The influence of bulk stoichiometry on near-ambient pressure reactivity of bare and Pt-loaded rutile TiO2(110)

The interaction of catalyst particles with reducible support materials can drastically change their reactivity. On rutile TiO2, processes like particle encapsulation (caused by the "strong metal-support interaction", SMSI) have long been known to depend on the initial reduction state of the oxide. Despite this knowledge, sample stoichiometry has rarely been controlled in a reproducible manner in the surface science literature. Here, we use scanning tunnelling microscopy (STM) to explore systematically how near-ambient pressures (0.1-1.0 mbar) of O-2, H-2, CO and CO2 affect blank and Pt-loaded rutile TiO2(110) surfaces of different bulk stoichiometry at 600 K. To this end, we present preparation recipes that result in a sample stoichiometry always converging back to the same value, which allows us to use the same samples with constant reduction state over hundreds of preparation cycles. Comparing a highly reduced and a near-stoichiometric TiO2 sample, we find that surface reactivity to all four gasses differs even without Pt loading. Most surprisingly, we find that the highly reduced TiO2(110) is oxidized by CO2, but this reaction is completely inhibited on the near-stoichiometric sample. Pt nanoparticles, in turn, become encapsulated after vacuum annealing on the reduced, but not on the near-stoichiometric sample. Encapsulation on the near-stoichiometric sample is achieved only after exposing it to 0.1 mbar H-2 at 600 K. Interestingly, we also see a further modification of the already encapsulated particles on the reduced sample under the same conditions, such that they become embedded deeper in the TiO2(110) surface.