Microcalorimetric and IR spectroscopic studies of CO adsorption on molybdenum nitride catalysts

The adsorption of CO on both nitrided and reduced passivated Mo(2)N catalysts in either alumina supported or unsupported forms was studied by adsorption microcalorimetry and infrared (IR) spectroscopy. The CO is adsorbed on nitrided Mo(2)N catalysts on three different surface sites: 4-fold vacancies, Mo(delta+) ( 0 < delta < 2) and N sites, with differential heats of CO adsorption decreasing in the same order. The presence of the alumina-support affects the energetic distribution of the adsorption sites on the nitrided Mo(2)N, i.e. weakens the CO adsorption strength on the different sites and changes the fraction of sites adsorbing CO in a specific form, revealing that the alumina supported Mo(2)N phase shows lower electron density than pure Mo(2)N. On reduced passivated Mo(2)N catalysts the CO was found to adsorb mainly on Mo(4+) sites, although some slightly different surface Mo(delta+) d (0 < delta < 2) sites are also detected. The nature, density and distribution of surface sites of reduced passivated Mo(2)N/gAl(2)O(3) were similar to those on reduced MoO(3)/gamma-Al(2)O(3).