Structural and Proton Conduction Modifications in RbH2PO4 Crystals upon Heating Under Different Environments

We used synchrotron X-ray diffraction (XRD) and ac-impedance spectroscopy (AIS) to uncover the structural and chemical modifications undergone by RbH2PO4 (RDP) at intermediate temperatures (150 °C < T < 300 °C) and investigate their relationship with RDP’s proton conductivity, σ. Nyquist plots collected on RDP samples sealed in a small volume (~50 mL) of dry air show a gradual increase in σ upon heating from 180 to 260 °C, but not the three-order-of-magnitude superprotonic jump observed in the Cs-based compound CsH2PO4 (CDP) within the same temperature range. Correspondingly, XRD measurements using synchrotron radiation (λ = 0.922 Å) on RDP crystalline powders sealed in a quartz capillary exhibit no evidence of a monoclinic-to-cubic superprotonic phase transition like the one observed in CDP. Instead, these temperature-resolved powder XRD patterns demonstrate that the intermediate-temperature RDP monoclinic phase (P21/m, a = 7.733 Å, b = 6.189 Å, c = 4.793 Å, and β = 109.21 deg) persists up to the melting point of the title compound. Our most significant finding comes from heating RDP under high pressure (P = 1 GPa), which leads to markedly different structural behavior. Indeed, our full profile refinements against XRD data collected on RDP crystals compressed at ~1 GPa show evidence of a polymorphic phase transition (at Tc = 300 °C) to a high-temperature cubic phase (Pm-3m, a = 4.784 Å) that is isomorphic with its CDP counterpart. This is significant, as it indicates that the superprotonic conduction in phosphate solid acids is not cation-specific, and a general highly efficient proton conduction mechanism is present in the high-temperature phases of these materials.