Catalysts are widely used to increase reaction rates. They function by stabilizing the transition state of the reaction at their active site, where the atomic arrangement ensures favourable interactions . However, mechanistic understanding is often limited when catalysts possess multiple active sites-such as sites associated with either the step edges or the close-packed terraces of inorganic nanoparticles-with distinct activities that cannot be measured simultaneously. An example is the oxidation of carbon monoxide over platinum surfaces, one of the oldest and best studied heterogeneous reactions. In 1824, this reaction was recognized to be crucial for the function of the Davy safety lamp, and today it is used to optimize combustion, hydrogen production and fuel-cell operation. The carbon dioxide products are formed in a bimodal kinetic energy distribution; however, despite extensive study , it remains unclear whether this reflects the involvement of more than one reaction mechanism occurring at multiple active sites. Here we show that the reaction rates at different active sites can be measured simultaneously, using molecular beams to controllably introduce reactants and slice ion imaging to map the velocity vectors of the product molecules, which reflect the symmetry and the orientation of the active site . We use this velocity-resolved kinetics approach to map the oxidation rates of carbon monoxide at step edges and terrace sites on platinum surfaces, and find that the reaction proceeds through two distinct channels: it is dominated at low temperatures by the more active step sites, and at high temperatures by the more abundant terrace sites. We expect our approach to be applicable to a wide range of heterogeneous reactions and to provide improved mechanistic understanding of the contribution of different active sites, which should be useful in the design of improved catalysts.
SHELXL2013 contains improvements over the previous versions that facilitate the refinement of macromolecular structures against neutron data. This article highlights several features of particular interest for this purpose and includes a list of restraints for H-atom refinement.
We describe a new instrument that uses ion imaging to study molecular beam-surface scattering and surface desorption kinetics, allowing independent determination of both residence times on the surface and scattering velocities of desorbing molecules. This instrument thus provides the capability to derive true kinetic traces, i.e., product flux versus residence time, and allows dramatically accelerated data acquisition compared to previous molecular beam kinetics methods. The experiment exploits non-resonant multiphoton ionization in the near-IR using a powerful 150-fs laser pulse, making detection more general than previous experiments using resonance enhanced multiphoton ionization. We demonstrate the capabilities of the new instrument by examining the desorption kinetics of CO on Pd(111) and Pt(111) and obtain both pre-exponential factors and activation energies of desorption. We also show that the new approach is compatible with velocity map imaging.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.