Surface properties of Ru particles supported on carbon materials: A microcalorimetric study of the effects over the CO chemisorptions of residual anionic species

Chemisorption of CO combined with microcalorimetry has been applied to study the nature, number and adsorption strength distribution of surface sites exposed by carbon-supported Ru catalysts. A comparative analysis of the CO chemisorption on different Ru catalysts, prepared using two different metal precursors, RuCl3·xH2O and Ru(NO)(NO3)3, has been carried out. An activated carbon and the corresponding derivative where oxygen surface groups were incorporated, as well as carbon nanotubes and a high surface area graphite, were used as catalytic supports. Based on previous temperature programmed reduction studies, all the catalysts were reduced under hydrogen flow at 523 K or at 573 K. The CO adsorption differential enthalpy profiles show that Ru(NO)(NO3)3 precursor produces more homogeneous surface site distribution in the Ru nanocrystals, in comparison with those prepared from RuCl3, as well as higher values of enthalpies in the medium range of coverage. As a possible explanation for this effect, residual chloride species remaining after reduction treatment in the ex-chloride catalysts, that can be anchored to the Ru nanoparticles weakening the CO adsorption, have been considered. This behavior occurs for the three studied carbon supports. On the other hand, the oxygen surface groups incorporated on the activated carbon seem not to modify the CO adsorption properties of the catalysts, independently of the precursor employed.

► Enthalpies of CO adsorption on Ru/carbon catalysts ex-RuCl3 are diminished.
► Oxygen groups at activated carbon surfaces do not modified the Ru surface sites.
► Homogeneity of surface site distributions is higher for Ru-CNTs than for Ru-HSAG.
► A possible poisoning effect of Cl species over Ru surface sites has been detected.