ABSTRACT
The present study is focused on the kinetic investigation of the effects of H(2) and CO(2) on the rates related to the elementary steps of CO sorption over Au/gamma-Al(2)O(3). The kinetic study was carried out in a wide temperature range (50-300 degrees C) by the novel methodology of reversed flow gas chromatography (RF-GC). The findings of preliminary coadsorption studies of CO with H(2), O(2) and O(2)+H(2) indicate that a reductive pre-treatment of the Au catalyst with a mixture of CO in excess of H(2) can be more beneficial concerning CO oxidation activity at low temperatures, compared to the usual reduction in a diluted hydrogen atmosphere, most probably due to the easier activation of oxygen molecules. At high temperatures the rate of reversed water gas shift reaction becomes significant resulting in H(2) and CO(2) consumption. The kinetic findings indicate that hydrogen strongly influences the adsorption of CO over Au/gamma-Al(2)O(3), by enhancing CO adsorption at lower temperatures and weakening the strength CO binding. On the other hand, CO(2) adsorption competes that of CO under hydrogen-rich conditions. However, the strength of CO(2) bonding is higher compared to that of CO and it further increases at higher temperatures, in agreement with the observed deactivation of the selective CO oxidation in the presence of CO(2).
Subject(s)
Aluminum Oxide/chemistry , Carbon Dioxide/chemistry , Carbon Monoxide/chemistry , Catalysis , Gold/chemistry , Hydrogen/chemistry , Adsorption , Chromatography, Gas/methods , Nanotechnology , TemperatureABSTRACT
Nanometer-sized Au particles on oxide supports exhibit extraordinary activity for the selective oxidation of CO (SCO) under conditions compatible with the operation of polymer electrolyte membrane fuel cells (PEM-FCs). In the present work, the novel methodology of reversed flow inverse gas chromatography (RF-IGC) is further extended to the study of the nature of the active sites related to CO adsorption over Au/gamma-Al(2)O(3) catalyst both in the presence as well as in the absence of hydrogen in a wide temperature range. The main findings are as follows: (i) higher amounts of CO can be bound on the catalyst active sites, at conditions compatible with the operation of PEM-FCs. (ii) At rising temperatures, catalyst adsorptive capacity decreases while the degree of surface heterogeneity increases since new groups of active sites appear, both in the presence and in the absence of hydrogen. (iii) The experimentally observed high-activity of Au/gamma-Al(2)O(3) for SCO at ambient temperatures can be explained as the consequence of CO weaker bonding over metallic Au actives sites in comparison with stronger CO bonding taking place at active sites located on gamma-Al(2)O(3) support, which is related to deactivation.
Subject(s)
Aluminum Oxide/chemistry , Carbon Monoxide/chemistry , Chromatography, Gas/methods , Gold/chemistry , Hydrogen/chemistry , Nanostructures/chemistry , Adsorption , Chromatography, Gas/instrumentation , Kinetics , Particle Size , TemperatureABSTRACT
In the present work, the novel methodology of reversed-flow gas chromatography (RF-GC) is extended in a topic of contemporary scientific and technological interest, such as the effect of hydrogen in the "topography" of the active sites related to CO adsorption. This study concerns CO adsorption on a silica-supported Rh catalyst, at 90 degrees C. The topography of the catalyst in the absence of hydrogen consists of both randomly and islands of CO bound over chemisorbed CO molecules. In contrast, under H2-rich conditions, the observed topography is almost entirely patchwise ascribed to long-range lateral attractions between adsorbate molecules. In excess of hydrogen, CO adsorption is shifted at higher lateral attractions values which correspond to weaker adsorbate-adsorbent interactions and lower surface coverage. This provides an indication of a H2-induced desorption, which can be attributed to the formation of an H-CO complex desorbing from the catalyst surface below the temperature required for CO desorption, in the absence of H2, and it may explain the well-known enhancement of the rate of selective CO oxidation in excess of hydrogen by H2.
