CO chemisorption on TiO2(110): Oxygen vacancy site influence on CO adsorption

CO chemisorption has been studied on TiO2(110) under surface conditions where oxygen anion vacancy sites are not present (oxidized surface), compared to conditions where the vacancy sites are present (annealed surface). The binding energy of CO on the nondefective TiO2(110) surface is 9.9 kcal/mole in the limit of zero coverage. CO...CO repulsive interactions have been observed at higher coverages. When anion vacancy sites are produced under controlled annealing conditions in vacuum at 900 K, a significant increase in the desorption temperature of a portion of the chemisorbed CO is observed. This observation, coupled with measurements showing that defective TiO2(110) does not have enhanced CO chemisorption capacity, suggests that CO adsorbs more strongly on lattice Ti sites in the vicinity of anion vacancy sites. It is postulated that enhanced CO bonding occurs via the interaction of the O moiety of CO with the anion vacancy site while primary adsorbate bonding occurs via the C moiety to Ti lattice sites. Neither CO2 production nor oxygen exchange in CO occurs when CO desorbs from defective TiO2(110).