Karl C. C. Kharas

The Preparation of Highly Dispersed Au/Al2O3 by Aqueous Impregnation

In this work, we report an impregnation method for preparing Au supported on alumina from HAuCl4. In the literature, impregnation under acidic conditions has been found to lead to poor dispersions of Au and the resulting catalysts are not as active as those prepared by deposition-precipitation. To overcome these problems, we have developed a two-step procedure: in the first step, the acidified Au solution is contacted with alumina to adsorb the Au chloride on the alumina. After washing off the excess Au precursor, we treat the solid with a strong base to convert the chloride to an absorbed hydroxide. Drying and calcination at 400 °C yields a catalyst with Au particles having a number average diameter of 2.4 nm. The reactivity for CO oxidation at room temperature is comparable to catalysts prepared by deposition-precipitation. These catalysts are stable to hydrothermal sintering, with average particle size around 4 nm after sintering in 10 mol% H2O at 600 °C for 100 h. This work shows that stable Au/Al2O3 catalysts having a high reactivity for CO oxidation can be prepared by impregnation under acidic conditions.

The Sintering of Supported Pd Automotive Catalysts

This work is directed at investigating the contribution of metal particle sintering to catalyst deactivation in close‐coupled automotive catalysts that are aged at elevated temperatures. We focus on the evolution of metal particle sizes in Pd/Al2O3 under conditions typically used for accelerated aging of automotive exhaust catalysts (10 mol % H2O at 900 °C). By using multiple analytical techniques (transmission electron microscopy, X‐ray diffraction, chemisorption, and CO oxidation) we can determine the role of support surface area collapse (encapsulation) versus metal particle sintering. The final dispersion (% metal atoms exposed) after sintering for 96 h ranged from 1.94 to 0.86 % for metal loadings ranging from 0.1 to 7.0 wt % (a 70‐fold variation). Thus, it appears that metal loading (over the range studied) has only a limited effect on the final dispersion in the sintered catalyst. The sintering kinetics were found to obey a relationship dn−

Particle size distributions in heterogeneous catalysts: What do they tell us about the sintering mechanism?

{d{{n\hfill \atop 0\hfill}}}

Alloyed metal catalysts for the reduction of NOx in the exhaust gases from internal combustion engines containing excess oxygen

=kt for which the exponent n is approximately 2.0 and d is the number average particle diameter at time t. This relationship and the fact that metal particle size continues to grow with time are both consistent with Ostwald ripening as the dominant mechanism. Furthermore, no limiting (equilibrium) particle size was achieved within the sintering times studied here (up to 200 h). These results have important implications for the design of thermally stable automotive catalysts.