxide particles and the cerium-containing composite oxide, Fine palladium particles that were arranged in contact with both the surfaces of the zinc oxide or antimony oxide particles and the surface of the cerium-containing composite oxide were also confirmed.
【００５２】実施例１３〜１８．実施例１〜６で得たセ
リウム含有複合酸化物付きの酸化亜鉛粒子および酸化ア
ンチモン粒子について、実施例１〜６と同様の方法で、
ジニトロアンミン白金硝酸の代わりに硝酸ロジウムを用
いてロジウム微細粒子を付着させ、セリウム含有複合酸
化物付きの酸化亜鉛粒子および酸化アンチモン粒子に、
さらにロジウム微細粒子を付着配置したＮＯx浄化用触
媒粉末を得た。Embodiments 13 to 18 About the zinc oxide particles and the antimony oxide particles with the cerium-containing composite oxide obtained in Examples 1 to 6, in the same manner as in Examples 1 to 6,
Using rhodium nitrate instead of dinitroammineplatinic nitrate to attach rhodium fine particles, zinc oxide particles with cerium-containing composite oxide and antimony oxide particles,
To give an additional the NO x purification catalyst powder adhered arranged rhodium fine particles.
【００５３】これらのＮＯx浄化用触媒粉末の断面を拡
大率１００万倍の透過型電子顕微鏡で観察したところ、
酸化亜鉛粒子または酸化アンチモン粒子の表面にセリウ
ム含有複合酸化物が配置され、酸化亜鉛粒子または酸化
アンチモン粒子の表面およびセリウム含有複合酸化物の
表面にロジウム微細粒子が配置されているのが確認さ
れ、酸化亜鉛粒子または酸化アンチモン粒子の表面とセ
リウム含有複合酸化物の表面との両方に接触して配置さ
れているロジウム微細粒子も確認された。The cross section of these NO x purification catalyst powders was observed with a transmission electron microscope at a magnification of 1,000,000 times.
The cerium-containing composite oxide is arranged on the surface of the zinc oxide particles or the antimony oxide particles, and it is confirmed that rhodium fine particles are arranged on the surfaces of the zinc oxide particles or the antimony oxide particles and the cerium-containing composite oxide, Rhodium fine particles which were arranged in contact with both the surfaces of the zinc oxide or antimony oxide particles and the surface of the cerium-containing composite oxide were also confirmed.
【００５４】実施例１９〜２４．実施例１〜６で得たセ
リウム含有複合酸化物付きの酸化亜鉛粒子および酸化ア
ンチモン粒子について、実施例１〜６と同様の方法で、
ジニトロアンミン白金硝酸の代わりに硝酸オスミウムを
用いてオスミウム微細粒子を付着させ、セリウム含有複
合酸化物付きの酸化亜鉛粒子および酸化アンチモン粒子
に、さらにオスミウム微細粒子を付着配置したＮＯx浄
化用触媒粉末を得た。Embodiments 19 to 24. About the zinc oxide particles and the antimony oxide particles with the cerium-containing composite oxide obtained in Examples 1 to 6, in the same manner as in Examples 1 to 6,
Instead of Jinitoroanmin platinum nitrate deposited osmium fine particles with nitric acid osmium, zinc oxide particles and antimony oxide particles with the cerium-containing composite oxide, the the NO x purification catalyst powder was further adhered arranged osmium fine particles Obtained.
【００５５】これらのＮＯx浄化用触媒粉末の断面を拡
大率１００万倍の透過型電子顕微鏡で観察したところ、
酸化亜鉛粒子または酸化アンチモン粒子の表面にセリウ
ム含有複合酸化物が配置され、酸化亜鉛粒子または酸化
アンチモン粒子の表面およびセリウム含有複合酸化物の
表面にオスミウム微細粒子が配置されているのが確認さ
れ、酸化亜鉛粒子または酸化アンチモン粒子の表面とセ
リウム含有複合酸化物の表面との両方に接触して配置さ
れているオスミウム微細粒子も確認された。When the cross section of these NO x purification catalyst powders was observed with a transmission electron microscope at a magnification of 1,000,000 times,
The cerium-containing composite oxide is arranged on the surface of the zinc oxide particles or the antimony oxide particles, and it is confirmed that the osmium fine particles are arranged on the surfaces of the zinc oxide particles or the antimony oxide particles and the cerium-containing composite oxide, Osmium fine particles which were arranged in contact with both the surfaces of the zinc oxide particles or antimony oxide particles and the surface of the cerium-containing composite oxide were also confirmed.
【００５６】実施例２５〜３０．実施例１〜６で得たセ
リウム含有複合酸化物付きの酸化亜鉛粒子および酸化ア
ンチモン粒子について、実施例１〜６と同様の方法で、
ジニトロアンミン白金硝酸の代わりに硝酸イリジウムを
用いてイリジウム微細粒子を付着させ、セリウム含有複
合酸化物付きの酸化亜鉛粒子および酸化アンチモン粒子
に、さらにイリジウム微細粒子を付着配置したＮＯx浄
化用触媒粉末を得た。Embodiments 25 to 30. About the zinc oxide particles and the antimony oxide particles with the cerium-containing composite oxide obtained in Examples 1 to 6, in the same manner as in Examples 1 to 6,
Instead of Jinitoroanmin platinum nitrate deposited iridium fine particles using iridium nitrate, zinc oxide particles and antimony oxide particles with the cerium-containing composite oxide, the the NO x purification catalyst powder was further adhered disposed iridium fine particles Obtained.
【００５７】これらのＮＯx浄化用触媒粉末の断面を拡
大率１００万倍の透過型電子顕微鏡で観察したところ、
酸化亜鉛粒子または酸化アンチモン粒子の表面にセリウ
ム含有複合酸化物が配置され、酸化亜鉛粒子または酸化
アンチモン粒子の表面およびセリウム含有複合酸化物の
表面にイリジウム微細粒子が配置されているのが確認さ
れ、酸化亜鉛粒子または酸化アンチモン粒子の表面とセ
リウム含有複合酸化物の表面との両方に接触して配置さ
れているイリジウム微細粒子も確認された。The cross section of these NO x purification catalyst powders was observed with a transmission electron microscope at a magnification of 1,000,000 times.
The cerium-containing composite oxide is arranged on the surface of the zinc oxide particles or antimony oxide particles, and it is confirmed that the iridium fine particles are arranged on the surfaces of the zinc oxide particles or the antimony oxide particles and the cerium-containing composite oxide, Iridium fine particles which were arranged in contact with both the surface of the zinc oxide particles or the antimony oxide particles and the surface of the cerium-containing composite oxide were also confirmed.
【００５８】実施例３１〜３６．実施例１〜６で得たセ
リウム含有複合酸化物付きの酸化亜鉛粒子および酸化ア
ンチモン粒子について、実施例１〜６と同様の方法で、
ジニトロアンミン白金硝酸の代わりに硝酸ルテニウムを
用いてルテニウム微細粒子を付着させ、セリウム含有複
合酸化物付きの酸化亜鉛粒子および酸化アンチモン粒子
に、さらにルテニウム微細粒子を付着配置したＮＯx浄
化用触媒粉末を得た。Embodiments 31 to 36. About the zinc oxide particles and the antimony oxide particles with the cerium-containing composite oxide obtained in Examples 1 to 6, in the same manner as in Examples 1 to 6,
Instead of Jinitoroanmin platinum nitrate deposited ruthenium fine particles using a ruthenium nitrate, zinc oxide particles and antimony oxide particles with the cerium-containing composite oxide, the the NO x purification catalyst powder was further adhered arranged ruthenium fine particles Obtained.
【００５９】これらのＮＯx浄化用触媒粉末の断面を拡
大率１００万倍の透過型電子顕微鏡で観察したところ、
酸化亜鉛粒子または酸化アンチモン粒子の表面にセリウ
ム含有複合酸化物が配置され、酸化亜鉛粒子または酸化
アンチモン粒子の表面およびセリウム含有複合酸化物の
表面にルテニウム微細粒子が配置されているのが確認さ
れ、酸化亜鉛粒子または酸化アンチモン粒子の表面とセ
リウム含有複合酸化物の表面との両方に接触して配置さ
れているルテニウム微細粒子も確認された。The cross section of these NO x purification catalyst powders was observed with a transmission electron microscope at a magnification of 1,000,000 times.
The cerium-containing composite oxide is arranged on the surface of the zinc oxide particles or the antimony oxide particles, and it is confirmed that the ruthenium fine particles are arranged on the surfaces of the zinc oxide particles or the antimony oxide particles and the cerium-containing composite oxide, Ruthenium fine particles which were arranged in contact with both the surfaces of the zinc oxide or antimony oxide particles and the surface of the cerium-containing composite oxide were also confirmed.
【００６０】実施例３７〜４２．実施例１〜６で得たセ
リウム含有複合酸化物付きの酸化亜鉛粒子および酸化ア
ンチモン粒子について、実施例１〜６と同様の方法で、
ジニトロアンミン白金硝酸の代わりにジニトロアンミン
白金硝酸と硝酸ルテニウムとをモル比１：１で混合した
ものを用いて白金微細粒子とルテニウム微細粒子を付着
させ、セリウム含有複合酸化物付きの酸化亜鉛粒子およ
び酸化アンチモン粒子に、さらに白金微細粒子とルテニ
ウム微細粒子を付着配置したＮＯx浄化用触媒粉末を得
た。Embodiments 37 to 42. About the zinc oxide particles and the antimony oxide particles with the cerium-containing composite oxide obtained in Examples 1 to 6, in the same manner as in Examples 1 to 6,
Platinum fine particles and ruthenium fine particles are adhered using a mixture of dinitroammineplatinic nitrate and ruthenium nitrate at a molar ratio of 1: 1 instead of dinitroammineplatinum nitrate, and zinc oxide particles with a cerium-containing composite oxide and the antimony oxide particles, to obtain a the NO x purification catalyst powder was further adhered arranged platinum fine particles and ruthenium fine particles.
【００６１】これらのＮＯx浄化用触媒粉末の断面を拡
大率１００万倍の透過型電子顕微鏡で観察したところ、
酸化亜鉛粒子または酸化アンチモン粒子の表面にセリウ
ム含有複合酸化物が配置され、酸化亜鉛粒子または酸化
アンチモン粒子の表面およびセリウム含有複合酸化物の
表面に白金微細粒子とルテニウム微細粒子が配置されて
いるのが確認され、酸化亜鉛粒子または酸化アンチモン
粒子の表面とセリウム含有複合酸化物の表面との両方に
接触して配置されている白金微細粒子とルテニウム微細
粒子も確認された。The cross section of these NO x purification catalyst powders was observed with a transmission electron microscope at a magnification of 1,000,000 times.
The cerium-containing composite oxide is placed on the surface of the zinc oxide or antimony oxide particles, and the platinum fine particles and ruthenium fine particles are placed on the surfaces of the zinc oxide or antimony oxide particles and the cerium-containing composite oxide. Was confirmed, and platinum fine particles and ruthenium fine particles arranged in contact with both the surfaces of the zinc oxide particles or antimony oxide particles and the surface of the cerium-containing composite oxide were also confirmed.
【００６２】実施例４３．硝酸セリウムと硝酸サマリウ
ムとをセリウム：サマリウムの元素モル比８：２で混合
して水中に均一に溶解させ、イオン伝導性物質の前駆体
水溶液を作製した。次に、シュウ酸無水物を溶解させた
水溶液中に、ニッケル粒子を分散させ、均一分散液を作
製した。この均一分散液中に前記のイオン伝導性物質の
前駆体水溶液を滴下し、水に不溶のシュウ酸セリウムお
よびシュウ酸サマリウム混合体を生成・析出させた。こ
の析出の際に、電子伝導性物質粒子である前記のニッケ
ル粒子がシュウ酸セリウム・シュウ酸サマリウムの混合
体に包合される。その後溶液を静置して析出物を沈殿さ
せた後、濾過を行い、さらに濾別した固体を再度水中に
分散展開して洗浄を行った後に静置して濾過を行い、沈
殿物を濾別した。この固体を１５０℃で２時間加熱した
後、８００℃で３時間焼成し、ニッケル粒子の表面の一
部にセリウムサマリウム複合酸化物（Ｃｅ0.8Ｓｍ0.2Ｏ
1.9）を付着配置した粒子（セリウムサマリウム複合酸
化物付きニッケル粒子）を得た。Embodiment 43 FIG. Cerium nitrate and samarium nitrate were mixed at an elemental molar ratio of cerium: samarium of 8: 2 and uniformly dissolved in water to prepare an aqueous precursor solution of an ion conductive substance. Next, nickel particles were dispersed in an aqueous solution in which oxalic anhydride was dissolved to prepare a uniform dispersion. The precursor aqueous solution of the above-mentioned ion-conductive substance was dropped into this uniform dispersion to produce and precipitate a water-insoluble cerium oxalate and samarium oxalate mixture. At the time of this deposition, the nickel particles, which are electron conductive material particles, are encapsulated in a mixture of cerium oxalate and samarium oxalate. After that, the solution was allowed to stand to precipitate a precipitate, followed by filtration, and the filtered solid was dispersed and developed again in water, washed, and then allowed to stand, filtered, and the precipitate was separated by filtration. did. After heating this solid at 150 ° C. for 2 hours, it is fired at 800 ° C. for 3 hours, and a part of the surface of the nickel particles is coated with a cerium-samarium composite oxide (Ce 0.8 Sm 0.2 O).
1.9 ) were attached to obtain particles (nickel particles with cerium-samarium composite oxide).
【００６３】このセリウムサマリウム複合酸化物付きニ
ッケル粒子を水中に分散させ、触媒活性を有する金属の
前駆体水溶液としてジニトロアンミン白金硝酸を溶解さ
せた水溶液を所定量添加して充分撹拌した。この分散溶
液のｐHが８になるまでアンモニア水を添加した後、濾
過を行い、分離した固体を１２０℃で３時間、２５０℃
で３時間の焼成処理を行い、セリウムサマリウム複合酸
化物付きニッケル粒子の表面にさらに白金微細粒子を付
着配置したＮＯx浄化用触媒粉末を得た。The nickel particles provided with the cerium-samarium composite oxide were dispersed in water, and a predetermined amount of an aqueous solution in which dinitroammineplatinic nitric acid was dissolved as a precursor aqueous solution of a metal having catalytic activity was added and sufficiently stirred. After adding ammonia water until the pH of the dispersion solution becomes 8, filtration was performed, and the separated solid was heated at 120 ° C for 3 hours at 250 ° C.
In baked for 3 hours to obtain the NO x purification catalyst powder was further adhered arranged platinum fine particles to the surface of the cerium samarium composite oxide with nickel particles.
【００６４】このＮＯx浄化用触媒粉末の断面を拡大率
１００万倍の透過型電子顕微鏡で観察したところ、ニッ
ケル粒子の表面にセリウムサマリウム複合酸化物が配置
され、ニッケル粒子の表面およびセリウムサマリウム複
合酸化物の表面に白金微細粒子が配置されているのが確
認され、ニッケル粒子の表面とセリウムサマリウム複合
酸化物の表面との両方に接触して配置されている白金微
細粒子も確認された。When the cross section of the NO x purification catalyst powder was observed with a transmission electron microscope at a magnification of 1,000,000, the cerium-samarium composite oxide was disposed on the surface of the nickel particles, and the surface of the nickel particles and the cerium-samarium composite oxide were observed. It was confirmed that platinum fine particles were arranged on the surface of the oxide, and platinum fine particles arranged in contact with both the surface of the nickel particles and the surface of the cerium-samarium composite oxide were also confirmed.
【００６５】実施例４４．イオン伝導性物質の水溶性前
駆体として硝酸セリウム水和物と硝酸サマリウム水和物
とをセリウム：サマリウムの元素モル比８：２で混合し
て水中に均一に溶解させ、イオン伝導性物質の前駆体水
溶液を作製した。次に、シュウ酸無水物を溶解させた水
溶液中に、酸化ニッケル粒子を分散させ、均一分散液を
作製した。この均一分散液に前記のイオン伝導性物質の
前駆体水溶液を滴下し、水に不溶のシュウ酸セリウムお
よびシュウ酸サマリウム混合体を生成・析出させた。こ
の析出の際に、電子伝導性物質粒子である前記の酸化ニ
ッケル粒子がシュウ酸セリウム・シュウ酸サマリウムの
混合体に包合される。その後溶液を静置して析出物を沈
殿させた後、濾過を行い、さらに濾別した固体を再度水
中に分散展開して洗浄を行った後に静置して濾過を行
い、沈殿物を濾別した。この固体を１５０℃で２時間加
熱した後、８００℃で３時間焼成し、酸化ニッケル粒子
の表面の一部にセリウムサマリウム複合酸化物（Ｃｅ
0.8Ｓｍ0.2Ｏ1.9）を付着配置した粒子（セリウムサマ
リウム複合酸化物付き酸化ニッケル粒子）を得た。Embodiment 44 FIG. Cerium nitrate hydrate and samarium nitrate hydrate are mixed as a water-soluble precursor of an ion-conductive substance at an elemental molar ratio of cerium: samarium of 8: 2 and uniformly dissolved in water to form a precursor of the ion-conductive substance. An aqueous body solution was prepared. Next, nickel oxide particles were dispersed in an aqueous solution in which oxalic anhydride was dissolved to prepare a uniform dispersion. The precursor aqueous solution of the ion-conductive substance was dropped into the uniform dispersion to produce and precipitate a water-insoluble cerium oxalate and samarium oxalate mixture. At the time of this deposition, the above-mentioned nickel oxide particles, which are electron conductive material particles, are encapsulated in a mixture of cerium oxalate and samarium oxalate. After that, the solution was allowed to stand to precipitate a precipitate, followed by filtration, and the filtered solid was dispersed and developed again in water, washed, and then allowed to stand, filtered, and the precipitate was separated by filtration. did. After heating this solid at 150 ° C. for 2 hours, it is baked at 800 ° C. for 3 hours, and cerium-samarium composite oxide (Ce)
0.8 Sm 0.2 O 1.9 ) was attached to obtain particles (nickel oxide particles with cerium-samarium composite oxide).
【００６６】このセリウムサマリウム複合酸化物付き酸
化ニッケル粒子を水中に分散させ、触媒活性を有する金
属の前駆体水溶液としてジニトロアンミン白金硝酸を溶
解させた水溶液を所定量添加して充分撹拌した。この分
散溶液のｐHが８になるまでアンモニア水を添加した
後、濾過を行い、分離した固体を１２０℃で３時間、２
５０℃で３時間の焼成処理を行い、セリウムサマリウム
複合酸化物付き酸化ニッケル粒子の表面にさらに白金微
細粒子を付着配置したＮＯx浄化用触媒粉末を得た。The nickel oxide particles with cerium-samarium composite oxide were dispersed in water, and a predetermined amount of an aqueous solution in which dinitroammineplatinic nitric acid was dissolved as a precursor aqueous solution of a metal having catalytic activity was added and sufficiently stirred. After adding aqueous ammonia until the pH of the dispersion solution becomes 8, filtration is performed, and the separated solid is separated at 120 ° C. for 3 hours for 2 hours.
A baking treatment was performed at 50 ° C. for 3 hours to obtain a NO x purification catalyst powder in which fine platinum particles were further adhered and arranged on the surfaces of the nickel oxide particles with the cerium-samarium composite oxide.
【００６７】このＮＯx浄化用触媒粉末の断面を拡大率
１００万倍の透過型電子顕微鏡で観察したところ、酸化
ニッケル粒子の表面にセリウムサマリウム複合酸化物が
配置され、酸化ニッケル粒子の表面およびセリウムサマ
リウム複合酸化物の表面に白金微細粒子が配置されてい
るのが確認され、酸化ニッケル粒子の表面とセリウムサ
マリウム複合酸化物の表面との両方に接触して配置され
ている白金微細粒子も確認された。When the cross section of the NO x purification catalyst powder was observed with a transmission electron microscope at a magnification of 1,000,000, the cerium-samarium composite oxide was disposed on the surface of the nickel oxide particles, and the surface of the nickel oxide particles and the cerium It is confirmed that platinum fine particles are arranged on the surface of the samarium composite oxide, and platinum fine particles arranged in contact with both the surface of the nickel oxide particles and the surface of the cerium samarium composite oxide are also confirmed. Was.
【００６８】実施例４５．イオン伝導性物質の水溶性前
駆体として硝酸セリウム水和物と硝酸サマリウム水和物
とを、電子伝導性物質の水溶性前駆体として硝酸銀を、
セリウム：サマリウム：銀の元素モル比８：２：２で混
合して水中に均一に溶解させ、前駆体水溶液を作製し
た。次に、シュウ酸無水物を溶解させた水溶液中に、前
記の前駆体水溶液を滴下し、水に不溶のシュウ酸セリウ
ム、シュウ酸サマリウム、およびシュウ酸銀の混合体を
生成・析出させた。その後溶液を静置して析出物を沈殿
させた後、濾過を行い、さらに濾別した固体を再度水中
に分散展開して洗浄を行った後に静置して濾過を行い、
沈殿物を濾別した。この固体を１５０℃で２時間加熱し
た後、８００℃で３時間焼成した。この焼成後の粉体の
Ｘ線回折ピークを測定したところ、セリウムサマリウム
複合酸化物の回折ピークと酸化銀の回折ピークとが重畳
した回折パターンが観測された。これより酸化銀粒子の
表面の一部にセリウムサマリウム複合酸化物（Ｃｅ0.8
Ｓｍ0.2Ｏ1.9）を付着配置した粒子（セリウムサマリウ
ム複合酸化物付き酸化銀粒子）を得た。Embodiment 45 FIG. Cerium nitrate hydrate and samarium nitrate hydrate as water-soluble precursors of ion-conductive substances, silver nitrate as water-soluble precursors of electron-conductive substances,
Cerium: samarium: silver was mixed at an elemental molar ratio of 8: 2: 2 and uniformly dissolved in water to prepare an aqueous precursor solution. Next, the precursor aqueous solution was dropped into an aqueous solution in which oxalic anhydride was dissolved, and a mixture of water-insoluble cerium oxalate, samarium oxalate, and silver oxalate was generated and precipitated. After that, the solution was allowed to stand to precipitate a precipitate, followed by filtration, and the filtered solid was dispersed and developed again in water, washed, and then allowed to stand for filtration.
The precipitate was filtered off. This solid was heated at 150 ° C. for 2 hours and then calcined at 800 ° C. for 3 hours. When the X-ray diffraction peak of the fired powder was measured, a diffraction pattern in which the diffraction peak of the cerium-samarium composite oxide and the diffraction peak of silver oxide were superimposed was observed. Thus, the cerium-samarium composite oxide (Ce 0.8
Sm 0.2 O 1.9 ) was attached to obtain silver oxide particles with cerium-samarium composite oxide.
【００６９】このセリウムサマリウム複合酸化物付き酸
化銀粒子を水中に分散させ、触媒活性を有する金属の前
駆体水溶液としてジニトロアンミン白金硝酸を溶解させ
た水溶液を所定量添加して充分撹拌した。この分散溶液
のｐHが８になるまでアンモニア水を添加した後、濾過
を行い、分離した固体を１２０℃で３時間、２５０℃で
３時間の焼成処理を行い、セリウムサマリウム複合酸化
物付き酸化銀粒子の表面にさらに白金微細粒子を付着配
置したＮＯx浄化用触媒粉末を得た。The silver oxide particles with the cerium-samarium composite oxide were dispersed in water, and a predetermined amount of an aqueous solution in which dinitroammineplatinic nitric acid was dissolved as a precursor aqueous solution of a metal having catalytic activity was added and stirred sufficiently. After adding ammonia water until the pH of the dispersion solution becomes 8, filtration is performed, and the separated solid is subjected to a baking treatment at 120 ° C. for 3 hours and at 250 ° C. for 3 hours to obtain a silver oxide with cerium-samarium composite oxide. It was obtained the NO x purification catalyst powder was further adhered arranged platinum fine particles to the surface of the particle.
【００７０】このＮＯx浄化用触媒粉末の断面を拡大率
１００万倍の透過型電子顕微鏡で観察したところ、酸化
銀粒子の表面にセリウムサマリウム複合酸化物が配置さ
れ、酸化銀粒子の表面およびセリウムサマリウム複合酸
化物の表面に白金微細粒子が配置されているのが確認さ
れ、酸化銀粒子の表面とセリウムサマリウム複合酸化物
の表面との両方に接触して配置されている白金微細粒子
も確認された。When the cross section of the NO x purification catalyst powder was observed with a transmission electron microscope at a magnification of 1,000,000, a cerium-samarium composite oxide was arranged on the surface of the silver oxide particles, and the surface of the silver oxide particles and the cerium It is confirmed that platinum fine particles are arranged on the surface of the samarium composite oxide, and platinum fine particles arranged in contact with both the surface of the silver oxide particles and the surface of the cerium samarium composite oxide are also confirmed. Was.
【００７１】実施例４６．イオン伝導性物質の水溶性前
駆体として硝酸セリウム水和物と硝酸サマリウム水和物
とを、電子伝導性物質の水溶性前駆体として硝酸ニッケ
ルを、セリウム：サマリウム：ニッケルの元素モル比
８：２：２で混合して水中に均一に溶解させ、前駆体水
溶液を作製した。次に、シュウ酸無水物を溶解させた水
溶液中に、前記の前駆体水溶液を滴下し、水に不溶のシ
ュウ酸セリウム、シュウ酸サマリウム、およびシュウ酸
ニッケルの混合体を生成・析出させた。その後溶液を静
置して析出物を沈殿させた後、濾過を行い、さらに濾別
した固体を再度水中に分散展開して洗浄を行った後に静
置して濾過を行い、沈殿物を濾別した。この固体を１５
０℃で２時間加熱した後、８００℃で３時間焼成した。
この焼成後の粉体のＸ線回折ピークを測定したところ、
セリウムサマリウム複合酸化物の回折ピークと酸化ニッ
ケルの回折ピークとが重畳した回折パターンが観測され
た。これより酸化ニッケル粒子の表面の一部にセリウム
サマリウム複合酸化物（Ｃｅ0.8Ｓｍ0.2Ｏ 1.9）を付着
配置した粒子（セリウムサマリウム複合酸化物付き酸化
ニッケル粒子）を得た。Embodiment 46 FIG. Before water solubility of ion conductive material
Cerium nitrate hydrate and samarium nitrate hydrate as precursors
And nickel nitrate as a water-soluble precursor of an electron conductive substance
To the elemental molar ratio of cerium: samarium: nickel
8: 2: 2 mixed and uniformly dissolved in water, precursor water
A solution was prepared. Next, water containing oxalic anhydride
The above precursor aqueous solution is dropped into the solution, and the water-insoluble
Cerium oxalate, samarium oxalate, and oxalic acid
A mixture of nickel was produced and deposited. Then let the solution stand
To precipitate the precipitate, and then perform filtration and further filtration.
The washed solid is dispersed and developed again in water, washed,
The mixture was placed and filtered, and the precipitate was separated by filtration. 15 of this solid
After heating at 0 ° C. for 2 hours, baking was performed at 800 ° C. for 3 hours.
When the X-ray diffraction peak of this fired powder was measured,
Cerium samarium composite oxide diffraction peaks and nickel oxide
A diffraction pattern superimposed on the Kell diffraction peak is observed.
Was. From this, cerium is applied to part of the surface of the nickel oxide particles.
Samarium composite oxide (Ce0.8Sm0.2O 1.9Attach)
Disposed particles (oxidation with cerium-samarium composite oxide
Nickel particles).
【００７２】このセリウムサマリウム複合酸化物付き酸
化ニッケル粒子を水中に分散させ、触媒活性を有する金
属の前駆体水溶液としてジニトロアンミン白金硝酸を溶
解させた水溶液を所定量添加して充分撹拌した。この分
散溶液のｐHが８になるまでアンモニア水を添加した
後、濾過を行い、分離した固体を１２０℃で３時間、２
５０℃で３時間の焼成処理を行い、セリウムサマリウム
複合酸化物付き酸化ニッケル粒子の表面にさらに白金微
細粒子を付着配置したＮＯx浄化用触媒粉末を得た。The nickel oxide particles with the cerium-samarium composite oxide were dispersed in water, and a predetermined amount of an aqueous solution in which dinitroammineplatinic nitric acid was dissolved as a precursor aqueous solution of a metal having catalytic activity was added and sufficiently stirred. After adding aqueous ammonia until the pH of the dispersion solution becomes 8, filtration is performed, and the separated solid is separated at 120 ° C. for 3 hours for 2 hours.
A baking treatment was performed at 50 ° C. for 3 hours to obtain a NO x purification catalyst powder in which fine platinum particles were further adhered and arranged on the surfaces of the nickel oxide particles with the cerium-samarium composite oxide.
【００７３】このＮＯx浄化用触媒粉末の断面を拡大率
１００万倍の透過型電子顕微鏡で観察したところ、酸化
ニッケル粒子の表面にセリウムサマリウム複合酸化物が
配置され、酸化ニッケル粒子の表面およびセリウムサマ
リウム複合酸化物の表面に白金微細粒子が配置されてい
るのが確認され、酸化ニッケル粒子の表面とセリウムサ
マリウム複合酸化物の表面との両方に接触して配置され
ている白金微細粒子も確認された。When the cross section of the NO x purification catalyst powder was observed with a transmission electron microscope at a magnification of 1,000,000, the cerium-samarium composite oxide was disposed on the surface of the nickel oxide particles, and the surface of the nickel oxide particles and the cerium It is confirmed that platinum fine particles are arranged on the surface of the samarium composite oxide, and platinum fine particles arranged in contact with both the surface of the nickel oxide particles and the surface of the cerium samarium composite oxide are also confirmed. Was.
【００７４】実施例１〜４６で得たＮＯx浄化用触媒粉
末９重量部と、シリカバインダー粉末１重量部とを混合
して水中に分散させてスラリーを作製した。このスラリ
ーを４００セル／インチ、６ミルのハニカム（材質：コ
ージェライト）内部に塗工した後、大気中で５００℃で
２時間焼成して、ＮＯx浄化用触媒粉末を担持させたハ
ニカムを得た。なお、ハニカム中の触媒活性微細金属成
分担持量は０．１ｇ／Ｌ〜１．５ｇ／Ｌであった。9 parts by weight of the NO x purification catalyst powder obtained in Examples 1 to 46 and 1 part by weight of a silica binder powder were mixed and dispersed in water to prepare a slurry. This slurry is applied inside a 400 cell / inch, 6 mil honeycomb (material: cordierite), and then fired at 500 ° C. for 2 hours in the air to obtain a honeycomb supporting the NO x purification catalyst powder. Was. The amount of the catalytically active fine metal component carried in the honeycomb was 0.1 g / L to 1.5 g / L.
【００７５】比較例１．γ結晶型アルミナを水中に分散
させ、ジニトロアンミン白金硝酸とジニトロアンミンパ
ラジウム硝酸と硝酸ロジウムとをモル比で５：５：１で
混合、溶解させた水溶液を所定量添加して充分撹拌し
た。この分散溶液のｐＨが８になるまでアンモニア水を
添加したのち、濾過を行ない、分離した固体を１２０℃
で３時間、２５０℃で３時間の焼成処理を行ない、貴金
属を担持させたγアルミナ粉末を得た。この白金担持ア
ルミナ粉末９重量部とシリカバインダー粉末１重量部と
を混合して水中に分散させてスラリーを作製した。この
スラリーを４００セル／インチ、６ミルのハニカム（材
質：コージェライト）内部に塗工したのち、大気中で５
００℃で２時間焼成して、貴金属担持γアルミナを担持
させたハニカムを得た。なお、ハニカム中の金属粒子成
分担持量は２．０ｇ／Ｌであった。Comparative Example 1 The γ-crystalline alumina was dispersed in water, and a predetermined amount of an aqueous solution in which dinitroammineplatinic nitric acid, dinitroamminepalladium nitric acid, and rhodium nitrate were mixed and dissolved at a molar ratio of 5: 5: 1 was added and sufficiently stirred. After adding ammonia water until the pH of this dispersion solution becomes 8, filtration was performed, and the separated solid was heated to 120 ° C.
For 3 hours at 250 ° C. for 3 hours to obtain a γ-alumina powder carrying a noble metal. 9 parts by weight of the platinum-carrying alumina powder and 1 part by weight of the silica binder powder were mixed and dispersed in water to prepare a slurry. This slurry was applied to the inside of a honeycomb (material: cordierite) of 400 cells / inch, 6 mils, and then applied in air.
By firing at 00 ° C. for 2 hours, a honeycomb supporting noble metal-supported γ-alumina was obtained. The amount of the metal particle component carried in the honeycomb was 2.0 g / L.
【００７６】評価１．実施例１で得たＮＯx浄化用触媒
粉末を担持させたハニカムおよび比較例１で得たハニカ
ム内に、空燃比１４．７（ストイキ燃焼状態）における
排ガスの模擬ガスを通し、ＮＯx転化率（浄化率）の評
価を実施した。Evaluation 1. A simulated gas of exhaust gas at an air-fuel ratio of 14.7 (stoichiometric combustion state) was passed through the honeycomb supporting the catalyst powder for NO x purification obtained in Example 1 and the honeycomb obtained in Comparative Example 1 to obtain a NO x conversion rate. (Purification rate) was evaluated.
【００７７】図３に、これらのハニカムの、ＮＯｘ転化
率温度依存性を示す。これより本発明により得られた触
媒は、従来の三元触媒の基本構成である白金・パラジウ
ム・ロジウム担持アルミナ触媒と比べて、白金のみが担
持されているにも関わらず、特に低温（特に３００℃以
下）での転化効率が高い。以上より、本発明により得た
触媒は、ＮＯx浄化性能に優れることは明らかである。FIG. 3 shows the temperature dependence of the NOx conversion of these honeycombs. Thus, the catalyst obtained according to the present invention has a particularly low temperature (especially 300 ° C.) despite the fact that only platinum is supported, compared to the platinum / palladium / rhodium supported alumina catalyst which is the basic structure of the conventional three-way catalyst. (Less than ° C) conversion efficiency is high. From the above, a catalyst obtained by the present invention, it is clear that excellent the NO x purification performance.
【００７８】評価２．実施例１〜４６で得たＮＯx浄化
用触媒粉末を担持させたハニカムおよび比較例１で得た
ハニカム内に、ストイキ燃焼状態における排ガスの模擬
ガスを通し、排気ガス温度２５０℃および３００℃での
各実施例におけるＮＯx浄化率の評価を実施した。その
結果を表１〜表９にまとめる。Evaluation 2. In a honeycomb obtained in Example the NO x purification catalyst powder honeycomb and Comparative Example 1 was supported obtained in 1-46, through a simulated gas of the exhaust gas in the stoichiometric combustion state, the exhaust gas temperature 250 ° C. and 300 ° C. The evaluation of the NO x purification rate in each of Examples was performed. The results are summarized in Tables 1 to 9.
【００７９】[0079]
【表１】 [Table 1]
【００８０】[0080]
【表２】 [Table 2]
【００８１】[0081]
【表３】 [Table 3]
【００８２】[0082]
【表４】 [Table 4]
【００８３】[0083]
【表５】 [Table 5]
【００８４】[0084]
【表６】 [Table 6]
【００８５】[0085]
【表７】 [Table 7]
【００８６】[0086]
【表８】 [Table 8]
【００８７】[0087]
【表９】 [Table 9]
【００８８】以上より、本発明により得られた触媒が、
従来の三元触媒（アルミナ基材に貴金属が担持されたも
の）に比べて優れた性能を有することは明らかである。As described above, the catalyst obtained according to the present invention is:
It is apparent that the catalyst has superior performance as compared with a conventional three-way catalyst (a precious metal supported on an alumina substrate).
【００８９】[0089]
【発明の効果】本発明の第１の構成によれば、電子伝導
性物質粒子表面の一部にイオン伝導性物質が配置され、
かつ触媒活性を有する複数個の微細金属粒子が、前記イ
オン伝導性物質表面と電子伝導性物質粒子表面との両方
に接触して配置され、前記イオン伝導性物質および電子
伝導性物質を介してそれぞれイオンおよび電子が移動す
ることにより、前記微細金属粒子におけるＮＯxの還元
反応と還元剤の酸化反応とを電気化学的に行なうので、
異なる微細金属粒子間にＮＯxと還元剤とが吸着した場
合でも酸化還元反応を起こすことが可能となるため、Ｎ
Ｏx浄化効率をより高めることが可能となる。According to the first aspect of the present invention, an ion conductive substance is arranged on a part of the surface of an electron conductive substance particle,
And a plurality of fine metal particles having catalytic activity are arranged in contact with both the surface of the ion conductive material and the surface of the electron conductive material particles, each via the ion conductive material and the electron conductive material The movement of ions and electrons causes the reduction reaction of NO x and the oxidation reaction of the reducing agent in the fine metal particles to be performed electrochemically.
Even when NO x and a reducing agent are adsorbed between different fine metal particles, an oxidation-reduction reaction can be caused.
Ox purification efficiency can be further increased.
【００９０】本発明の第２の構成によれば、電子伝導性
物質が金属であるので、電子伝導性が良好となり、ＮＯ
x浄化効率をより高めることが可能となる。According to the second configuration of the present invention, since the electron conductive substance is a metal, the electron conductivity is improved, and the NO.
x It is possible to further increase the purification efficiency.
【００９１】本発明の第３の構成によれば、電子伝導性
物質が金属酸化物であるので、耐熱性が向上し、高温で
の材料安定性が高くなる。その結果、高速運転時に起こ
る触媒の急速昇温にも耐えることが可能となり、触媒の
耐久性が増す。According to the third structure of the present invention, since the electron conductive substance is a metal oxide, heat resistance is improved and material stability at high temperatures is improved. As a result, it is possible to withstand the rapid temperature rise of the catalyst during high-speed operation, and the durability of the catalyst is increased.
【００９２】本発明の第４の構成によれば、イオン伝導
性物質が化学式Ｃｅ1-xＡxＯy（ｘは０．５から０．１
までの数値、ｙは１．７５から２までの数値、ＡはＹ
ｂ、Ｙ、Ｇｄ、Ｓｍ、ＮｄまたはＬａである。）で示さ
れる複合酸化物であるので、酸素イオンの伝導をより低
温で実現することができ、その結果、より低温での触媒
活性を高めることが可能となる。According to the fourth configuration of the present invention, the ion-conductive substance has the chemical formula Ce 1-x A x O y (x is 0.5 to 0.1).
, Y is a number from 1.75 to 2, A is Y
b, Y, Gd, Sm, Nd or La. ), Oxygen ions can be conducted at lower temperatures, and as a result, the catalytic activity at lower temperatures can be increased.
【００９３】本発明の第５の構成によれば、微細金属粒
子が、白金、パラジウム、ロジウム、オスミウム、ルテ
ニウム、イリジウムのうち少なくとも１種の元素よりな
るので、ＮＯxおよび還元剤であるＨＣやＣＯが解離吸
着するため、酸化還元反応がより起こりやすくなる。そ
の結果、ＮＯx浄化効率をさらに高めることが可能とな
る。According to the fifth configuration of the present invention, since the fine metal particles are made of at least one element of platinum, palladium, rhodium, osmium, ruthenium and iridium, NO x and the reducing agent such as HC and Since CO is dissociated and adsorbed, an oxidation-reduction reaction is more likely to occur. As a result, it is possible to further enhance the the NO x purification efficiency.
【００９４】本発明の第１の方法によれば、電子伝導性
物質粒子を分散させた有機酸水溶液中にイオン伝導性物
質の水溶性前駆体を混合し、生成した沈殿物を焼成する
ことにより、電子伝導性物質粒子表面の一部にイオン伝
導性物質を高分散に配置する。その結果、電子伝導体と
イオン伝導体の界面領域面積を増やすことが可能とな
り、高い反応効率を有するＮＯx浄化用触媒を得ること
が可能となる。According to the first method of the present invention, a water-soluble precursor of an ion-conductive substance is mixed in an organic acid aqueous solution in which particles of an electron-conductive substance are dispersed, and the resulting precipitate is calcined. In addition, an ion conductive material is arranged in a high dispersion on a part of the surface of the electron conductive material particles. As a result, it becomes possible to increase the interfacial area area of the electron conductor and the ion conductor, it is possible to obtain the NO x purification catalyst having a high reaction efficiency.
【００９５】本発明の第２の方法によれば、有機酸水溶
液にイオン伝導性物質の水溶性前駆体と電子伝導性物質
の水溶性前駆体とを混合し、生成した沈殿物を焼成する
ことにより、電子伝導性物質粒子表面の一部にイオン伝
導性物質を高分散に配置する。その結果、電子伝導体と
イオン伝導体の界面領域面積を増やすことが可能とな
り、高い反応効率を有するＮＯx浄化用触媒を得ること
が可能となる。According to the second method of the present invention, a water-soluble precursor of an ion conductive substance and a water-soluble precursor of an electron conductive substance are mixed with an aqueous solution of an organic acid, and the resulting precipitate is calcined. As a result, the ion-conductive substance is highly dispersed on a part of the surface of the electron-conductive substance particles. As a result, it becomes possible to increase the interfacial area area of the electron conductor and the ion conductor, it is possible to obtain the NO x purification catalyst having a high reaction efficiency.
【００９６】本発明の第３の方法によれば、有機酸水溶
液がシュウ酸またはクエン酸の水溶液であるので、焼成
物中の不純物含有量を抑えることが可能となり、イオン
伝導性物質のイオン伝導性能が増し、より高い反応効率
を有するＮＯx浄化用触媒を得ることが可能となる。According to the third method of the present invention, since the organic acid aqueous solution is an aqueous solution of oxalic acid or citric acid, the content of impurities in the calcined product can be suppressed, and the ion conductivity of the ion conductive material can be reduced. increases the performance, it is possible to obtain a the NO x purification catalyst having a higher reaction efficiency.
【００９７】本発明の第４の方法によれば、イオン伝導
性物質の水溶性前駆体が硝酸化合物であるので、焼成物
中の不純物含有量を抑えることが可能となり、イオン伝
導性物質のイオン伝導性能が増し、より高い反応効率を
有するＮＯx浄化用触媒を得ることが可能となる。According to the fourth method of the present invention, since the water-soluble precursor of the ion-conductive substance is a nitric acid compound, the content of impurities in the calcined product can be suppressed, and the ion- increased conduction performance, it is possible to obtain a the NO x purification catalyst having a higher reaction efficiency.
【００９８】本発明の第５の方法によれば、表面の一部
にイオン伝導性物質を配置した電子伝導性物質粒子を、
触媒活性を有する金属の前駆体溶液に浸漬し、前記イオ
ン伝導性物質および電子伝導性物質粒子の表面を、前記
触媒活性を有する金属の前駆体で被覆したのち、焼成を
行なうことにより、イオン伝導性物質および電子伝導性
物質粒子の表面に触媒活性を有する微細金属粒子を配置
するので、電子伝導性物質粒子およびイオン伝導性物質
表面に、触媒活性を有するより細かい微細金属粒子を、
付着配置することができる。その結果、より少ない金属
量でより大きい表面積を得ることができ、金属量あたり
の触媒活性も向上し、ＮＯx反応効率を向上させること
が可能となる。According to the fifth method of the present invention, an electron conductive material particle having an ion conductive material disposed on a part of its surface is provided by:
Immersion in a precursor solution of a metal having catalytic activity, coating the surface of the ion-conductive substance and the particles of the electron-conductive substance with a precursor of the metal having catalytic activity, followed by baking to obtain an ion-conductive substance. Since the fine metal particles having catalytic activity are arranged on the surface of the conductive material and the electron conductive material particles, the finer metal particles having catalytic activity are formed on the electron conductive material particles and the ion conductive material surface,
It can be attached and placed. As a result, it is possible to obtain a larger surface area with a smaller amount of metal, the catalytic activity per amount of metal is improved, and also possible to improve the NO x reaction efficiency.
【図１】 本発明の一実施の形態によるＮＯx浄化用触
媒の構造を模式的に示す断面図である。FIG. 1 is a cross-sectional view schematically illustrating a structure of a NO x purification catalyst according to an embodiment of the present invention.
【図２】 本発明における複数の微細金属粒子上で起こ
るＮＯx浄化酸化還元電気化学反応に関する電位図であ
る。FIG. 2 is a potential diagram relating to a NO x purification redox electrochemical reaction occurring on a plurality of fine metal particles in the present invention.
【図３】 本発明によるＮＯx浄化用触媒触媒粉末を担
持させたハニカムの、ＮＯx浄化効率温度依存性の一例
である。[Figure 3] a honeycomb having supported thereon a catalyst catalyst powder for the NO x purification according to the invention, which is an example of the NO x purification efficiency temperature dependence.
【図４】 従来のガソリンエンジン用三元触媒に関する
空気と燃料の重量比（空燃比）とＮＯx、ＨＣ、ＣＯの
転化（浄化）率の関係を示す図である。FIG. 4 is a diagram showing the relationship between the weight ratio of air and fuel (air-fuel ratio) and the conversion (purification) rates of NO x , HC, and CO for a conventional three-way catalyst for gasoline engines.
【図５】 従来の排気ガス用ＮＯx浄化用触媒の作用を
示す説明図である。FIG. 5 is an explanatory view showing an operation of the conventional exhaust gas the NO x purification catalyst.
１ 電子伝導性物質、２ イオン伝導性物質、３ａ，３
ｂ，４ 触媒活性を有する微細金属粒子。1 electron conductive material, 2 ion conductive material, 3a, 3
b, 4 Fine metal particles having catalytic activity.
───────────────────────────────────────────────────── フロントページの続き (51)Int.Cl.7 識別記号 ＦＩ テーマコート゛(参考） Ｆ０１Ｎ 3/08 Ｆ０１Ｎ 3/24 Ｃ 3/10 3/28 Ｑ 3/24 ３０１Ｃ 3/28 ３０１Ｐ ３０１ Ｂ０１Ｄ 53/36 １０２Ｂ Ｂ０１Ｊ 23/74 ３２１Ａ (72)発明者 佐藤 稔 東京都千代田区丸の内二丁目２番３号 三 菱電機株式会社内 (72)発明者 白神 昭 東京都千代田区丸の内二丁目２番３号 三 菱電機株式会社内 (72)発明者 中宗 浩昭 東京都千代田区丸の内二丁目２番３号 三 菱電機株式会社内 (72)発明者 光田 憲朗 東京都千代田区丸の内二丁目２番３号 三 菱電機株式会社内 (72)発明者 藤田 洋司 東京都千代田区丸の内二丁目２番３号 三 菱電機株式会社内 (72)発明者 和知 敏 東京都千代田区丸の内二丁目２番３号 三 菱電機株式会社内 (72)発明者 片柴 秀昭 東京都千代田区丸の内二丁目２番３号 三 菱電機株式会社内 Ｆターム(参考） 3G091 AA02 AB02 AB04 BA07 BA14 BA39 CA16 CA18 GA16 GB01X GB04X GB05W GB06W GB07W GB10X GB19X 4D048 AA06 AB02 BA16X BA18X BA19X BA22X BA30X BA31X BA32X BA33X BA34X BA38X BA41X BA42X BB02 4G069 AA03 AA08 AA09 AA11 AA12 BA17 BB04A BB04B BB06A BB06B BC26A BC26B BC32A BC32B BC35A BC35B BC40A BC40B BC42A BC42B BC43A BC43B BC44A BC44B BC68A BC68B BC70A BC70B BC71A BC71B BC72A BC72B BC73A BC73B BC74A BC74B BC75A BC75B CA02 CA03 CA08 CA13 DA06 EA01X EA01Y EA18 FB08 FB09 ──────────────────────────────────────────────────の Continued on the front page (51) Int.Cl. 7 Identification symbol FI Theme coat ゛ (Reference) F01N 3/08 F01N 3/24 C 3/10 3/28 Q 3/24 301C 3/28 301P 301 B01D 53 / 36 102B B01J 23/74 321A (72) Minoru Sato, 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Mitsui Electric Co., Ltd. (72) Akira Shirakami 2-3-2, Marunouchi, Chiyoda-ku, Tokyo Inside Mitsubishi Electric Corporation (72) Inventor Hiroaki Nakamune 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Electric Corporation (72) Inventor Norio Mitsuta 2-3-2 Marunouchi, Chiyoda-ku, Tokyo Mitsubishi Electric Corporation (72) Inventor Yoji Fujita 2-3-2 Marunouchi, Chiyoda-ku, Tokyo 2-3-2 Mitsubishi Electric Corporation (72) Inventor Satoshi Wachi Chiyo, Tokyo 2-3-2 Marunouchi-ku, Mitsui Electric Co., Ltd. (72) Inventor Hideaki Katashiba 2-3-2 Marunouchi, Chiyoda-ku, Tokyo F-term in Mitsubishi Electric Co., Ltd. 3G091 AA02 AB02 AB04 BA07 BA14 BA39 CA16 CA18 GA16 GB01X GB04X GB05W GB06W GB07W GB10X GB19X 4D048 AA06 AB02 BA16X BA18X BA19X BA22X BA30X BA31X BA32X BA33X BA34X BA38X BA41X BA42X BB02 4G069 AA03 AA08 AA09 AA11 AA12 BA17 BB04A BB04B BB06A BB06B BC26A BC26B BC32A BC32B BC35A BC35B BC40A BC40B BC42A BC42B BC43A BC43B BC44A BC44B BC68A BC68B BC70A BC70B BC71A BC71B BC72A BC72B BC73A BC73B BC74A BC74B BC75A BC75B CA02 CA03 CA08 CA13 DA06 EA01X EA01Y EA18 FB08 FB09
Claims (10)
伝導性物質が配置され、かつ触媒活性を有する複数個の
微細金属粒子が、前記イオン伝導性物質表面と電子伝導
性物質粒子表面との両方に接触して配置され、前記イオ
ン伝導性物質および電子伝導性物質を介してそれぞれイ
オンおよび電子が移動することにより、前記微細金属粒
子におけるＮＯxの還元反応と還元剤の酸化反応とを電
気化学的に行なうことを特徴とするＮＯx浄化用触媒。1. A method according to claim 1, wherein the ion conductive material is disposed on a part of the surface of the electron conductive material particles, and a plurality of fine metal particles having catalytic activity are formed on the surface of the ion conductive material and the surface of the electron conductive material particles. is disposed in contact with both, by ions and electrons each migrate through the ion conductive material and an electron conductive substance, an oxidation reaction of the reducing reaction with a reducing agent of the NO x in the fine metal particles the NO x purification catalyst, wherein electrochemically be performed.
とする請求項１記載のＮＯx浄化用触媒。2. The NO x purifying catalyst according to claim 1, wherein the electron conductive substance is a metal.
を特徴とする請求項１記載のＮＯx浄化用触媒。3. The NO x purifying catalyst according to claim 1, wherein the electron conductive substance is a metal oxide.
y（ｘは０．５から０．１までの数値、ｙは１．７５か
ら２までの数値、ＡはＹｂ、Ｙ、Ｇｄ、Ｓｍ、Ｎｄまた
はＬａである。）で示される複合酸化物であることを特
徴とする請求項１記載のＮＯx浄化用触媒。4. The method according to claim 1, wherein the ion conductive material has a chemical formula of Ce 1-x A x O.
a composite oxide represented by y (x is a numerical value from 0.5 to 0.1, y is a numerical value from 1.75 to 2, and A is Yb, Y, Gd, Sm, Nd or La). the NO x purification catalyst of claim 1, wherein the certain.
ジウム、オスミウム、ルテニウム、イリジウムのうち少
なくとも１種の元素よりなる請求項１記載のＮＯx浄化
用触媒。5. The fine metal particles, platinum, palladium, rhodium, osmium, ruthenium, at least one consisting of elements according to claim 1 NO x purifying catalyst according of iridium.
x浄化用触媒の製造方法であって、電子伝導性物質粒子
を分散させた有機酸水溶液中にイオン伝導性物質の水溶
性前駆体を混合し、生成した沈殿物を焼成することによ
り、電子伝導性物質粒子表面の一部にイオン伝導性物質
を配置することを特徴とするＮＯx浄化用触媒の製造方
法。6. The NO according to any one of claims 1 to 5,
x A method for producing a purification catalyst, comprising mixing a water-soluble precursor of an ion-conductive substance in an organic acid aqueous solution in which electron-conductive substance particles are dispersed, and baking the resulting precipitate to obtain an electron-conductive substance. manufacturing method of the NO x purifying catalyst, characterized by arranging the ion conductive material in a part of the sexual material particle surfaces.
x浄化用触媒の製造方法であって、有機酸水溶液にイオ
ン伝導性物質の水溶性前駆体と電子伝導性物質の水溶性
前駆体とを混合し、生成した沈殿物を焼成することによ
り、電子伝導性物質粒子表面の一部にイオン伝導性物質
を配置することを特徴とするＮＯx浄化用触媒の製造方
法。7. The NO according to any one of claims 1 to 5,
x a method for producing a purification catalyst, wherein a water-soluble precursor of an ion-conductive substance and a water-soluble precursor of an electron-conductive substance are mixed in an organic acid aqueous solution, and the resulting precipitate is calcined to obtain an electron-emitting material. manufacturing method of the NO x purifying catalyst, characterized by arranging the ion conductive material in a portion of the conductive material particle surfaces.
の水溶液であることを特徴とする請求項６または７記載
のＮＯx浄化用触媒の製造方法。8. The method of claim 6 or 7 NO x production method of purifying catalyst, wherein the organic acid aqueous solution is an aqueous solution of oxalic acid or citric acid.
化合物であることを特徴とする請求項６または７記載の
ＮＯx浄化用触媒の製造方法。9. The method of claim 6 or 7 NO x production method of purifying catalyst, wherein the water soluble precursor of the ion conductive material is a nitrate compound.
Ｏx浄化用触媒の製造方法であって、表面の一部にイオ
ン伝導性物質を配置した電子伝導性物質粒子を、触媒活
性を有する金属の前駆体溶液に浸漬し、前記イオン伝導
性物質および電子伝導性物質粒子の表面を、前記触媒活
性を有する金属の前駆体で被覆したのち、焼成を行なう
ことにより、イオン伝導性物質および電子伝導性物質粒
子の表面に触媒活性を有する微細金属粒子を配置するこ
とを特徴とするＮＯx浄化用触媒の製造方法。10. The N according to claim 1, wherein
A method for producing an O x purification catalyst, comprising immersing an electron conductive material particle having an ion conductive material disposed on a part of its surface in a precursor solution of a metal having catalytic activity, After coating the surface of the electron conductive material particles with the precursor of the metal having the catalytic activity, by firing, the fine metal particles having the catalytic activity are formed on the surfaces of the ion conductive material and the electron conductive material particles. manufacturing method of the NO x purifying catalyst, characterized by disposing.
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|---|---|---|---|
| JP2001010206A JP2002210365A (en) | 2001-01-18 | 2001-01-18 | CATALYST FOR CLEANING NOx AND ITS PRODUCTION METHOD |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001010206A JP2002210365A (en) | 2001-01-18 | 2001-01-18 | CATALYST FOR CLEANING NOx AND ITS PRODUCTION METHOD |
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|---|---|
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|---|---|---|---|
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