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Infrared spectroscopic investigation of CO adsorption on SBA-15- and KIT-6-supported nickel phosphide hydrotreating catalysts.

The infrared (IR) spectra of CO adsorbed on 10, 20, and 30 wt % nickel phosphide-containing reduced SBA-15 and KIT-6 mesoporous silica-supported catalysts have been studied at 300-473 K. On the catalysts containing a stoichiometric amount of phosphorus with 20 wt % loading, the most intense IR absorption band was observed at 2097-2099 cm(-1), which was assigned to CO terminally bonded to coordinatively unsaturated Ni(delta+) (0 < delta < 1) sites. The frequency of this band was 15 cm(-1), higher than that in the spectrum of a reduced Ni2P/SiO2 catalyst, indicating a modified Ni-P charge distribution. This band shifted to lower wavenumbers, and its intensity decreased, while the relative intensity of another band at 2191-2194 cm(-1) assigned to CO terminally bonded to P increased going to catalytically less active, excess-P-containing SBA-15-supported catalysts. CO also adsorbed as a bridged carbonyl (1910 cm(-1)) and as Ni(CO)4 (2050 cm(-1)) species, and the formation of surface carbonates was also identified. The nature of the surface acidity was studied by temperature-programmed desorption of ammonia (NH3-TPD). Weak and strong acid sites were revealed, and the high excess-P-containing catalyst released the highest amount of ammonia, indicating that a high concentration of strong acidity can be disadvantageous for reaching high hydrotreating catalytic activity. The modified Ni-P charge distribution, the mode of CO adsorption on surface nickel phosphide sites, as well as the acidity can be directly connected to the catalytic activity of these mesoporous silica-supported catalysts.