Yeohoon Yoon

The Role of Reducible Oxide–Metal Cluster Charge Transfer in Catalytic Processes: New Insights on the Catalytic Mechanism of CO Oxidation on Au/TiO2 from ab Initio Molecular Dynamics

To probe metal particle/reducible oxide interactions density functional theory based ab initio molecular dynamics studies were performed on a prototypical metal cluster (Au20) supported on reducible oxides (rutile TiO2(110)) to implicitly account for finite temperature effects and the role of excess surface charge in the metal oxide. It is found that the charge state of the Au particle is negative in a reducing chemical environment whereas in the presence of oxidizing species coadsorbed to the oxide surface the cluster obtained a net positive charge. In the context of the well-known CO oxidation reaction, charge transfer facilitates the plasticization of Au20, which allows for a strong adsorbate induced surface reconstruction upon addition of CO leading to the formation of mobile Au-CO species on the surface. The charging/discharging of the cluster during the catalytic cycle of CO oxidation enhances and controls the amount of O2 adsorbed at oxide/cluster interface and strongly influences the energetics of all redox steps in catalytic conversions. A detailed comparison of the current findings with previous studies is presented, and generalities about the role of surface-adsorbate charge transfer for metal cluster/reducible oxide interactions are discussed.

Probing equilibrium of molecular and deprotonated water on TiO2(110)

Significance Understanding how water binds and dissociates on surfaces has broad implications in a vast range of physical and chemical processes. The relative stability of molecularly and dissociatively bound water has been debated for decades on many oxide surfaces, but it has never been successfully measured. Our study describes unique instrumentation, direct measurements, and a state-of-the-art computation and theory approach that yield a detailed kinetic and dynamic description of water deprotonation equilibrium on TiO2(110), a prototypical surface commonly used in mechanistic studies of photocatalytic water splitting. This unique study demonstrates that the molecularly bound water on TiO2(110) is preferred over the surface-bound hydroxyls by only 0.035 eV. Understanding adsorbed water and its dissociation to surface hydroxyls on oxide surfaces is key to unraveling many physical and chemical processes, yet the barrier for its deprotonation has never been measured. In this study, we present direct evidence for water dissociation equilibrium on rutile-TiO2(110) by combining supersonic molecular beam, scanning tunneling microscopy (STM), and ab initio molecular dynamics. We measure the deprotonation/protonation barriers of 0.36 eV and find that molecularly bound water is preferred over the surface-bound hydroxyls by only 0.035 eV. We demonstrate that long-range electrostatic fields emanating from the oxide lead to steering and reorientation of the molecules approaching the surface, activating the O–H bonds and inducing deprotonation. The developed methodology for studying metastable reaction intermediates prepared with a high-energy molecular beam in the STM can be readily extended to other systems to clarify a wide range of important bond activation processes.

Anticorrelation between surface and subsurface point defects and the impact on the redox chemistry of TiO2(110)

By using a combination of scanning tunneling microscopy (STM), density functional theory (DFT), and secondary-ion mass spectroscopy (SIMS), we explored the interplay and relative impact of surface versus subsurface defects on the surface chemistry of rutile TiO2 . STM results show that surface O vacancies (VO ) are virtually absent in the vicinity of positively charged subsurface point defects. This observation is consistent with DFT calculations of the impact of subsurface defect proximity on VO formation energy. To monitor the influence of such lateral anticorrelation on surface redox chemistry, a test reaction of the dissociative adsorption of O2 was employed and was observed to be suppressed around them. DFT results attribute this to a perceived absence of intrinsic (Ti), and likely extrinsic interstitials in the nearest subsurface layer beneath inhibited areas. We also postulate that the entire nearest subsurface region could be devoid of any charged point defects, whereas prevalent surface defects (VO ) are largely responsible for mediation of the redox chemistry at the reduced TiO2 (110).

Site-Specific Imaging of Elemental Steps in Dehydration of Diols on TiO2(110)

Scanning tunneling microscopy is employed to follow elemental steps in conversion of ethylene glycol and 1,3-propylene glycol on partially reduced TiO2(110) as a function of temperature. Mechanistic details about the observed processes are corroborated by density functional theory calculations. The use of these two diol reactants allows us to compare and contrast the chemistries of two functionally similar molecules with different steric constraints, thereby allowing us to understand how molecular geometry may influence the observed chemical reactivity. We find that both glycols initially adsorb on Ti sites, where a dynamic equilibrium between molecularly bound and deprotonated species is observed. As the diols start to diffuse along the Ti rows above 230 K, they irreversibly dissociate upon encountering bridging oxygen vacancies. Surprisingly, two dissociation pathways, one via O-H and the other via C-O bond scission, are observed. Theoretical calculations suggest that the differences in the C-O/O-H bond breaking processes are the result of steric factors enforced upon the diols by the second Ti-bound OH group. Above ∼400 K, a new stable intermediate centered on the bridging oxygen (Ob) row is observed. Combined experimental and theoretical evidence shows that this intermediate is most likely a new dioxo species. Further annealing leads to sequential C-Ob bond cleavage and alkene desorption above ∼500 K. Simulations demonstrate that the sequential C-Ob bond breaking process follows a homolytic diradical pathway, with the first C-Ob bond breaking event accompanied with a nonadiabatic electron transfer within the TiO2(110) substrate.