UC Berkeley

Surface structure, mobility, and composition of transition metal catalysts were studied by high-pressure scanning tunneling microscopy (HP-STM) and ambient-pressure X-ray photoelectron spectroscopy (AP-XPS) at high gas pressures. HP-STM makes it possible to determine the atomic or molecular rearrangement at catalyst surfaces, particularly at the low-coordinated active surface sites. AP-XPS monitors changes in elemental composition and chemical states of catalysts in response to variations in gas environments. Stepped Pt and Cu single crystals, the hexagonally reconstructed Pt(100) single crystal, and Pt-based bimetallic nanoparticles with controlled size, shape and composition, were employed as the model catalysts for experiments in this thesis.

Surface reconstruction at low-coordinated step sites at high gas pressures was first explored on a stepped Pt(557) single crystal surface under O₂. At 298 K, 1 Torr of O₂ is able to create nanometer-sized clusters that are identified as surface Pt oxide by AP-XPS, which covers the entire Pt(557) surface. On the flat Pt(111) surface under 1 Torr of O₂, Pt oxide clusters can form but are mostly accumulated within 2 nm from the steps. The hexagonal oxygen chemisorption pattern is observed on the terraces. At lower pressures such as 10^-7 Torr, O₂ only adsorbs at the step edges on Pt(557). The majority of the Pt oxide clusters disappear on both Pt(557) and Pt(111) surfaces after O₂ is evacuated to the 10^-8 Torr range. Quantitative XPS analysis with depth profiles indicates that the Pt oxide formed on Pt(557) is less than 0.6 nm thick and that the Pt oxide concentration at surface together with oxygen coverage varies reversibly with the O₂ pressure.

The disappearance of Pt oxide clusters upon O₂ evacuation is ascribed to reactions of Pt oxide towards H₂ and CO in the vacuum background gases. The structure and surface chemistry of the Pt(557) surface was therefore studied under H₂-O₂ and CO-O₂ mixtures. After exposing Pt(557) to approximately 1 Torr of O₂ to induce the formation of Pt oxide clusters, H₂ was slowly added into the system. Both HP-STM and AP-XPS results show that the Pt oxide coverage decreases with the H₂ partial pressure and that all the Pt oxide disappears at H₂ partial pressures above 43 mTorr. Pt steps are restored with the removal of Pt oxide clusters. Water is produced in the gas-phase, which co-adsorbs with hydroxyl species on Pt(557). Detailed analysis shows that the consumption of surface Pt oxide is exclusively responsible for the decrease of oxygen coverage on Pt(557). In the coexistence of 1 Torr of CO and 1 Torr of O₂, Pt oxide clusters are not observed like under the H₂-O₂ mixture. Instead, triangular Pt clusters and double-sized terraces induced by CO are observed.

Influences of step configuration on the surface restructuring processes were studied on Pt(557) and Pt(332) that differ only in the step orientation. 500 mTorr of CO creates Pt clusters shaped as triangles and parallelograms on Pt(557) and Pt(332), respectively. When 500 mTorr of C₂H₄ was introduced afterwards, Pt clusters are removed on Pt(332) but preserved on Pt(557). The three-fold hollow sites at the (111) steps enable the Pt(332) surface to accommodate ethylidyne even covered by CO. As a result, kink Pt atoms at the cluster edges are driven to diffuse to form straight steps, so as to admit more ethylidyne at steps. In contrast, Pt(557) has (100) steps on which ethylidyne does not adsorb, therefore keeping the island structure after the introduction of C₂H₄. When 500 mTorr of C₂H₄ was added first into the high-pressure cell, a periodic pattern is resolved at step edges on Pt(332). In contrast, some bright species separated by more than 1 nm are observed on Pt(557). Further introducing 500 mTorr of CO does not facilitate the formation of Pt clusters.

The structure and mobility under C₂H₄, H₂, and CO were also studied on the Pt(100) surface, whose topmost layer is rearranged into a hexagonal overlayer in vacuum. Under 1 Torr of C₂H₄, the hexagonal reconstruction is preserved on Pt(100), which is covered by highly mobile adsorbates. Pt atoms on the hexagonal layer can also move as a result of the weakened interaction between the surface layer and the bulk. The mobility is enhanced under 1 Torr of 1:1 C₂H₄-H₂ mixture because the Pt(100)-hex surface is active in ethylene hydrogenation. The surface mobility along with the catalytic reaction is quenched after introducing 3 mTorr of CO. Meanwhile, the hexagonal reconstruction is lifted by the adsorption of CO. At 5 × 10^-6 Torr of C₂H₄, CO from background gases can also adsorb on Pt(100), creating Pt islands that do not revert to the hexagonal surface when the C₂H₄ pressure was further increased to 1 Torr.

In order to understand the effect of substrates on surface reconstruction, the structure of the stepped Cu(557) surface was monitored in equilibrium with high pressures of gases. Cu generally binds to the reducing gases such as CO, H₂, and C₂H₄ weaker than Pt, leading to a lower coverage on Cu than on Pt at the same gas pressure. Accordingly, 12 Torr of CO is required to induce clusters on Cu(557), because higher CO pressures are needed to keep a sufficient amount of CO that can stabilize clusters. At 1 Torr, large terraces with an average width of 23 nm are observed on Cu(557), because of the low diffusion barrier for Cu atoms both on terraces and along the steps. 500 mTorr of H₂ results in step coalescence on Cu(557), giving rise to 6 nm wide terraces. C₂H₄ adsorption at 500 mTorr results in 5 nm large clusters. CO does not change the Cu(557) surface structure while adding into C₂H₄, but causes the appearance of large terraces while co-adsorbing with H₂. Under oxidizing gases, for example 1 Torr of O₂, the Cu(557) surface is significantly oxidized, forming thick layers of Cu oxide.

Pt-based bimetallic nanoparticle catalysts were also investigated with AP-XPS under reaction conditions to study their surface chemistry. PtFe nanoparticles do not undergo any surface segregation at 298 K when the gas environment changes, but surface Fe atoms are partially reduced under the C₂H₄-H₂ mixture and partially oxidized under O₂. Neither does the surface composition of Pt₉Co-Co core-shell nanoparticles change while heating under H₂ even to 673 K nor do oxidation states. In Pt-Ni systems, at 393 K, Ni is oxidized under O₂ and migrates to the surface because Ni is more susceptible to oxidation than Pt. In contrast, when the surface is reduced by H₂, Pt segregates to the surface since the surface free energy of Pt is lower. Such segregation does not occur at 353 K owing to the low atomic mobility in lattice.