Operando Effects on the Structure and Dynamics of
Pt<i><sub>n</sub></i>Sn<sub><i>m</i></sub>/γ-Al<sub>2</sub>O<sub>3</sub> from Ab Initio Molecular Dynamics and X‑ray
Absorption Spectra
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Abstract
Alumina-supported
Pt–Sn nanocluster catalysts are widely
used in reforming processes, yet a theoretical understanding of their
structure and function is far from complete. In an attempt to elucidate
their behavior under operando conditions, we have carried out a detailed
investigation of nanoscale bimetallic clusters of Pt and Sn supported
on γ-Al<sub>2</sub>O<sub>3</sub> using a combination of finite
temperature ab initio molecular dynamics and theoretical X-ray absorption
spectroscopy (XAS). Our simulations reveal a rich nonequilibrium structure
over several time scales, with vibrational and anomalous structural
disorder and fluctuating charge transfer to the support. In contrast
with bulk Pt–Sn materials, the clusters are found to be markedly
inhomogeneous, with substantial differences between surface and internal
structure. The Sn atoms are preferentially segregated to the surface
and fluctuate between different Pt bonds over a picosecond time scale.
Importantly, these properties show how an improved XAS analysis of
these systems should take into account both their inhomogeneity and
dynamic structural disorder. Although our study is limited to small
nanoclusters due to the limitations of ab initio molecular dynamics,
we argue that their unusual dynamical structure also has important
implications for catalytic behavior of these systems, which is briefly
illustrated by the adsorption and dissociation reactivity of H<sub>2</sub>