Abstract:
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The frontiers between homogeneous and heterogeneous catalysis are progressively disappearing. The decoration
of transition metal nanoparticles (NPs) with ligands, also known as surface modifiers or capping
agents, primarily allows NP size control but dramatically impacts activity and selectivity in catalysis. Computational
tools have shown their capability of providing insight at atomic level in both homogeneous and
heterogeneous areas but, due to the complexity of these interfaces, the underlying reaction mechanisms
are often not described and certainly not well understood. In this mini-review, we describe the main challenges
in modelling and survey the most recent computational studies that emphasise the role of ligands in
tuning catalytic performance. We focus on density functional theory (DFT) simulations of the interfaces between
transition metals (ruthenium, palladium, platinum, gold) and organic ligands (NHC, amine, phosphine,
thiol), surfactants, and ionic liquids. Revealing the reaction pathways that operate at this hidden
interface between homogeneous and heterogeneous worlds will provide guiding rules to design new systems
that circumvent linear scaling relationships and foster a unified theory of catalysis. |