The influence of a cerium additive on ultrafine diesel particle emissions and kinetics of oxidation

The influence of a cerium additive on the kinetics of oxidation and size distribution of ultrafine diesel particles was studied using a high-temperature oxidation-tandem differential mobility analysis method over the temperature range 300-700°C. The addition of cerium to the diesel fuel was observed to cause significant changes in number-weighted size distributions, light-off temperature, and kinetics of oxidation. The peak number concentration in the accumulation mode decreased 50 and 65%, respectively, for 25 and 100 ppm dosing levels under 1400 rpm and 75% engine load. The light-off temperature was reduced by 250 and 300°C, respectively, for 25 and 100 ppm dosing levels. The oxidation rate increased significantly (×20) with the addition of cerium to the fuel; however, the rate was relatively insensitive to dosing level. The activation energy for cerium-dosed oxidation was, within experimental error, equivalent to that for undosed fuel (E_a=100-110 kJmol^-1). From a phenomenological kinetic rate perspective, the increase in oxidation rate was attributed solely to an increase in the preexponential factor. These results suggested that diesel particles using regular, undosed diesel fuels were already metal-catalyzed to some extent, most likely from metals in the lube oil. The addition of cerium likely increased the number of catalytic sites but had no effect on the overall activation energy due to the presence of other metals in the diesel particulate matter coming from lube oil. The characteristics of cerium-laden diesel particles were also investigated. Two principal types of aggregates were found using transmission electron microscopy and energy-dispersive spectrometry analysis. The first was composed mainly of agglomerates of carbonaceous spherules and a few, considerably smaller cerium oxide nanoparticles. The second consisted of metallic aggregates composed mainly of cerium oxide nanoparticles and some carbon.