Abstract: Designing electrocatalysts with optimal activity and selectivity relies on a thorough understanding of the surface structure under reaction conditions. In this study, experimental and computational approaches are combined to elucidate reconstruction processes on low-index Pd surfaces during H-insertion following proton electroreduction. While electrochemical scanning tunneling microscopy clearly reveals pronounced surface roughening and morphological changes on Pd(111), Pd(110), and Pd(100) surfaces during cyclic voltammetry, a complementary analysis using inductively coupled plasma mass spectrometry excludes Pd dissolution as the primary cause of the observed restructuring. Large-scale molecular dynamics simulations further show that these surface alterations are related to the creation and propagation of structural defects as well as phase transformations that take place during hydride formation.

Abstract: The palladium-hydrogen system is a prototype for hydrogen-metal interactions and underpins technologies such as hydrogen storage, catalysis and purification. Yet its nanoscale behaviour - where surface and interface energetics, elastic coherency strain and size-dependent thermodynamics govern phase separation - has eluded accurate atomistic simulation. Empirical potentials misrepresent the energetics of interstitial hydrogen, while existing machine-learning models are restricted to bulk phases at low-hydrogen environments. Here we introduce an atomic cluster expansion (ACE) for Pd-H that reproduces formation energies, phonon spectra, elastic constants, hydrogen migration barriers and surface adsorption with near-DFT accuracy, benchmarked directly against neutron-scattering, high-pressure and lattice-expansion experiments. Its near-linear scaling and CPU efficiency make molecular dynamics of PdH_x nanoparticles exceeding 28,000 atoms (∼12 nm in diameter) tractable over nanosecond timescales. These simulations resolve, at the atomic scale, the kinetic separation of α- and β-PdH_x into a core-shell architecture, reproduce the experimentally observed size dependence of the lattice parameter, and uncover a pronounced hydrogen-induced lowering of the nanoparticle melting temperature. The potential brings experimentally relevant scales of metal-hydride dynamics within quantitative reach.