Herein, we report a detailed structural, electric, thermal and optical analysis of a titanium and tantalum phosphate LiNaTiTa P O . The title compound is comprised of typical ReO -type layers constituted by corner-sharing TiO and TaO octahedra, bridged by PO tetrahedra, and the structure is closely related to monophosphate niobium bronzes. The existence of pentagonal tunnels, hosting the Li and Na ions, endows LiNaTiTa P O a moderate ion transportation behavior (4.67×10 S/cm at 823 K). In addition, the successful substitution of Nb for Ta in LiNaTiTa P O results in the optical absorption red-shift towards visible range with a narrowing band gap, which may provide a route of isomorphic replacement to band engineering for photo-catalysis.
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