Mari Uenishi

Design of the intelligent catalyst for Japan ULEV standard

We have reported the innovation of “An intelligent catalyst” which has the function for self-regeneration of Pd realized through the solid solution and segregation of Pd in a perovskite crystal. In this paper, the issues and the solutions for a practical perovskite catalyst for the Japan ULEV standards are discussed.

Regeneration of Palladium Subsequent to Solid Solution and Segregation in a Perovskite Catalyst: An Intelligent Catalyst

The object of this study was to provide a function for self-regeneration of precious metals in a usage ambience without auxiliary treatment. The strategy was to control the catalytic active site of those crystalline ceramics known as perovskite-type oxides at the atomic level in order to create the new, needed function. Three series of Pd-containing perovskite catalyst systems were prepared by coprecipitation of Pd with La, Fe, and Co using the alkoxide method. It was confirmed that Pd formed a solid solution of the perovskite-type oxide. And Pd in the perovskite crystal structure exhibited an abnormal oxidation number or higher binding energy than the normal bivalence, and it was presumed to be the reason for increasing the catalytic activity. The results of dissolution analysis for the aged Pd-perovskite catalyst suggested that Pd was not only dispersed on the surface of the perovskite crystal, but was present also in the solid solution of the perovskite crystal. The formation of a solid solution in this Pd-perovskite crystal was affected by the B site elements. And Pd in LaFe0.54Co0.36Pd0.10O3 system was more durable than in LaCo0.90Pd0.10O3 or in LaFe0.90Pd0.10O3. Furthermore, the formation of Pd solid solution into these perovskite crystals also depended on atmospheres and temperatures. It appeared that a high state of dispersion was maintained as Pd repeatedly forms solid solutions in the perovskite crystal or segregates out from the crystal depending on the fluctuation of redox conditions and temperatures in automotive catalyst ambience. We named such a catalyst, wherein a precious metal regenerates itself while in operation and remains highly active without requiring any auxiliary treatment, “an intelligent catalyst”.

NO dissociation on Cu(111) and Cu2O(111) surfaces: a density functional theory based study

NO dissociation on Cu(111) and Cu(2)O(111) surfaces is investigated using spin-polarized density functional theory. This is to verify the possibility of using Cu-based catalyst for NO dissociation which is the rate limiting step for the NO(x) reduction process. The dissociation of molecularly adsorbed NO on the surface is activated for both cases. However, from the reaction path of the NO-Cu(2)O(111) system, the calculated transition state lies below the reference energy which indicates the possibility of dissociation. For the NO-Cu(111) system, the reaction path shows that NO desorption is more likely to occur. The geometric and electronic structure of the Cu(2)O(111) surface indicates that the surface Cu atoms stabilize themselves with reference to the O atom in the subsurface. The interaction results in modification of the electronic structure of the surface Cu atoms of Cu(2)O(111) which greatly affects the adsorption and dissociation of NO. This phenomenon further explains the obtained differences in the dissociation pathways of NO on the surfaces.

Dynamic structural change in Pd-perovskite automotive catalyst studied by time-resolved dispersive x-ray absorption fine structure

Dynamic structural change in Pd-perovskite automotive catalyst, LaFe0.9Pd0.1O3, which has a high catalytic activity during aging, was studied by in situ time-resolved dispersive x-ray absorption fine structure spectroscopy at 200–500 °C. An Al2O3-based conventional catalyst was also studied. In a reductive atmosphere, both catalysts showed similar temperature dependences of structural transformation from an oxide to a metal. However, different temperature dependence was observed in an oxidative atmosphere. A faster response in the structural change was observed in the Pd-perovskite catalyst than in the Pd/Al2O3 catalyst. It was revealed that Pd-perovskite shows a considerably fast structural change to the oxidized state via the movement of Pd atoms into the perovskite crystal, in comparison with Pd/Al2O3 showing two-step structural change for making PdO.

Dynamic structural change of Pd particles on LaFeO3 under redox atmosphere and CO/NO catalytic reaction studied by dispersive XAFS

The local structure of Pd metal fine particles on LaFeO3 which has a high catalytic activity was observed by dispersive XAFS optics from the viewpoint of dynamical structure change of Pd during oxide-metal change and CO/NO catalytic reaction. The oxide-metal change of Pd nanoparticles on LaFeO3 and Al2O3 was investigated by 20–50 Hz rate. It was recognized that, under the reductive atmosphere, Pd atoms show similar speed of movement from oxide to metal state both on the two supports. However, under the oxidative atmosphere, Pd atoms on LaFeO3 show faster movement from metal to oxide state than those on Al2O3. CO/NO catalytic reaction on Pd metal nanoparticles was also observed by 0.2 Hz rate. Slow observation mode made the four EXAFS parameters: coordination number, interatomic distance, Debye-Waller factor and edge shift, precisely determined during catalytic reaction. There are two particular differences between Pd particles on LaFeO3 and Al2O3. Large enhancement of interatomic distance of Pd particle was only observed on Al2O3. Stable surface oxide layer of Pd particle is created on LaFeO3.

A theoretical study of the reactivity of Cu2O(111) surfaces: the case of NO dissociation

We compare the electronic properties of Cu(111) and Cu(2)O(111) surfaces in relation to the dissociation of NO using first principles calculations within density functional theory. We note a well-defined three-fold site on both O- and Cu-terminated Cu(2)O surfaces which is verified as the active site for the adsorption and dissociation of NO. The interaction of Cu with O atoms results in the forward shifting of the local density of states and formation of unoccupied states above the Fermi level, compared to the fully occupied d band of pure Cu. These results give valuable insights in the realization of a catalyst without precious metal for the dissociation of NO.

The Self-Regenerative "Intelligent" Catalyst for Automotive Emissions Control

Co-free LaFePdO3 perovskite catalyst with the self-regenerative function of Pd was developed. This technology was named the “intelligent catalyst”. Suppression capacity for Pd particle growth and catalytic activity of the Co-free perovskite LaFePdO3 were compared with those of LaFeCoPdO3. It was confirmed that Pd particles on LaFePdO3 maintained a nano-particle size by the results of XAFS analysis and TEM observation after aging in engine exhaust gas at 900 °C, and LaFePdO3 demonstrated an excellent light-off performance. Further, the design configuration for LaFePdO3 in the washcoat was investigated to maximize the self-regenerative function under practical conditions.

The Intelligent Catalyst: Pd-Perovskite Having the Self-Regenerative Function in a Wide Temperature Range

An innovative Pd-perovskite “Intelligent Catalyst”, which exhibits a greatly improved durability owing to the self-regeneration function of Pd nanoparticles, has been developed. The Pd-perovskite catalyst was prepared by the alkoxide method, and X-ray absorption fine structure (XAFS) measurements were carried out in SPring-8 using the 8-GeV synchrotron radiation. Pd occupied the B-site (6-fold coordination) of the perovskite lattice in the oxidative atmosphere, and segregated out to form metallic nanoparticles in the reductive atmosphere. The catalyst retained a predominantly perovskite structure throughout a redox cycle of the exhaust-gas, while the local structure around Pd could be changed in a completely reversible manner. The agglomeration and growth of the metal particles is suppressed as a result of the Pd movement between inside and outside the perovskite lattice. This function enables an automotive catalyst to regenerate itself into an active state in fluctuation typically encountered in the exhaust gas from the gasoline engine. And it is revealed, by in-situ and ex-situ XAFS analyses, that the self-regenerative function of Pd occurred in a wide temperature range from very low to high one. The intelligent catalyst is one solution for precious metals supply and demand problem, and is expected to become the global standard of the catalyst technology.

Intelligent catalysts with self-regenerative function

An “intelligent catalyst” that has the self-regenerative function of Pd (Palladium) achieved through solid solution and segregation of Pd in a perovskite crystal was first commercialised in 2002. Daihatsu has made attempts to apply this intelligent technology to other precious metals, such as Rh (Rhodium) and Pt (Platinum), and advanced intelligent catalysts with a self-regenerative function of Rh and Pt have been developed successfully.