Gold nanoparticles of 2-5 nm supported on woven fabrics of activated carbon fibers (ACF) were effective during CO oxidation at room temperature. To obtain a high metal dispersion, Au was deposited on ACF from aqueous solution of ethylenediamine complex [Au(en) 2 ]Cl 3 via ion exchange with protons of surface functional groups. The temperature-programmed decomposition method showed the presence of two main types of functional groups on the ACF surface: the first type was associated with carboxylic groups easily decomposing to CO 2 and the second one corresponded to more stable phenolic groups decomposing to CO. The concentration and the nature of surface functional groups was controlled using HNO 3 pretreatment followed by either calcination in He (300-1273 K) or by iron oxide deposition. The phenolic groups are able to attach Au 3+ ions, leading to the formation of small Au nanoparticles (< 5 nm) after reduction by H 2 . This was confirmed by high-resolution electron microscopy combined with X-ray energy-dispersive analysis. The catalyst with high Au dispersion demonstrated high activity in CO oxidation. The surface carboxylic groups decomposed during interaction with [Au(en) 2 ]Cl 3 solution and reduced Au 3+ to Au 0 , resulting in the formation of bigger (> 9 nm) Au agglomerates after reduction by H 2 . These catalysts demonstrated lower activity as compared to the ones containing mostly small Au nanoparticles. Complete removal of surface functional groups rendered an inert support that would not interact with the Au precursor. The oxidation state of gold in the Au/ACF catalysts was controlled by X-ray photoelectron spectroscopy before and after the reduction in H 2 . The high-temperature reduction in H 2 (673-773 K) was necessary to activate the catalyst, indicating that metallic gold nanoparticles are active during catalytic CO oxidation.  2004 Elsevier Inc. All rights reserved.

Selective Synthesis of Pd Nanoparticles in Complementary Micropores of SBA-15. -Pd or PdO nanoparticles are selectively synthesized within complementary micropores of SBA-15 located in the mesopore walls. This results in a novel bifunctional composite material with stable nanoparticles of about 1.1 nm size and highly ordered open mesopore channels. Such bifunctional materials are of interest in the nanotechnology field, gas adsorption, separation, and catalysis. -(YURANOV, I.; KIWI-MINSKER*, L.; BUFFAT, P.; RENKEN, A.; Chem. Mater. 16 (2004) 5, 760-761; Swiss Fed. Inst. Technol., CH-1015 Lausanne, Switz.; Eng.) -W. Pewestorf 21-225

The gas phase (1 atm, 453 K) hydrogenation of p-chloronitrobenzene (p-CNB) over a series of laboratory-synthesized and commercial Pd (1–10% wt) supported on activated carbon (AC) and non-reducible (SiO2 and Al2O3) and reducible (ZnO) oxides has been examined. Reaction over these catalysts generated the target p-chloroaniline (p-CAN) (via selective hydrogenation) and nitrobenzene (NB)/aniline (AN) as a result of a combined hydrodechlorination/hydrogenation. A range of Pd nanoparticles with mean sizes 2.4–12.6 nm (from HRTEM and H2/CO chemisorption) were generated. Both the p-CNB transformation rate and H2 chemisorption increased with decreasing Pd size. Residual Mo (from the stabilizer used in the synthesis of Pd colloids) suppressed activity, but this was circumvented by the use of poly(N-vinyl-2-pyrrolidone) (PVP). Pd/AC generated p-CAN and AN as principal products, Pd on SiO2 and Al2O3 exhibited hydrodechlorination character generating AN and NB, and Pd/ZnO promoted the sole formation of p-CAN at all levels of conversion. Reaction selectivity is linked to Pd electron density with the formation of Pdδ+ on AC and the occurrence of Pdδ− on SiO2 and Al2O3. Reaction exclusivity to p-CAN over Pd/ZnO is attributed to the formation of PdZn alloy (demonstrated by XPS), which selectively activates the −NO2 group. This is the first report that demonstrates 100% selectivity for p-CNB → p-CAN over supported Pd.

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