A multi-molecular beam/infrared reflection absorption spectroscopy apparatus for probing mechanisms and kinetics of heterogeneously catalyzed reaction from ultrahigh vacuum to near-ambient pressure conditions.

A novel multi-molecular beam/infrared reflection absorption spectroscopy (IRAS) apparatus is described, which was constructed for studying mechanisms and kinetics of heterogeneously catalyzed reactions following a rigorous surface science approach in the pressure range from ultrahigh vacuum (UHV, 1 × 10-10 mbar) to near-ambient pressure (NAP, 1000 mbar) conditions. The apparatus comprises a preparation chamber equipped with standard surface science tools required for the preparation and characterization of model heterogeneous catalysts and two reaction chambers operating at different pressure ranges: in UHV and in the variable pressure range up to NAP conditions. The UHV reaction chamber contains two effusive molecular beams (flux up to 1.

Adsorption and keto-enol-tautomerisation of butanal on Pd(111).

Microscopic-level understanding of the interaction of hydrocarbons with transition metal surfaces is an important prerequisite for rational design of new materials with improved catalytic properties. In this report, we present a mechanistic study on the keto-enol tautomerisation of butanal on Pd(111), which was theoretically predicted to play a crucial role in low-barrier hydrogenation of carbonyl compounds. These processes were addressed by a combination of reflection-absorption infrared spectroscopy, molecular beam techniques and theoretical calculations at the density functional theory level.

Competing Reaction Pathways in Heterogeneously Catalyzed Hydrogenation of Allyl Cyanide: The Chemical Nature of Surface Species.

We present a mechanistic study on the formation of an active ligand layer over Pd(111), turning the catalytic surface highly active and selective in partial hydrogenation of an α,β-unsaturated aldehyde acrolein. Specifically, we investigate the chemical composition of a ligand layer consisting of allyl cyanide deposited on Pd(111) and its dynamic changes under the hydrogenation conditions. On pristine surface, allyl cyanide largely retains its chemical structure and forms a layer of molecular species with the CN bond oriented nearly parallel to the underlying metal.

Understanding Ligand-Directed Heterogeneous Catalysis: When the Dynamically Changing Nature of the Ligand Layer Controls the Hydrogenation Selectivity.

We present a mechanistic study on the formation and dynamic changes of a ligand-based heterogeneous Pd catalyst for chemoselective hydrogenation of α,β-unsaturated aldehyde acrolein. Deposition of allyl cyanide as a precursor of a ligand layer renders Pd highly active and close to 100 % selective toward propenol formation by promoting acrolein adsorption in a desired configuration via the C=O end. Employing a combination of real-space microscopic and in-operando spectroscopic surface-sensitive techniques, we show that an ordered active ligand layer is formed under operational conditions, consisting of stable N-butylimine species.