CO oxidation on nanoporous gold: A combined TPD and XPS study of active catalysts

Disks of nanoporous gold (np-Au), produced by leaching of silver from AgAu alloy and prepared as active catalysts for CO oxidation in a continuous-flow reactor, were investigated in detail by x-ray photoelectron spectroscopy and temperature-programmed desorption spectroscopy in ultra-high vacuum. Np-Au exhibits several oxygen species on and in the surface: Chemisorbed oxygen (Oact), probably generated at residual silver sites at the surface, is readily available after np-Au preparation and consumed by CO oxidation. It can be replenished on activated np-Au by exposure to O2. In addition, strongly bound oxygen, probably at subsurface sites, is present as a major species and not consumed by CO oxidation. Pronounced CO desorption at temperatures above 200K observed after exposing np-Au to CO at 105K indicates an additional, more stable type of CO binding sites on np-Au as compared to pure gold. Only CO at these binding sites is consumed by oxidation reaction with Oact. It is proposed that the presence of strongly bound subsurface oxygen stabilizes CO adsorption on np-Au, thereby being as crucial for the observed catalytic activity of np-Au as residual silver. ► Catalytically active nanoporous gold was studied in UHV by XPS and TPD. ► Active and inactive surface oxygen species were identified on the catalyst surface. ► Active oxygen consumed by exposure to CO can be replenished by exposure to O2. ► CO2 evolution is linked to a CO desorption state at temperatures above 200K. ► Residual silver and inactive oxygen may cause O2 activation and CO stabilization.