RESUMO
The rutile TiO2(110) surface has long-served as a well-characterized, prototypical transition-metal oxide surface used in heterogeneous catalysis and photocatalytic water splitting. Naturally occurring defects on this surface, called bridging-oxygen (BO) vacancies, are important as they determine the overall reactivity of the surface. Herein, we report a bias-dependent, scanning tunneling microscopy (STM) signature of the BO vacancies on TiO2(110): for sample bias voltages past a threshold of +3 V, the bright vacancies are flanked on either side (along the oxygen row) by two dark spots approximately shaped like half-moons. The BO vacancies have a bright aspect below the threshold bias also but are not surrounded by half-moon dark depressions. Using generalized gradient approximation calculations with Hubbard correction (GGA + U) for projected density of states (DOS) and simulated STM images, we find that the bias-dependent STM signature originates from (i) local DOS maxima of all BOs (lighter background that occurs above the threshold bias) and (ii) the increased separation between the first and second BO atoms neighboring the vacancy which leads to an apparent dip between these neighboring oxygens. These results offer a new striking example of the STM signature that appears without switching the polarity of the bias. Similar approaches can be employed for seeking distinguishing features on the surfaces of other large band gap semiconductors and insulators.
RESUMO
Nanostructured noble-metal catalysts traditionally suffer from sintering under high operating temperatures, leading to durability issues and process limitations. The encapsulation of nanostructured catalysts to prevent loss of activity through thermal sintering, while maintaining accessibility of active sites, remains a great challenge in the catalysis community. Here, we report a robust and regenerable palladium-based catalyst, wherein palladium particles are intercalated into the three-dimensional framework of SBA-15-type mesoporous silica. The encapsulated Pd active sites remain catalytically active as demonstrated in high-temperature/pressure phenol hydrodeoxygenation reactions. The confinement of Pd particles in the walls of SBA-15 prevents particle sintering at high temperatures. Moreover, a partially deactivated catalyst containing intercalated particles is regenerated almost completely even after several reaction cycles. In contrast, Pd particles, which are not encapsulated within the SBA-15 framework, sinter and do not recover prior activity after a regeneration procedure.
RESUMO
The design and synthesis of shape-directed nanoscale noble metal particles have attracted much attention due to their enhanced catalytic properties and the opportunities to study fundamental aspects of nanoscale systems. As such, numerous methods have been developed to synthesize crystals with tunable shapes, sizes, and facets by adding foreign species that promote or restrict growth on specific sites. Many hypotheses regarding how and why certain species direct growth have been put forward, however there has been no consensus on a unifying mechanism of nanocrystal growth. Herein, we develop and demonstrate the capabilities of a mathematical growth model for predicting metal nanoparticle shapes by studying a well known procedure that employs AgNO3 to produce {111} faceted Pt nanocrystals. The insight gained about the role of auxiliary species is then utilized to predict the shape of Pd nanocrystals and to corroborate other shape-directing syntheses reported in literature. The fundamental understanding obtained herein by combining modeling with experimentation is a step toward computationally guided syntheses and, in principle, applicable to predictive design of the growth of crystalline solids at all length scales (nano to bulk).
