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The development of an alternative oxygen reduction electrocatalyst to platinum based electrocatalysts is critical for practical use of the polymer electrolyte membrane fuel cell (PEMFC). Transition metal sulfide chalcogenides have recently been reported as a possible candidate for Pt replacement. Our work focused on chalcogenides composed of ruthenium, molybdenum, and sulfur (RuMoS). We elucidate the factors affecting electrocatalytic activity of carbon supported RuXMoY SZ catalyst. This was demonstrated through a correlation of oxygen reduction reaction (ORR) activity of the catalysts with structural changes resulting from designed changes in sulfur composition in the catalysts.

To meet future stringent emission regulations such as Euro6, the design and control of diesel exhaust after-treatment systems will become more complex in order to ensure their optimum operation over time. Moreover, because of the strong pressure for CO₂ emissions reduction, the average exhaust temperature is expected to decrease, posing significant challenges on exhaust after-treatment. Diesel Oxidation Catalysts (DOCs) are already widely used to reduce CO and hydrocarbons (HC) from diesel engine emissions. In addition, DOC is also used to control the NO₂/NOx ratio and to generate the exothermic reactions necessary for the thermal regeneration of Diesel Particulate Filter (DPF) and NOx Storage and Reduction catalysts (NSR). The expected temperature decrease of diesel exhaust will adversely affect the CO and unburned hydrocarbons (UHC) conversion efficiency of the catalysts. Therefore, the development cost for the design and control of new DOCs is increasing.

This paper considers an application of reference governor (RG) to automotive diesel aftertreatment temperature control. Recently, regulations on vehicle emissions have become more stringent, and engine hardware and software are expected to be more complicated. It is getting more difficult to guarantee constraints in control systems as well as good control performance. Among model-based control methods that can directly treat constraints, this paper focuses on the RG, which has recently attracted a lot of attention as one method of model prediction-based control. In the RG, references in tracking control are modified based on future prediction so that the predicted outputs in a closed-loop system satisfy the constraints. This paper proposes an online RG algorithm, taking account of the real-time implementation on engine embedded controllers.

The details of Di-Air, a new NOx reduction system using continuous short pulse injections of hydrocarbons (HC) in front of a NOx storage and reduction (NSR) catalyst, have already been reported. This paper describes further studies into the deNOx mechanism, mainly from the standpoint of the contribution of HC and intermediates. In the process of a preliminary survey regarding HC oxidation behavior at the moment of injection, it was found that HC have unique advantages as a reductant. The addition of HC lead to the reduction or metallization of platinum group metals (PGM) while keeping the overall gas atmosphere in a lean state due to adsorbed HC. This causes local O₂ inhibition and generates reductive intermediate species such as R-NCO. Therefore, the specific benefits of HC were analyzed from the viewpoints of 1) the impact on the PGM state, 2) the characterization of intermediate species, and 3) Di-Air performance compared to other reductants.

The Diesel Particulate and NOx Reduction System (DPNR) is an effective technology as a diesel after-treatment system, which can reduce particulate matter (PM) and nitrogen oxides (NOx) simultaneously. However, it requires desulfurization control since the DPNR catalyst is poisoned by sulfur components in the exhaust gas from the fuel and lubricant. Desulfurization control causes some degree of fuel penalty and thermal deterioration of the DPNR catalyst because it requires control of rich air fuel ratio and high temperature simultaneously. In this paper, we investigated a new system with a sulfur trap catalyst which can trap sulfur components included in the exhaust gas as sulfates (Sulfur trap DPNR). In this system, desulfurization control is not performed because the sulfur poisoning of the DPNR catalyst is drastically suppressed by the sulfur trap catalyst. In the present DPNR, periodic desulfurization control is required.

A new HC adsorber system was developed to achieve California SULEV emission standards for a V8 5.0-liter engine application (i.e. LS600hL). A HC adsorber system was first released on 2001 PZEV Prius (1.5-liter engine) in U.S.A. For the 5.0L application the substrate volume of both catalyst and adsorber had to be enlarged for a large volume displacement. Prius-type adsorber system could not be adopted for LS600hL because of the problems of installation. So, a new constructional adsorber was proposed. However the increase of gas flow into the adsorber substrate was a problem for desorption. The gas flow into the adsorber substrate was found to be controllable by the specification adjustment of the “throat” and “retainer” parts of adsorber system. Thus the rapid desorption was successfully reduced, and the HC adsorber system achieved a 50% reduction of HC emission.

In order to enhance the catalytic performance of the NOx Storage-Reduction Catalyst (NSR Catalyst), the sulfur tolerance of the NSR catalyst was improved by developing new support and NOx storage materials. The support material was developed by nano-particle mixing of ZrO2-TiO2 and Al2O3 in order to increase the Al2O3-TiO2 interface and to prevent the ZrO2-TiO2 phase from sintering. A Ba-Ti oxide composite material was also developed as a new NOx storage material containing highly dispersed Ba. It was confirmed that the sulfur tolerance and activity of the developed NSR catalyst are superior to that of the conventional one.

Transmission electron microscope (TEM) is a powerful tool for studying catalyst materials at nano-size and/or atomic level. Conventional TEM usually needs to be observed at room temperature in high vacuum conditions. A gaseous atmosphere and high temperature condition may change the properties of catalyst materials. Recently we developed an in situ observation system in TEM for observing the oxidation and reduction under a gas atmosphere at high temperature. Using the new in situ observation system in TEM, the morphological changes of the nano particle and support were observed in the heated gaseous atmosphere at atomic level in real time.

Due to regulations for even lower levels of pollutants in exhaust gas, development of advanced combustion techniques and increasingly efficient catalysts has become more crucial than ever. One of the essential technologies to achieve this goal is an advanced measurement method, which can detect the characteristics of exhaust gas, such as temperature and chemical compositions, in real-time to clarify their reaction mechanisms. A direct and fast response (1ms) measurement technique was developed based on diode laser absorption spectroscopy and applied to practical engine exhaust measurement to prove the validity of this technology for various applications such as clarification of engine start phenomena and improvement of EGR controls.

Stringent emission regulations call for advanced catalyst substrates with thinner walls and higher cell density. However, substrates with higher cell density increase backpressure, thinner cell wall substrates have lower mechanical characteristics. Therefore we will focus on cell configurations that will show a positive effect on backpressure and emission performance. We found that hexagonal cells have a greater effect on emission and backpressure performance versus square or round cell configurations. This paper will describe in detail the advantage of hexagonal cell configuration versus round or square configurations with respect to the following features: 1 High Oxygen Storage Capacity (OSC) performance due to uniformity of the catalyst coating layer 2 Low backpressure due to the large hydraulic diameter of the catalyst cell 3 Quick light off characteristics due to efficient heat transfer and low thermal mass

Three-way catalyst shows high performance under stoichiometric atmosphere. The CeO2-ZrO2 based materials (CZ) are added as a buffer of O2 concentration. To improve the catalyst performance the larger O2 storage capacity (OSC) are needed. Theoretically, the sulfur oxidation-reduction reaction moves oxygen 8 times larger than cerium. We focused on this phenomenon and synthesized Ln2O2SO4 as a new OSC material. The experimental result under model gas shows that the OSC of Ln2O2SO4 is 5 times lager than CZ.

It is critical to develop high performance three-way catalysts to meet increasing regulations around the world. It was found that a double-layered catalyst loaded with Pt and Rh suppresses Pt-Rh alloying, thereby improving catalytic performance. A double-layered catalyst has the effect of decreasing OSC performance, but this has been overcome by a newly developed Rh support and suppressed Pt grain growth. The developed catalyst is capable of lowering the amount of PGM required by approximately 40%.

One primary result of the reduction of platinum group metals (PGM) within a catalytic converter is the decline in NOx conversion efficiency. This paper hypothesizes that the primary factor of this decline to be hydrocarbon (HC) poisoning. To maintain high NOx conversion efficiency as the PGM reduces, Rh activation improvement becomes significant to overcome the HC poisoning. Analysis of the Rh deterioration mechanism found that it is effective to separately arrange Rh and CeO2 on the converter, avoiding the Rh deactivation. By this improvement, we improved the catalyst activity at less than 25% of the original Rh loading.

Diesel particulate and NOx reduction system (DPNR) is an effective technology for the diesel after-treatment system, which can reduce particulate matter (PM) and nitrogen oxides (NOx) simultaneously. Further improvement of the DPNR is expected for cleaner air in the future. The catalyst for the DPNR (called DPNR catalyst) consists of a NOx Storage Reduction (NSR) catalyst coated onto a Diesel Particulate Filter (DPF). The development of the DPNR catalyst for the decrease of exhaust weight has been considered before now with respect to the PM combustion. But it will be necessary to focus on PM particle number emissions in the future. In this study, the relationship between the pore structure of the DPNR catalyst and the trapping of PM to lower particle number was clarified by evaluating a high-porosity, large-pore cordierite DPF with an average pore size of 20 μm or greater. Furthermore, the optimal pore structure to trap PM particles in a highly effective manner was discussed.

We, at Toyota, have been working to develop a new DPNR (Diesel Particulate-NOx Reduction) system to decrease both PM and NOx emissions by combining the NOx storage-reduction catalyst for direct injection gasoline engines with the most advanced engine control technologies. The purpose of the DPNR catalyst is to decrease PM and NOx in order to purify automotive exhaust gas. To reduce PM emissions, the PM trapping rate and PM oxidizing performance must be improved. Since the deposition of PM increases the pressure drop across the catalytic converter, it should also be suppressed. To attain these objectives, we have developed a new DPNR catalyst by the adoption of a new porous substrate structure and the improvement of the catalyst coating technique. The new DPNR catalyst will be mounted on the Avensis for commercial use in the European market.

Spark ignition direct injection (SIDI) engines have the potential to realize significant thermal efficiency improvements compared to conventional port fuel injection engines. The effects of fuel properties on efficiency and emissions have been investigated in a prototype of an Avensis Wagon equipped with a 2.0 liter, 4 cylinder spark ignition, direct injection (SIDI) engine designed to meet US 2000 emission standards. The vehicle employed a close coupled three-way catalyst and a NOx storage and reduction catalyst. Seven matrix fuels were blended to the same RON with varying levels of aromatics, olefins, ethanol, and volatility. Relative thermal efficiency, fuel economy, and tailpipe emissions were measured for the matrix fuels and a base fuel under the FTP LA4 driving cycle. The engine was operated in a lean burn mode in light load condition for approximately half of the driving cycle.

Our two types of NOx storage-reduction (NSR) catalyst have been tested under various conditions of thermal endurance; the performance of these catalysts have been regressed to give the formulas that enable to estimate the performance after thermal endurance; and we have found the method to simplify (shorten the duration of) the thermal endurance tests and that the thermal deterioration of NSR catalysts is controlled by the worst condition of endurance (at least approximately). The regression formula for the amount of potassium that contributes to the catalyst performance (active K) after the endurance has also been obtained. These formulas predict that the amount of active K is the least for the worst condition of endurance and suggest a difference in deterioration mechanism that reflects the performance between low and high temperatures and the portion of worse deterioration (front or rear).

By using analytical techniques (FT-IR, TG-MS, ICP) and DFT calculations, the potassium (K) used as a storage component in NOx Catalysts can be analyzed. The results from this study show that the, K exists as K2CO3, and that the amount, molecular structure, and thermal stability of K2CO3 are different, depending on the support material (ZrO2, Al2O3, or TiO2). If the amount of K that interacts with the support to form an inactive complex oxide is decreased, the amount of K2CO3 and NOx storage is increased. The amount of the inactive K varies with the basicity of the supports. K2CO3 that exists in unstable structures on the supports can be easy to react with NOx to form the nitrate. So, the higher the quantity of unstable K2CO3, the higher the NOx storage capacity. Based on these results, a development guideline was proposed to improve the NOx storage performance.

Through the basic research of the plasma assisted catalyst system using DeNOx catalysts and the gas analysis of the system, its conceptual use for automobile diesel engine applications has been studied. This study has shown that the length between the plasma reactor and the catalyst reactor does not affect the NOx conversion. To obtain an efficient NOx conversion, the plasma should affect both the HC as the reductant and NOx at the same time. In the case of γ-Al2O3 and C3H6, the main component for NOx reduction was CH3CHO generated by the plasma. Under 250 deg. C, the temperature was too low for the γ-Al2O3 to become effective. Therefore, the NOx conversion became low. At 400 deg. C, the NOx conversion became high. However, at 600 deg. C, the CH3CHO for reducing NOx was not generated, and the NOx conversion decreased.

A new after-treatment system called DPNR (Diesel Particulate-NOx Reduction System) has been developed for simultaneous and continuous reduction of particulate matter (PM) and nitrogen oxides (NOx) in diesel exhaust gas. This system consists of both a new catalytic technology and a new diesel combustion technology which enables rich operating conditions in diesel engines. The catalytic converter for the DPNR has a newly developed porous ceramic structure coated with a NOx storage reduction catalyst. A fresh DPNR catalyst reduced more than 80 % of both PM and NOx. This paper describes the concept and performance of the system in detail. Especially, the details of the PM oxidation mechanism in DPNR are described.