The hydrogen sublattice in hydrated molybdenum trioxides: Insight from multi-energy neutron scattering

Molybdenum oxides have attracted considerable attention in heterogeneous catalysis and energy storage applications owing to the unusual chemical flexibility of the Mo center. Unlike many transition metals, molybdenum can shift between several oxidation states without losing structural integrity, largely due to the stabilizing role of oxo-bridged linkages. This versatility gives rise to an extraordinary diversity of structural motifs that can be tailored for specific catalytic and electrochemical functions. In this study, we investigate the elusive structure and nuclear dynamics of the monohydrate (MoO₃ $·$ H₂O) and dihydrate (MoO₃ $·$  2H₂O) phases of $\beta$ -MoO₃, an important family of precursors for molybdenum oxide-based hybrid materials. We employ a combined experimental and computational approach to explore the local environment and nuclear dynamics of protons in water confined within the interlamellar space of the $\beta$ -MoO₃ layers. High-resolution neutron diffraction confirms the established structure of the dihydrate phase while revealing hydrogen-sublattice disorder in the metastable monohydrate. Complementary computational analysis, including harmonic lattice dynamics and ab initio Born-Oppenheimer molecular dynamics simulations, provides deeper insight into proton confinement in these systems, yielding plausible models of their local structure. These findings further validated through temperature-dependent inelastic neutron scattering and neutron Compton scattering, which probe the vibrational response and proton momentum distributions, respectively. The joint analysis of experimental data and molecular dynamics simulations identifies rotationally bound, orientationally disordered water molecules as the mechanism underlying proton disorder in $\beta$ -MoO₃ $·$ H₂O. Overall, the results reveal pronounced differences in water ordering and proton dynamics between the mono- and dihydrate forms, offering a detailed quantum-mechanical description of the hydrogen behavior in hydrated molybdenum trioxides and highlighting the interplay between the thermal effect and the confinement-induced local proton dynamics.