Teck L. Tan

A Comprehensive Search for Stable Pt-Pd Nanoalloy Configurations and Their Use as Tunable Catalysts

Using density-functional theory, we predict stable alloy configurations (ground states) for a 1 nm Pt-Pd cuboctahedral nanoparticle across the entire composition range and demonstrate their use as tunable alloy catalysts via hydrogen-adsorption studies. Unlike previous works, we use simulated annealing with a cluster expansion Hamiltonian to perform a rapid and comprehensive search that encompasses both high and low-symmetry configurations. The ground states show Pt(core)-Pd(shell) type configurations across all compositions but with specific Pd patterns. For catalysis studies at room temperatures, the ground states are more realistic structural models than the commonly assumed random alloy configurations. Using the ground states, we reveal that the hydrogen adsorption energy increases (decreases) monotonically with at. % Pt for the {111} hollow ({100} bridge) adsorption site. Such trends are useful for designing tunable Pd-Pt nanocatalysts for the hydrogen evolution reaction.

Configurational Thermodynamics of Alloyed Nanoparticles with Adsorbates

Changes in the chemical configuration of alloyed nanoparticle (NP) catalysts induced by adsorbates under working conditions, such as reversal in core-shell preference, are crucial to understand and design NP functionality. We extend the cluster expansion method to predict the configurational thermodynamics of alloyed NPs with adsorbates based on density functional theory data. Exemplified with PdRh NPs having O-coverage up to a monolayer, we fully detail the core-shell behavior across the entire range of NP composition and O-coverage with quantitative agreement to in situ experimental data. Optimally fitted cluster interactions in the heterogeneous system are the key to enable quantitative Monte Carlo simulations and design.