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Palladium catalysts are known to show higher methane oxidation performance than platinum and/or rhodium catalysts. In this paper, the higher oxidative dehydrogenation activity on palladium is proposed as a reason for the superior methane oxidation. When other oxidation reactions are considered, higher affinity of palladium to oxygen has also been suggested[1]. In this study, oxygen chemical potential on platinum and palladium catalyst surfaces under oxidation conditions was measured using a specially designed electrochemical sensor. The oxygen chemical potential was calculated from the sensor potential by the Nernst equation. As a result, oxygen potential on palladium during the methane oxidation reaction was found to be much higher than that of platinum, correlating with affinity to oxygen and higher methane oxidation performance. The rate of oxygen adsorption and desorption on platinum and palladium was evaluated in an engine experiment using a dual lambda-sensor procedure.

To predict how DOC performance deteriorates with a lifetime of use, it is important to understand the mechanisms of catalyst aging. In off-road applications, due to the continuous high load usage and relatively high oil consumption rate, poisoning of the Diesel Oxidation Catalyst (DOC) with Phosphorus may become an important durability issue. In this study, 3D modeling has been performed to study the P poisoning mechanism and 1D modeling has been performed to investigate P poisoning parameters that effect DOC performance deterioration. From postmortem analysis on engine aged DOCs there is a general trend that P deposits tend to collect at the outermost catalyst surface. Two types of 3D modeling were performed in this study to understand how P migrates into the bulk of the catalyst. In one case, P migrates into catalyst layer by gas phase diffusion and in the other case P first adsorbs on the catalyst surface and then migrates by solid diffusion into the bulk.

Pre-filter diesel oxidation catalyst (DOC) development for a DOC-CSF system has been conducted. The pre-filter DOC is required to efficiently oxidize fuel and generate heat to regenerate accumulated soot within the catalyzed soot filter (CSF). Therefore, high thermal durability is required. In addition, good transient hydrocarbon (HC) activity is required for the DOC to reduce tailpipe HC emissions. The required performance is dependent on the OEM's system control strategy. A DOC catalyst designed to have well dispersed Pt showed high fuel combustion performance. Such high Pt dispersion was obtained by using high specific surface area Al2O3. Zeolite included into the catalyst formulation showed higher transient HC performance compared to a catalyst without zeolite. The effective catalyst layer depth with respect to transient HC activity was studied by computer simulation.

The transient HC performance of diesel oxidation catalysts is known to be greatly improved by addition of Zeolite material. The authors already reported how to estimate the effective washcoat thickness in our previous study [1]. To understand in more detail the effective catalyst layer thickness, a precise gas diffusion model and parameters of HC adsorption and desorption rate were determined in this study. The random pore model was used for a gas diffusion calculation to simulate the macro porosity of the catalyst layer and micro porosity of the Zeolite material. HC adsorption capacity as a function of temperature and HC concentration was measured by Temperature Programmed Desorption (TPD). HC desorption rate was evaluated by changing the TPD ramping rate. HC reaction rate was evaluated by using a model gas reactor. Calculated catalyst performance correlated to the experimental results, thus validating the model.

Palladium is well known to catalyze methane (CH4) oxidation more efficiently than platinum (Pt) and/or rhodium (Rh) catalysts. The mechanism for methane oxidation on palladium is hypothesized to proceed via a radical intermediate. Direct identification of a radical species was not detected by Electron Spin Resonance Spectroscopy (ESR). However, indirect evidence for a radical intermediate was found by identification of ethane (C2H6), the methyl radical(CH3 ˙ ) coupling product, by Mass spectroscopy analysis under CH4/O2 conditions.