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On-Board Diagnostics for emissions-related components require the monitoring of the catalytic converter performance. Currently, the dual Exhaust Gas Oxygen (EGO) sensor method is the only proven method for monitoring the catalyst performance for hydrocarbons (HC). The premise for using the dual oxygen sensor method is that a catalyst with good oxygen storage capacity (OSC) will perform better than a catalyst with lower OSC. A statistical relationship has been developed to correlate HC performance with changes in OSC. The current algorithms are susceptible to false illumination of the Malfunction Indication Light (MIL) due to: 1. The accuracy with which the diagnostic algorithm can predict a catalyst malfunction condition, and 2. The precision with which the algorithm can consistently predict a malfunction. A new algorithm has been developed that provides a significant improvement in correlation between the EGO sensor signals and hydrocarbon emissions.

Three-way catalysts (TWC) to remove the HC, CO, and NOx pollutants from the exhaust of gasoline powered vehicles employ rhodium in combination with platinum and palladium. Of these precious metals, rhodium is by far the most expensive. Since it is so heavily used for its NOx reduction capabilities, the amount per vehicle approaches and sometimes exceeds the naturally occurring mine ratio. A program was conducted to determine the feasibility of a non-rhodium TWC catalyst. It showed that Pt and Pd in conjunction with other washcoat support materials exhibited relatively good TWC characteristics compared to a Pt/Rh catalyst after engine dynamometer aging. In FTP evaluations this new REDOX type catalyst gave comparable HC and CO efficiency and 85% of the NOx efficiency of a Pt/Rh-containing catalyst. Presently the operating window is being defined but comparisons to conventional Pt/Pd and Pt/Rh catalysts have been made under a number of conditions.

A new technique has been developed to assess the deterioration of hydrocarbon lightoff during FTP Phase 1. This method maps the dynamic real time data onto the hydrocarbon conversion/gas phase temperature plane to show the instantaneous hydrocarbon activity as a function of the exhaust temperature. Clearly, the map exhibits an apparent hysteresis bifurcation. The bifurcation is thought to be predominantly related to catalyst surface temperature. The hysteresis envelope of the map expands with aging severity. Therefore, the map can be used as a measure of catalyst deactivation.

The technical issues related to NOx abatement for diesel applications are summarized. Data on improved catalysts and a novel approach which involves temporarily trapping of NOx before reduction are presented. New high temperature lean NOx materials have been identified which have better hydrothermal stability than the state of the art Cu/ZSM-5. One of these materials, Catalyst A, was shown to reduce the NOx emitted from a 2.5 L diesel engine at temperatures ≥ 350°C using injected diesel fuel as a reductant. Catalyst A also showed reasonably good durability after aging for 500 h at ca. 500°C on a 14 L diesel truck engine. Pt/Al2O3, a low temperature lean NOx reduction catalyst (200-300°C), demonstrated fairly good performance after 125 h of aging on a 4 L diesel truck engine, however sulfate make and N2O formation are high on this material. New low temperature NOx traps show promise for transient removal of NOx below 200-400°C.

The plasma assisted catalytic reactor (PACR) approach to lean NOx abatement is a two step process. The non-thermal plasma oxidizes the engine out NO to NO2, which is then reduced to N2 over a catalyst using a hydrocarbon reductant. Whereas it was once believed that the plasma itself directly reduces NOx to N2, it has been shown that the plasma's principle function is to oxidize NO to NO2. This is accomplished without oxidizing SO2 to SO3, resulting in lower sulfate particulate when compared to standard lean NOx catalysis using platinum or reducible oxide catalysts. We have performed reactor studies comparing the relative reducibility of NO2 and NO in a synthetic diesel exhaust using diesel fuel as the hydrocarbon reductant, with attention to time-on stream behavior and determination of NOx reversibly adsorbed on the catalyst. We find that at 200°C, 50% of the NO2 disappearance over Na-ZSM5 is attributable to reversible adsorption on the catalyst.

The desire for improved fuel economy, and lower emissions of green house gases, such as CO2, is projected to increase the demand for diesel and lean-burn gasoline engines throughout the world. Several commercial diesel oxidation catalysts (DOCs) were developed in the last 3-4 years to reduce hydrocarbon, CO, and particulates emitted from the exhaust of diesel passenger cars and trucks. To meet future U.S. and European NOx standards, it is essential to develop catalyst technology that will allow NOx reduction in addition to the other three pollutants. Two materials that attracted great attention as lean NOx catalysts are the Cu/ZSM-5 and Pt based. Cu containing ZSM-5 are active for lean-NOx reduction at temperatures above 350°C, provided sufficient hydrocarbons are present as reductants.

A novel process for coating and assembling metal converters utilizing precoated foil as building blocks has been developed which yields a converter capable of withstanding typical industry specified hot vibration protocols. The precoating process used here results in uniform catalyst coating distributions with coating adhesion to the foil on a par with the coatings' adhesion to ceramic substrates. FTP and MVEG vehicle emission performance of this unique precoated metal converter design versus a more conventional dip-coated metal monolith (parts with the same volume, cell density, and tri-metal catalyst coating), exhibited improved catalyst emission breakthrough efficiencies with respect to HC, CO, and NOx after two different engine-aging protocols. These advantages were observed on three different test vehicles across most phases of these driving cycles.

Catalytic reduction of NOx from heavy duty diesel engines via addition of reductant to the exhaust is accompanied by a substantial exotherm in the catalyst bed which does not occur, for example, in a diesel oxidation catalyst. Engine tests show that thermal management in the aftertreatment system is required for optimum reductant use and maximum NOx conversion by the low-temperature (200-300°C) catalyst NSP-5, but of less importance with the high temperature (> 350°C) Catalyst A. Understanding thermal effects is also important for reconciling test results in the near-adiabatic environment of a full-sized catalyst on an engine with the near-isothermal one of a test piece in a laboratory reactor. The effects of reductant type and concentration on NOx conversion on NSP-5 were shown to result in part from non-steady state behavior of the catalyst during steady state engine operation.

Base metal oxide diesel oxidation catalyst technology having low sulfate making tendencies was evaluated using the ECE R-49 Test procedure on medium and heavy duty diesel engines and found to achieve substantial reduction of particulate, gas phase HC and CO emissions. Although the engines met the current European standards, further reduction in these emissions for vehicles operated in congested urban areas, such as buses, would have a positive impact on general air quality. A study of varying fuel sulfur levels (110-770 ppm S) showed that the catalyst was effective for control of sulfate-make such that overall particulate removal in the test was not compromised. However, it was found that lower fuel sulfur levels (< 550 ppm S) gave the best results for the ECE R-49 test which places emphasis on test modes yielding the highest exhaust temperatures.

Strategic Materials at Reaction Temperatures (SMART) is an approach used to design washcoat systems for passive 4-way emission control catalysts. Light duty diesel vehicles need to meet the European Motor Vehicle Emissions Group (MVEG) cycle or U. S. Federal test procedure (FTP 75). Emissions that are monitored include hydrocarbon (HC), nitrogen oxides (NOx), carbon monoxide (CO) and total particulate matter (TPM). Low engine-exhaust temperatures (< 200°C during city driving) and high temperatures (> 500-800°C under full load and wide-open throttle) make emission control a formidable task for the catalyst designer Gas phase HC, CO and NOx reactions must be balanced with the removal of the soluble organic fraction for the vehicle to be in compliance with regulations. The SMART approach uses model gases under typical operating conditions in the laboratory to better understand the function of individual washcoat components.

A NOx trap catalyst was evaluated in a light-duty diesel engine bench under steady-state speed/load conditions with alternating lean and rich exhaust streams. The NOx conversion was correlated with several engine operating and control parameters, such as speed, lean / rich timing and catalyst temperature. The NOx conversion is a result of balance between stored NOx in a lean stream and the quantity of reductant applied in a rich transient pulse. The conversion is inversely proportional to the lean / rich ratio, R, (at R< 17) and engine speed. At a given speed and lean/rich ratio, the conversion is proportional to the catalyst inlet temperature. If the temperature is too high, thermal NOx release may decrease the overall NOx conversion. With a fully regenerated NOx trap catalyst, its cumulative NOx storage, at a given trapping period (or an instantaneous NOx trapping efficiency), is proportional to engine speed.