Novel Nanostructured Pd/Co-Alumina Materials for the Catalytic Oxidation of Atmospheric Pollutants.

Cobalt-doped alumina catalysts were prepared using different methods, either conventional wet impregnation (WI) and/or advanced spray impregnation (SI), and they were evaluated as novel oxidation catalysts for CO and MeOH oxidation. The spray impregnation technique was used with the aim of achieving the synthesis of core-shell catalytic nanostructures to secure the chemical/thermal stability of active sites on the catalyst carrier. The catalysts were further promoted with a low Pd content (0.5 wt.%) incorporated via either incipient wetness impregnation (DI) or spray impregnation. The results revealed the superior performance of the spray-impregnated catalysts (Co/γ-Al2O3-SI) for both reactions. The deposition of Co oxide on the outer surface of the alumina particle (SEM images) and the availability of the active Co phase resulted in the enhancement of the Co/γ-Al2O3 catalysts' oxidation activity. Pd incorporation increased the catalysts' reducibility (TPR-H2) and improved the catalysts' performance for both reactions. However, the Pd incorporation method affected the catalytic performance; with the SI method, the active phase of Co3O4 was probably covered with PdO and was not available for the oxidation reactions. On the contrary, the incorporation of Pd with the DI method resulted in a better dispersion of PdO all over the Co/Al catalyst surface, maintaining available Co active sites and a better Pd-Co interaction. MeOH desorption studies revealed the methanol oxidation mechanism: the Co/Al catalysts promoted the partial oxidation of MeOH to formaldehyde (HCHO) and dehydration to dimethyl ether (DME), while the Pd-based Co/Al catalysts enhanced the complete oxidation of methanol to CO2 and H2O.

Relating n-pentane isomerization activity to the tungsten surface density of WO(x)/ZrO2.

Zirconia-supported tungsten oxide (WO(x)/ZrO(2)) is considered an important supported metal oxide model acid catalyst, for which structure-property relationships have been studied for numerous acid-catalyzed reactions. The catalytic activity for xylene isomerization, alcohol dehydration, and aromatic acylation follows a volcano-shape dependence on tungsten surface density. However, WO(x)/ZrO(2) has not been studied for more acid-demanding reactions, like n-pentane isomerization, with regard to surface density dependence. In this work, WO(x)/ZrO(2) was synthesized using commercially available amorphous ZrO(x)(OH)(4-2x) and model crystalline ZrO(2) as support precursors. They were analyzed for n-pentane isomerization activity and selectivity as a function of tungsten surface density, catalyst support type, and calcination temperature. Amorphous ZrO(x)(OH)(4-2x) led to WO(x)/ZrO(2) (WZrOH) that exhibited maximum isomerization activity at ∼5.2 W·nm(-2), and the crystalline ZrO(2) led to a material (WZrO(2)) nearly inactive at all surface densities. Increasing the calcination temperature from 773 to 973 K increased the formation of 0.8-1 nm Zr-WO(x) clusters detected through direct imaging on an aberration-corrected high-resolution scanning transmission electron microscope (STEM). Calcination temperature further increased catalytic activity by at least two times. Brønsted acidity was not affected but Lewis acidity decreased in number, as quantified via pyridine adsorption infrared spectroscopy. WO(x)/ZrO(2) exhibited isomerization activity that peaked within the first 2 h time-on-stream, which may be due to Zr-WO(x) clusters undergoing an activation process.