Computational Investigations in Materials and Surface Science: Elucidation of the Reaction Pathway for the Nickel-Catalysed Dehydrogenation of Monomethylamine to Cyanide

Significant Achievements, Anticipated Outcomes and Future Work

The widespread use of amines in industry, together with the technological importance of heterogeneous catalytic processes, lends great significance to the study of amine bonding and reaction on metal surfaces. The adsorption and reaction of monomethylamine, the simplest organic amine, on nickel surfaces has been investigated in this laboratory with photoelectron spectroscopy, providing information on the electronic structure of the adsorption complex and its change during reaction. While it is known that monomethylamine dehydrogenates on nickel to form cyanide, the precise sequence of events taking place during this transformation is unknown. The possible reaction pathways for this transformation are shown below in Figure 1. By performing electronic structure calculations on the various possible intermediates on nickel clusters, and comparison with the experimental data, we hope to identify the key intermediates in this reaction and hence, identify the reaction pathway.

The range of multiplicities nickel is likely to adopt complicates these calculations and the preliminary geometry optimisations have been performed using relatively small (10 atom) clusters. It will be desirable to use these optimised geometries as initial guesses for calculations involving larger clusters. Increasing the cluster size gives a better representation of the conduction and charge transfer processes of the metal bulk, thereby improving the accuracy of the calculations.