Despite tremendous efforts having been made in the exploration of new high-performance proton-conducting materials, systems with superprotonic conductivity higher than 10−1 S·cm−1 are scarcely reported. We show here the utilization of bridging uranyl oxo atoms, traditionally termed cation–cation interaction (CCI), as the hydrogen bond acceptor to build a dense and ordered hydrogen bond network, affording a unique uranyl-based proton-conducting coordination polymer (H3O)4UO2(PO4)2 (HUP-1). This compound contains a densely connected hydronium network that is substantially stabilized by uranyl oxo atoms and exhibits high proton conductivities over a wide temperature range. At 98 °C, 98% relative humidity, a superprotonic conductivity of 1.02 × 10−1 S·cm−1 is observed for the system, one of the highest values reported for a solid-state proton-conducting material. This property originates from the thermally induced phase transformation from HUP-1 to another uranyl compound also with a CCI bond, (H3O)UO2PO4·(H2O)3 (HUP-2), accompanied by the partial generation of phosphorus acid that is further trapped in the structure of HUP-2, demonstrated by solid-state NMR analysis. The superprotonic conductivity of H3PO4@HUP-2 is persistent under the testing condition.
Synthesis, Structure and Diffusion Pathways of Fast Lithium-Ion Conductors in the Polymorphs α- and β-Li8SnP4