Three-way catalyst oxygen storage is typically provided by rare earth oxide materials, including oxides of cerium. The air/fuel mixture in a closed loop system is constantly changing from slightly rich to slightly lean of stoichiometric and back again at a cycle rate between 0.25 to 1.0 seconds. The A/F mixture is only very briefly at the stoichiometric point. Thus, when the cycle is slightly lean there is excess oxygen which will pass through the catalyst and out the tailpipe. Rare earth oxide materials are incorporated within the catalyst to capture the excess oxygen and store it for use when the A/F mixture is rich and short of oxygen. Cerium oxide- based oxygen storage materials possess two oxidation states which change easily from one to the other with oxygen content in the exhaust. Thus, oxygen is captured when in excess and given up for oxidative reactions when it is in short supply. The result is a more efficient use of stored oxygen to oxidize CO and HC and more efficient reduction of NO by CO while oxygen storage takes place.
The quantity and form of rare earth oxides employed determines the oxygen storage capacity. Gasoline fuel sulfur has been found to reduce oxygen storage by absorbing to the oxygen sites as a sulfate. This blocks subsequent oxygen storage until the catalyst is cleaned through a high acceleration and high temperature exhaust event (9). Oxygen storage is an important factor for OBDII-compliant vehicle systems which rely on it as a catalyst monitoring technique.
2. TWC Catalyst Design Factors. Three-way catalyst designs are complex. Three-way catalysts are designed to provide separate functions - NOx reduction, and HC and CO oxidation. A Pd-only three-way catalyst designed for close coupled operation needs to have high temperature resistance, quick light-off performance, and maximum oxygen storage capacity. Pt/Rh and Pd/Rh three-way catalysts have to avoid unwanted alloy formation. Each has to be designed in combination with base metal promoters in such a way as to optimize all functions. The design has to be durable over the complete temperature range with a minimum of base metal and precious metal sintering and little loss of support surface area.
In addition to sulfur poisoning of advanced TWCs, sulfur can impact advanced gasoline emission control technologies in other ways. As discussed previously, sulfur degrades the performance of NOx adsorber catalysts used in lean gasoline, direct injection applications (see Figure 19 below, taken from SAE paper 2000-01-2019). Fuel sulfur levels can also impact TWC emissions of NH3 and N2O. A CRC study found that catalyst aging effects on NH3 emissions were found to be statistically significant for the FTP and for the US06 test cycles, with higher emissions for the aged catalysts. Fleet average NH3 emissions were 50% higher for the aged catalysts over the FTP and 17% higher for the aged catalysts over the US06 (16). These catalyst aging impacts include exposure to fuel sulfur.