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CN1206036C - 陶瓷体和陶瓷催化剂体 - Google Patents

陶瓷体和陶瓷催化剂体 Download PDF

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Publication number
CN1206036C
CN1206036C CNB031371701A CN03137170A CN1206036C CN 1206036 C CN1206036 C CN 1206036C CN B031371701 A CNB031371701 A CN B031371701A CN 03137170 A CN03137170 A CN 03137170A CN 1206036 C CN1206036 C CN 1206036C
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China
Prior art keywords
composition
ceramic
ceramic body
catalyst
catalyst component
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Expired - Fee Related
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CNB031371701A
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English (en)
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CN1468658A (zh
Inventor
长谷川顺
长谷智实
小池和彦
伊藤三甫
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Denso Corp
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Denso Corp
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    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
    • C04B35/195—Alkaline earth aluminosilicates, e.g. cordierite or anorthite
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
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    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
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Abstract

本发明的目的是提供可以负载需要量的催化剂成分的陶瓷体，而并不降低诸如强度之类的特征，并且在制备过程中没有形成涂层，从而提供了实用性和耐用性良好的高性能陶瓷催化剂。根据本发明，将贵金属催化剂直接负载到陶瓷体的表面上，并且将第二种成分(它由电子轨道内具有d或f轨道的元素，诸如W、Co、Ti、Fe、Ga和Nb的化合物和复合化合物组成)分散在由堇青石等(陶瓷基质)构成的第一种成分内。通过共享第二种成分的d或f轨道而产生的键合强度，或者通过与在第一种成分和第二种成分之间的界面内产生的悬空键之间的相互作用，可以直接负载贵金属催化剂。

Description

陶瓷体和陶瓷催化剂体
                    技术领域
本发明涉及用作汽车发动机等的废气净化催化剂的催化剂载体的陶瓷体以及陶瓷催化剂体。
                  相关领域描述
堇青石因其较高的耐热冲击性而被广泛用作催化剂载体的陶瓷体。通过将γ-氧化铝涂层涂覆到蜂窝状的堇青石的表面上、然后在其上负载贵金属催化剂来制备催化剂。因为堇青石的比表面积太小而不能负载需要量的催化剂成分，所以需要形成涂层。因此，通过使用比表面积大的γ-氧化铝可以增加载体的表面积。
但是，当载体表面涂有γ-氧化铝时，载体的热容量因质量的增加而增加。最近，为了达到催化剂的预先活化，研究人员已经尝试了通过使蜂窝状载体的胞壁变薄来减小热容量的方法。但是，这种尝试的效果因涂层的形成而减小。还存在诸如载体的热膨胀系数因存在涂层而变大以及晶胞的开孔面积的减小增加了压力损失之类的问题。
研究人员已进行了各种研究以得到能负载催化剂成分的陶瓷体并避免形成涂层。例如，日本审查专利公开(Kokoku)号5-50338提出了通过在酸浸过程之后进行热处理来提高堇青石自身的比表面积的方法。但是，该方法不实用，因为酸浸过程和热处理破坏了堇青石的晶格，并因此导致其机械强度的降低。
因此，本发明的目的是解决上述的现有技术的问题并提供能负载需要量的催化剂成分并避免形成涂层，同时也不降低诸如机械强度之类的特征，从而提供实用性和耐用性良好的高性能的陶瓷催化剂。
                     发明概述
本发明的第一方面是能在表面上直接负载催化剂成分的陶瓷体，该陶瓷体含有构成陶瓷基质的第一种成分和不同于第一种成分的第二种成分，其中第二种成分至少分散在陶瓷基质的表面部分内。
在本发明的陶瓷体上能直接负载催化剂成分，将不同于第一种成分的第二种成分至少分散在陶瓷基质的表面部分内。因此，不会出现因晶格损坏而引起的机械强度降低的问题，不同于现有技术的通过酸浸过程等洗脱构成成分来增加陶瓷基质的比表面积的方法。结果，陶瓷体可以直接负载催化剂成分，同时保持了足够的强度并具有良好的实用性和耐用性而且不形成涂层。
具体地讲，将催化剂成分负载到第二种成分上或者负载到第一种成分和第二种成分之间的界面内。例如，当将化合物(其包括与催化剂成分的键合强度大于第一种成分的元素)作为第二种成分引入时，催化剂受到强的吸附力的作用而被直接负载。第一种成分和第二种成分之间的界面包括可能产生诸如扭结或平台之类的缺陷的晶格错配。该部分包括易于与催化剂成分成键的悬空键。结果，由于催化剂的负载性能提高并且与催化金属粒子负载到孔内的常规载体的情况相比，催化剂成分能更均匀地分散到载体内，所以在较长的使用期间内催化剂成分很少可能聚集、老化。
对于构成陶瓷基质的第一种成分，可以使用陶瓷材料诸如堇青石、Al2O3、SiC、TiO2、MgO、Si3N4、ZrO2、CeO2或SiO2。根据操作环境所需的陶瓷基质的应用和特征，可以使用选自上述的陶瓷材料中的一种或数种物质。
总体上确定陶瓷体中第二种成分的含量，使得构成第二种成分的金属元素的原子总数是构成第一种成分和第二种成分的金属元素的原子总数的0.1至70原子％。分散在陶瓷体内的第二种成分的量在总体上位于上述范围内，并保持陶瓷基质的特征的同时可以负载需要量的催化剂成分。
优选确定表面部分中第二种成分的含量，使得构成第二种成分的金属元素的原子总数是构成第一种成分和第二种成分的金属元素的原子总数的0.1至100原子％。在表面部分内第二种成分的含量升高时，可以在保持陶瓷基质的特征的同时负载更大量的催化剂成分。
此外，第二种成分优选是含有一种或多种在其电子轨道内具有d或f轨道元素的化合物，或者是第一种成分包括的金属元素与一种或多种在其电子轨道内具有d或f轨道的元素的复合化合物。由于含有d或f轨道的元素的能级接近于催化剂成分，所以它们易于给出电子使得成键。第二种成分还可以是具有d或f轨道的元素与第一种成分包括的金属元素形成的化合物。
此外，第二种成分还可以是一种或多种选自W、Co、Ti、Fe、Ga和Nb的元素的化合物，或者是第一种成分包括的金属元素和一种或多种选自W、Co、Ti、Fe、Ga和Nb的元素的复合化合物。
上面提到的化合物或复合化合物优选是一种或多种选自下列的物质：WO3、MgWO4、CoWO4、Mg2TiO5、MgTiO3、Mg2TiO4、MgSiO3、MgWO4、MgAl2O3、TiO2、FeWO4、MgFe2O4、FeAlO3、Fe2SiO4、MgAl2O4、Al2TiO5、GaAlO3、Nb2WO3和AlNbO4。
第二种成分的平均粒径优选为50μm或更小。将小粒径的第二种成分浓密地分散于陶瓷体的表面部分可以增加其中负载的催化剂成分的量。
陶瓷体的形状可以选自各中形状诸如蜂窝体、泡沫块、中空纤维、纤维、粉末或颗粒。在任何这样的形状上，可以通过加入第二种成分来直接负载催化剂成分。
本发明的第二方面是通过将催化剂成分直接负载到上述的陶瓷体上来制备的陶瓷催化剂。由于陶瓷催化剂将催化剂成分直接负载于其上并不需要涂层，所以不会出现因涂层引起的热容量和热膨胀系数的增加。催化剂还可以是预先活化的并且耐用性高。
此外，在本发明的陶瓷催化剂中，将催化剂成分负载到第二种成分上或者负载到第一种成分和第二种成分之间的界面内。例如，当第二种成分包括电子轨道内具有d或f轨道的元素时，更易于与催化剂成分成键。第一种成分和第二种成分之间的界面有可能包括其中形成的悬空键，这也使得它易于与催化剂成分成键。
此外，本发明的陶瓷催化剂使用包括作为催化剂成分的贵金属的催化剂。具体地讲，根据目的不同可以使用一种或多种选自Pt、Rh、Pd、Ru、Au、Ag、Ir和In的元素。
在本发明的陶瓷催化剂中，催化剂成分的平均粒径优选为100nm或更小。粒径越小，催化剂成分的分布就越紧密，从而使催化剂性能得到提高。
                      附图简述
图1(a)至1(c)表示本发明的陶瓷催化剂体的微观结构。
图2表示研究第二种成分的含量变化对第一种成分的微观结构的影响的结果。
                 优选实施方案的描述
下面将详细地描述本发明。本发明的陶瓷体含有构成陶瓷基质的第一种成分和不同于第一种成分的第二种成分，其中第二种成分至少分散在陶瓷基质的表面部分内，从而在其表面上可以直接负载催化剂成分。催化剂成分可以通过与分散在陶瓷基质内的第二种成分成键的形式进行负载，或者通过与存在于第一种成分和第二种成分之间的界面内的悬空键之间的相互作用来进行负载。对于陶瓷体的形状没有限制，可以选自诸如蜂窝体、泡沫块、中空纤维、纤维、粉末或颗粒之类的各种形状。本发明的陶瓷体被用作催化剂载体，并且通过将催化剂成分直接负载到陶瓷体上所制备的陶瓷催化剂体可用作例如发动机等的废气净化催化剂。
构成陶瓷基质的第一种成分可以是理论组成为2MgO2·2Al2O3·5SiO2的堇青石或陶瓷材料诸如Al2O3、SiC、TiO2、MgO、Si3N4、ZrO2、CeO2或SiO2。根据陶瓷基质的应用和所需要的特征，可以使用选自上面提到的陶瓷材料中的一种或多种物质。例如使用堇青石作为第一种成分的陶瓷基质，具有较高的耐热冲击性，并因此适于用作需要耐高温的废气净化催化剂的载体。
对于第二种成分，优选其所含有的元素与陶瓷基质的第一种成分中的金属元素(在堇青石的情况下为Si、Al和/或Mg)相比，能够与所负载的催化剂成分之间形成更强的键合力。这样的元素的例子是在其电子轨道内具有d或f轨道的元素，优选使用在d或f轨道内具有空轨道的元素。在d或f轨道内具有空轨道的元素的能级接近于被负载的催化剂成分诸如贵金属的并且易于给出电子。具有两个或多个氧化态的元素也易于给出电子，从而易与催化剂成分成键。
在其d或f轨道内具有空轨道的元素包括诸如Sc、Ti、V、Cr、Mn、Fe、Co、Ni、Y、Zr、Nb、Mo、Tc、Ru、Rh、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Lu、Hf、Ta、W、Re、Os、Ir和Pt之类的元素。在这些元素中，Ti、V、Cr、Mn、Fe、Co、Ni、Nb、Mo、Tc、Ru、Rh、Ce、Pr、Eu、Tb、Ta、W、Re、Os、Ir和Pt具有两个或多个氧化态。优选使用选自Ti、V、Cr、Mn、Fe、Co、Ni、Zr、Mo、Ru、Rh、Ce、W、Ir和Pt中的一种或多种元素，更优选使用选自W、Co、Ti、Fe、Ga和Nb中的一种或多种元素。
第二种成分由在d或f轨道内具有空轨道的元素的化合物、通常是由氧化物构成。第二种成分还可以由复合化合物诸如包括许多具有空的d或f轨道的元素的复合氧化物。将一种或多种所述的化合物或复合化合物分散在陶瓷基质内。此外，第二种成分还可以是上述的在d或f轨道内具有空轨道的元素和第一种成分所包括的金属元素的复合氧化物。例如，当将第一种成分的原材料(该材料包含在d或f轨道内具有空轨道的元素)在空气中煅烧时，在该过程中可以形成构成第一种成分的元素和在d或f轨道内具有空轨道的元素的固体溶液。由于该固体溶液还包括在d或f轨道内具有空轨道的元素，所以提供了上面描述的与催化剂的高键合强度。
如上所述，第二种成分由包括至少一种在d或f轨道内具有空轨道的元素的化合物或复合化合物组成，或者由至少一种在d或f轨道内具有空轨道的元素和至少一种第一种成分所包括的金属元素的复合化合物构成。不需要说明第二种成分还包括两种或多种化合物或复合化合物作为其构成成分。例如，如果第一种成分是包含Si、Al和/或Mg的堇青石并且包括在第二种成分内的在d或f轨道内具有空轨道的元素是一种或多种选自W、Co、Ti、Fe、Ga和Nb的元素，则构成第二种成分的化合物或复合化合物可以更具体地是WO3、MgWO4、CoWO4、Mg2TiO5、MgTiO3、Mg2TiO4、MgSiO3、MgWO4、MgAl2O3、TiO2、FeWO4、MgFe2O4、FeAlO3、Fe2SiO4、MgAl2O4、Al2TiO5、GaAlO3、Nb2WO3和AlNbO4，并且可以使用选自这些化合物和复合化合物中的一种或多种物质。
总体上确定陶瓷体中第二种成分的含量，使得构成第二种成分的金属元素的原子总数是构成第一种成分和第二种成分的金属元素的原子总数的0.1至70原子％，优选10至70原子％。当构成第二种成分的金属元素的原子总数小于0.1原子％时，将使催化剂成分进行负载的活性位的数目不足。当构成第二种成分的金属元素的原子总数大于70原子％时，将失去所需要的陶瓷基质(第一种成分)的特征，这是不希望的。因此，将第二种成分的含量进行确定，以便负载需要量的催化剂，而并不降低机械特性诸如强度和热膨胀系数以及其它的特征诸如耐热性和耐候性。
以上的讨论并不适用于负载催化剂成分的表面部分，并且在该部分可以增加第二种成分的含量。具体地讲，确定含量使得构成第二种成分的金属元素的原子总数是构成第一种成分和第二种成分的金属元素的原子总数的0.1至100原子％，优选10至100原子％。由于通过确定基质中第二种成分的含量为70原子％或更小可以保证所需要的载体特征，所以即便当表面部分中第二种成分的含量超过70原子％时也不会失去所需要的陶瓷基质(第一种成分)的特征，由此提供了因第二种成分的含量增加而可以负载的大量催化剂的优点。在第二种成分的含量为100原子％的情况下，第二种成分将以涂层的形式覆盖表面。表面部分是指距离陶瓷体的表面约数微米深的部分。
第二种成分的平均粒径优选为50μm或更小。使用平均粒径更小的第二种成分并且将其高度分散于陶瓷体内，这增加了可以负载催化剂成分的活性位数并且增加了可以负载的催化剂的量。
本发明的陶瓷体可以例如按照如下生产。当制备物质以制得构成陶瓷基质的第一种成分时，加入预定量的第二种成分的粉末或者能生成第二种成分的物质并且将其它物质混合、压模、干燥，然后脱脂并在空气中煅烧。该过程能够将第二种成分的粒子均匀地分散在第一种成分内。还可以将第二种成分的原材料以溶液态的形式进行混合。例如，如果第二种成分是WO3，则可以将硅钨酸的水溶液用作原材料。如果第二种成分是TiO2，可以使用过氧钛酸的水溶液、四氯化钛的水溶液等，以便达到更均匀的混合的目的。
对于利用按照上面的描述所形成的陶瓷体来负载的催化剂成分，例如，可以优选使用选自贵金属元素，诸如Pt、Rh、Pd、Ru、Au、Ag、Ir和In中的一种或多种元素。贵金属催化剂的平均粒径优选为100nm或更小。通过使得平均粒径为100nm或更小可以增加每单位重量内的催化剂的纯化粉末。需要时还可以加入各种助催化剂。助催化剂可以是诸如Hf、Ti、Cu、Ni、Fe、Co、W、Mn、Cr、V、Se、Rb、Sr、Y、Zr、Nb、Mo、Tc、Ru、Sc、Ba和K之类的金属元素或镧系元素(La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu)或其氧化物或复合氧化物。根据目的(诸如减轻老化、提供吸附氧的能力以及监测催化剂的老化)的不同可以使用这些元素中的一种或多种。
为了将催化剂成分负载到本发明的陶瓷体上，通常将陶瓷体浸入包括所需的催化剂成分的溶液中，然后干燥并煅烧。如果组合使用两种或多种催化剂成分，可以将陶瓷体浸入包括多种催化剂成分的溶液中。例如当将Pt和Rh用作主催化剂成分时，可以使用包括六氯铂酸和氯化铑的溶液。每单位体积负载的催化剂成分的量优选为0.05至10g/L的贵金属和1至250g/L的助催化剂。
通过上述方法可以得到催化剂成分负载到第二种成分上或第一种成分和第二种成分之间的界面内的陶瓷催化剂，如图1(a)至1(c)所示。图1(a)表示第一种成分的一种多晶结构，其中第二种成分分散在晶界内和晶粒内。图1(b)表示第一种成分基本上形成单晶结构，并且与第二种成分融为一体。图1(c)表示第一种成分基本上形成单晶和多晶结构，而第二种成分独立存在的烧结结构。在这些结构中的任何一个中，通过分散于陶瓷基质内的第二种成分所包括的元素的d或f轨道，和贵金属元素或其它的相互重叠的催化剂成分所包括的元素的d或f轨道，或者通过与第一种成分和第二种成分之间的界面内产生的高键合强度的悬空键之间的相互作用，可以直接负载贵金属元素或其它的催化剂成分，由此形成化学键或吸附。存在于第一种成分和第二种成分之间的界面内的晶格错配可以产生扭结或平台，由此易于产生悬空键。
因此，本发明的陶瓷催化剂可以直接负载催化剂成分，在第二种成分的表面上或者在第一种成分和第二种成分之间的界面内具有较高的键合强度。结果，陶瓷体和催化剂金属之间的成键变强，所以与用物理方法将催化剂负载到孔、微裂缝内的方法相比，本方法能够有效地抑制因热振动而出现的导致热老化的催化剂金属的迁移和聚集。本陶瓷催化剂优选用于汽车发动机等的废气净化催化剂，并且在降低热容量、热膨胀系数和压力损失方面有效，因为催化剂成分可以直接负载到表面上而没有形成诸如氧化铝等之类的涂层。
实施例
按照上述方法，通过使用堇青石作为构成陶瓷基质的第一种成分，然后分散作为第二种成分的氧化钨(WO3)和二氧化钛(TiO2)来生产本发明的陶瓷体。确定第二种成分的含量，按照构成堇青石的金属元素(Al、Mg、Si)和构成第二种成分的金属元素(W和Ti)的总含量计算，使得构成第二种成分的WO3中W的比率是10至30原子％且TiO2中Ti的比率为10至60原子％。首先，将平均粒径为1μm的WO3粉末和平均粒径为30nm的TiO2粉末以上述范围内的比率加入到由滑石、高岭土、氧化铝等组成的堇青石材料中。将混合物进行常规的湿混合过程并压模形成蜂窝状的预成型品。将该预成型品干燥、在900℃下在空气中脱脂，然后以5℃/小时至75℃/小时的速率将其加热并在1200至1350℃的温度下煅烧。
通过X-射线衍射分析来研究按照上面的描述得到的陶瓷体的构成。除了构成第一种成分的堇青石的衍射峰以外，还观察到WO3和TiO2的衍射峰。因此，可以证实得到了本发明的陶瓷体，其中作为第二种成分的WO3和TiO2分散于堇青石的第一种成分内。
图2表示研究第二种成分中的金属元素W和Ti的含量(原子％)对堇青石结构的影响的结果。从图可以看出，堇青石的衍射峰在W和Ti的总量不高于50原子％的区域是尖形的，并且在W和Ti的总量约为70原子％的区域则变宽，然而当含量超过70原子％时，堇青石呈现类似非晶形的形状。这意味着：当WO3和TiO2作为第二种成分分散在由堇青石构成的第一种成分内时，第二种成分包括的金属元素的总量优选为70原子％或更小，这样可以减小对于从第一种成分构成的陶瓷基质的特征的影响。
按照上面的描述，通过将陶瓷体浸入含有六氯铂酸的溶液，由此将Pt催化剂成分负载到分散有WO3和TiO2的陶瓷体上。干燥后，将陶瓷体在空气中煅烧，由此得到陶瓷催化剂。在沉积Pt之前和之后，用XPS测定W在陶瓷催化剂上的键能。测定结果表明W的衍射峰因Pt的负载而有变化，这说明了因负载的催化剂成分所引起的W的成键条件的变化。类似地，在沉积Pt之前和之后测定Ti的键能的结果表明键能因Pt的负载而有变化。相反地，没有观察到构成堇青石的Si、Al和Mg的键能的变化。
陶瓷催化剂的ICP分析表明有1.2g/L Pt负载到陶瓷催化剂上，然而仅有0.02g/L负载到仅有堇青石而没有第二种成分构成的陶瓷体上。因此，可以证实通过分散的第二种成分可以在很大程度上提高催化剂的负载能力。这意味着本发明的陶瓷催化剂因存在W和Ti而增强了贵金属催化剂和陶瓷体之间的键合强度。

Claims (15)

1、一种能在其表面上直接负载催化剂成分的陶瓷体，所述的陶瓷体含有构成陶瓷基质的第一种成分和不同于所述的第一种成分的第二种成分，其中所述的第二种成分至少分散在所述的陶瓷基质的表面部分内。
2、根据权利要求1所述的陶瓷体，其中所述的催化剂成分负载在所述的第二种成分上或者负载在所述的第一种成分和所述的第二种成分之间的界面内。
3、根据权利要求1或2所述的陶瓷体，其中所述的第一种成分含有至少一种选自堇青石、Al2O3、SiC、TiO2、MgO、Si3N4、ZrO2、CeO2和SiO2的物质。
4、根据权利要求1或2所述的陶瓷体，其中从整体上确定陶瓷体中所述的第二种成分的含量，使得构成所述的第二种成分的金属元素的原子总数是构成所述的第一种成分和所述的第二种成分的金属元素的原子总数的0.1至70原子％。
5、根据权利要求1或2所述的陶瓷体，确定所述的表面部分中所述的第二种成分的含量，使得构成所述的第二种成分的金属元素的原子总数是构成所述的第一种成分和所述的第二种成分的金属元素的原子总数的0.1至100原子％。
6、根据权利要求3所述的陶瓷体，其中所述的第二种成分是含有一种或多种在其电子轨道内具有d或f轨道的元素的化合物，或者是所述的第一种成分包括的金属元素与一种或多种在其电子轨道内具有d或f轨道的元素的复合化合物。
7、根据权利要求6所述的陶瓷体，其中所述的第二种成分是含有一种或多种选自W、Co、Ti、Fe、Ga和Nb的元素的化合物，或者是第一种成分包括的金属元素和一种或多种选自W、Co、Ti、Fe、Ga和Nb的元素的复合化合物。
8、根据权利要求7所述的陶瓷体，其中所述的化合物或复合化合物是一种或多种选自下列的物质：WO3、MgWO4、CoWO4、Mg2TiO5、MgTiO3、Mg2TiO4、MgSiO3、MgWO4、MgAl2O3、TiO2、FeWO4、MgFe2O4、FeAlO3、Fe2SiO4、MgAl2O4、Al2TiO5、GaAlO3、Nb2WO3和AlNbO4。
9、根据权利要求1或2所述的陶瓷体，其中所述的第二种成分的平均粒径为50μm或更小。
10、根据权利要求1或2所述的陶瓷体，其中陶瓷体的形状是选自蜂窝体、泡沫块、中空纤维、纤维、粉末及颗粒的各种形状。
11、通过将催化剂成分直接负载到权利要求1至10中任何一项所述的陶瓷体上所制备的陶瓷催化剂。
12、根据权利要求11所述的陶瓷催化剂，其中所述的催化剂成分负载在所述的第二种成分上或负载在所述的第一种成分和所述的第二种成分之间的界面内。
13、根据权利要求11或12所述的陶瓷催化剂，其中所述的催化剂成分包括贵金属元素。
14、根据权利要求11或12所述的陶瓷催化剂，其中所述的催化剂成分是一种或多种选自Pt、Rh、Pd、Ru、Au、Ag、Ir和In的元素。
15、根据权利要求11或12所述的陶瓷催化剂，其中所述的催化剂成分的平均粒径为100nm或更小。
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