Decomposition of guaiacol on a subnanometric platinum cluster: a DFT investigation followed by microkinetic analysis

The use of biomass as renewable feedstock for commodity chemicals may largely benefit from the successful development and application of heterogeneous catalysts for decomposition processes. The present investigation combines density functional theory and Christiansen-like microkinetic analysis to describe, at the atomistic level, the mechanisms related to the conversion of oxygenated biomass compounds to deoxygenated and semi-saturated hydrocarbons on a subnanometric Pt10 cluster. The DFT calculations and the kinetic analysis based on the evaluated free energy variations, associated with both elementary step barriers and rearrangement/desorption processes occurring on the cluster, suggest that benzene is the preferred product, together with a compound still bearing oxygen, cyclopentadienone, which would form as a minor product only at high temperature. Other than highlighting the role of the peculiar interaction between carbon and platinum, the reported investigation underlines the importance of cluster fluxionality and reorganization ability in promoting catalyzed reactions.