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.

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.

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We present a new implementation of ion imaging for the study of surface scattering processes. The technique uses a combination of spatial ion imaging with laser slicing and delayed pulsed extraction. The scattering velocities of interest are parallel to the imaging plane, allowing speed and angular distributions to be extracted from a single image. The first results of direct scattering of N2 from a clean, single-crystal Au(111) surface are reported, and the speed resolution is shown to be competitive with current state-of-the-art time-of-flight methods for velocity measurements while providing simultaneous measurements of in-plane angular distributions.