Predicting the Energetics of Hydrogen Intercalation in Metal Oxides Using Acid-Base Properties

The ability to predict intercalation energetics from first principles is attractive for identifying candidate materials for energy storage, chemical sensing, and catalysis. In this work, we introduce a computational framework that can be used to predict the thermodynamics of hydrogen intercalation in tungsten trioxide (WO₃). Specifically, using density functional theory (DFT), we investigated intercalation energetics as a function of adsorption site and hydrogen stoichiometry. Site-specific acid-base properties determined using DFT were used to develop linear structure screening models that informed a kernel ridge energy prediction model. These regressions provided a series of hydrogen binding energy predictions across stoichiometries ranging from WO₃ to H_0.625WO₃, which were then converted to equilibrium potentials for hydrogen intercalation. Experimental validation using cyclic voltammetry measurements yielded good agreement with the predicted intercalation potentials. This methodology enables fast exploration of a large geometric configuration space and reveals an intuitive physical relationship between acidity, basicity, and the thermodynamics of hydrogen intercalation. Furthermore, the combination of theoretical and experimental results suggests H_0.500WO₃ as a maximum stable stoichiometry for the bronzes that arises from competition with hydrogen evolution rather than the inability of WO₃ to accommodate additional hydrogen. Our experimental results further indicate hydrogen insertion in WO₃ is highly irreversible for low H-stoichiometries, which we propose to be a consequence of the semiconductor-to-metal transition that occurs upon initial H-intercalation. Overall, the agreement between theory and experiment suggests that local acid-base characteristics govern hydrogen intercalation in tungsten trioxide, and this insight can aid the accelerated discovery of redox-active metal oxides for catalytic hydrogenations.