Determination of the surface area of dispersed ruthenium by reactive nitrous oxide chemisorption

The interaction of nitrous oxide with ruthenium surfaces was studied in order to develop a fast and reliable method for the determination of the metallic surface area and dispersity of ruthenium catalysts as alternative to the established chemisorption methods using hydrogen, carbon monoxide or oxygen as probe molecule. Studies of the temperature dependence of the reactive or dissociative chemisorption of nitrous oxide using pulse technique showed that an oxygen monolayer of almost constant stoichiometry is formed in a narrow temperature range around 403 K. However, so-called 'rest nitrogen peaks' were observed after saturation of an O-monolayer revealing a small additional nitrous oxide conversion which could be attributed to formation of subsurface oxygen by means of back-titration of the oxygen totally uptaken. This additional nitrous oxide consumption can be minimised by an adjustment of both the N2O-sampling loop volume and the catalyst sample weight in order to obtain an oxygen monolayer saturation by few pulses, and moreover, it can be considered as a correction for the calculation of the oxygen monolayer. A specific nitrous oxide consumption of 13.5 mu mol/m(Ru)(2) has been determined on ruthenium black by means of alternating measurements of the nitrogen physisorption and N2O-pulse chemisorption. The reliability of the new method for characterisation of the dispersity or surface area of supported ruthenium was proved with ruthenium highly dispersed on gamma-alumina. (C) 1999 Elsevier Science B.V. All rights reserved.