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Journal Article

Study of Oxide Supports for PEFC Catalyst

Polymer electrolyte membrane fuel cell (PEFC) systems for fuel cell vehicles (FCVs) require both performance and durability. Carbon is the typical support material used for PEFC catalysts. However, hydrogen starvation at the anode causes high electrode potential states (e.g., 1.3 V with respect to the reversible hydrogen electrode) that result in severe carbon support corrosion. Serious damage to the carbon support due to hydrogen starvation can lead to irreversible performance loss in PEFC systems. To avoid such high electrode potentials, FCV PEFC systems often utilize cell voltage monitor systems (CVMs) that are expensive to use and install. Simplifying PEFC systems by removing these CVMs would help reduce costs, which is a vital part of popularizing FCVs. However, one precondition for removing CVMs is the adoption of a durable support material to replace carbon.
Technical Paper

Study of Large OSC Materials (Ln2O2SO4) on the Basis of Sulfur Redox Reaction

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.
Technical Paper

Study of Improvements in NOx Reduction Performance on Simultaneous Reduction System of PM and NOx

Performance improvements were studied for the diesel particulate and NOx reduction system (DPNR), a system that simultaneously reduces NOx and Particulate Matter (PM) from diesel engine exhaust gas. The experimental system (hereinafter called the “dual DPNR”) consists of two DPNR catalysts arranged in parallel, each provided with an exhaust throttle valve downstream to control the exhaust gas flow to the catalyst, plus a fuel injector that precisely controls the air-fuel ratio and the catalyst bed temperature. The fuel injector is used to supply a rich mixture to the DPNR catalyst, and the flow of exhaust gas is switched between the two catalysts by operating the exhaust throttle valves alternately. Tests were conducted with the engine running at steady state. The results indicated that the NOx reduction performance dramatically improved and the loss of fuel economy from the NOx reduction reduced.
Journal Article

Study of Alternative Oxygen Reduction Electrocatalyst for Pt Based on Transition Metal Chalcogenides

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.
Technical Paper

Simultaneous PM and NOx Reduction System for Diesel Engines

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.
Journal Article

Reaction Mechanism Analysis of Di-Air-Contributions of Hydrocarbons and Intermediates

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.
Technical Paper

Model-Based OBD Logic Utilizing Adsorption and Desorption Model of NH3 in SCR Catalyst

Urea selective catalytic reduction (SCR) systems are a promising technology for helping to lower NOx emissions from diesel engines. These systems also require on-board diagnostic (OBD) systems to detect malfunctioning catalysts. Conventional OBD methodology for a SCR catalyst involves the measurement of NOx concentration downstream of the catalyst. However, considering future OBD regulations, erroneous diagnostics may occur due to variations in the actual environment. Therefore, to enhance OBD accuracy, a new methodology was examined that utilizes NH3 slip as a new diagnostic parameter in addition to NOx. NH3 slip increases as the NOx reduction performance degrades, because both phenomena are based on deterioration in the capability of the SCR catalyst to adsorb NH3. Furthermore, NH3 can be measured by existing NOx sensors because NH3 is oxidized to NO internally. To make use of NH3 slip, an estimation model was developed.
Technical Paper

Influence of Sulfur Concentration in Gasoline on NOx Storage - Reduction Catalyst

Influence of sulfur poisoning on NOx storage - reduction catalysts (NSR catalysts) was examined using both model gas and an actual vehicle. Deterioration of NSR catalysts is explained as the balance of sulfate formation in lean operating conditions and the amount of sulfate decomposed under rich operating conditions. This study focused on sulfate decomposition characteristics of NSR catalysts. First, sulfate decomposition characteristics of an NSR catalyst were examined in a model gas test. It was found that the initial temperature of SOx release was higher than the sulfur poisoning temperature. Crystal growth of sulfate by increasing temperature was assumed, and hence suppressed SOx release. Second, various sulfur concentrations (8 - 500 ppm) in gasoline were used for vehicle durability. The duration of one durability cycle was 1,260 seconds, including a 60 second regeneration of sulfur poisoning (AFR 14.2, 700 °C).
Journal Article

In-Situ Liquid TEM Study on the Degradation Mechanism of Fuel Cell Catalysts

Electrode catalyst (platinum) degradation represents a major challenge to the performance and durability of polymer electrolyte membrane fuel cells (PEMFCs) in Fuel Cell Vehicles (FCVs). While various mechanisms have been proposed and investigated previously, there is still a need to develop in situ imaging techniques that can characterize and provide direct evidence to confirm the degradation process. In the present study, we report an in situ transmission electron microscopy (TEM) method that enables real time, high-resolution observation of carbon-supported platinum nanoparticles in liquid electrolyte under working conditions. By improving the design of the Micro Electro Mechanical Systems (MEMS) sample holder, the migration and aggregation of neighboring platinum nanoparticles could be visualized consistently and correlated to applied electrode potentials during aging process (i.e., cyclic voltammetry cycles).
Technical Paper

In Situ Observation of Catalysis Reactions Using Transmission Electron Microscope

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.
Technical Paper

Improvement of NOx Storage-Reduction Catalyst

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.
Technical Paper

Hexagonal Cell Ceramic Substrates for Lower Emission and Backpressure

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
Technical Paper

HC Adsorber System for SULEVs of Large Volume Displacement

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.
Technical Paper

Fuel Property Requirement for Advanced Technology Engines

The effects of gasoline fuel properties on exhaust emissions were investigated. Port injection LEVs, a ULEV, a prototype SULEV which were equipped with three–way (3–way) catalysts and also two vehicles with direct injection spark ignition (DISI) engines equipped with NOx storage reduction (NSR) catalysts were tested. Fuel sulfur showed a large effect on exhaust emissions in all the systems. In the case of the DISI engine with the NSR catalyst, NOx conversion efficiency and also regeneration from sulfur poisoning were dramatically improved by reducing sulfur from 30ppm to 8ppm. Distillation properties also affected the HC emissions significantly. The HC emissions increased in both the LEV and the ULEV with a driveability index (DI) higher than about 1150 (deg.F). The ULEV was more sensitive than the LEV. These results show that fuel properties will be important for future technologies required to meet stringent emission regulations.
Technical Paper

Fuel Effects on SIDI Efficiency and Emissions

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.
Technical Paper

Feasibility Study of Exhaust Emissions in a Natural Gas Diesel Dual Fuel (DDF) Engine

The Diesel Dual Fuel (DDF) vehicle is one of the technologies to convert diesel vehicles for natural gas usage. The purpose of this research was to study the possibility of a DDF vehicle to meet emission standards for diesel vehicles. This research was done for small passenger vehicles and commercial vehicles. The exhaust emissions compliance of such vehicles in a New European Driving Cycle (NEDC) mode which was composed of Urban Driving Cycles (UDC) and an Extra Urban Driving Cycle (EUDC) was evaluated. (see APPENDIXFigure A1) In this study, the passenger vehicle engine, compliant with the EURO4 standard, was converted to a DDF engine. Engine bench tests under steady state conditions showed similar result to previous papers. Total hydrocarbon (HC) emission was extremely high, compared to diesel engine. The NEDC mode emissions of the DDF vehicle were estimated based on these engine bench test results.
Technical Paper

Experimental and Numerical Analysis for a Urea-SCR Catalytic Converter

Urea-SCR (Selective Catalytic Reduction) systems are getting a lot of attention as the most promising NOx reduction technology for heavy-duty diesel engine exhaust. In order to promote an effective development for an optimal urea-SCR after-treatment system, it is important to clarify the decomposition behavior of the injected urea and a detailed reaction chemistry of the reactants on the catalyst surface in exhaust gases. In this paper we discuss experimental and numerical studies for the development of a numerical simulation model for the urea-SCR catalyst converter. As a first step, in order to clarify the behavior of reductants in an urea-SCR converter, two types of diagnostic technique were developed; one is for measuring the amount of NH3, and the other is for measuring the amount of total reductants including unreacted urea and iso-cyanic acid. These techniques were applied to examine the behavior of reductants at the inlet and inside the SCR converter.
Technical Paper

Enhancing PtCo Electrode Catalyst Performance for Fuel Cell Vehicle Application

While carbon supported PtCo alloy nanoparticles emerged recently as the new standard catalyst for oxygen reduction reaction in polymer membrane electrolyte fuel cells, further improvement of catalyst performance is still of great importance to its application in fuel cell vehicles. Herein, we report two examples of such efforts, related to the improvements of catalyst preparation and carbon support design, respectively. First, by lowering acid treatment voltage, the effectiveness for the removal of unalloyed Co was enhanced significantly, leading to less Co dissolution during cell operation and about 40% higher catalyst mass activity. It has been also found that the use of nonporous carbon support material promoted mass transfer and resulted in substantial drop of overpotential at high current and low humidity. This result may suggest an effective strategy towards the development of fuel cell systems that operate without additional humidification.
Technical Paper

Effects of Fuel Properties on the Performance of Advanced Diesel NOx Aftertreatment Devices

In the Japan Clean Air Program II (JCAP II) Diesel WG, effects of fuel properties on the performance of two types of diesel NOx emission aftertreatment devices, a Urea-SCR system and a NOx storage reduction (NSR) catalyst system, were examined. For a Urea-SCR system, the NOx emission reduction performance with and without an oxidation catalyst installed in front of the SCR catalyst at low exhaust gas temperature operation was compared. For an NSR catalyst system, the effect of fuel sulfur on both emissions and fuel economy during 50,000 km driving was examined. Furthermore, effects of other fuel properties such as distillation on exhaust emissions were investigated. The results show that sulfur is the influential factor for both devices. Namely, high NOx emission reduction performance of the Urea-SCR system with the oxidation catalyst at low exhaust gas temperature operation is influenced by sulfur.
Technical Paper

Effect of Sulfur-free and Aromatics-free Diesel Fuel on Vehicle Exhaust Emissions using Simultaneous PM and NOx Reduction System

A new diesel after-treatment system, Diesel Particulate and NOx Reduction System (DPNR), is being developed for reducing PM and NOx emissions. We examined the effects of sulfur content in lubricants on exhaust NOx emission from DPNR catalyst, and examined the PM reduction ability using sulfur-free and aromatics-free fuel. After vehicle durability testing of 40,000 km without forced regeneration of PM and sulfur poisoning on DPNR catalyst, deterioration of DPNR was lower than using higher sulfur contents in fuel and oil. In addition to decreasing fuel sulfur, decreasing oil sulfur was also effective to maintain high NOx conversion efficiency. Although the catalyst was poisoned by sulfur in the lubricants, the influence of oil sulfur poisoning on the catalyst was lower than fuel sulfur poisoning. On the other hand, engine out PM emissions decreased by 70 % because of aromatics-free fuel. The pressure drop of DPNR did not increase during the 40,000 km vehicle durability test.