Polyoxometalate-Bridged Synthesis of Superstructured Mesoporous Polymers and Their Derivatives for Sodium–Iodine Batteries

Despite the impressive progress in mesoporous materials over past decades, for those precursors having no well-matched interactions with soft templates, there are still obstacles to be guided for mesoporous structure via soft-template strategies. Here, a polyoxometalate-assisted co-assembly route is proposed for controllable construction of superstructured mesoporous materials by introducing polyoxometalates as bifunctional bridge units, which weakens the self-nucleation tendency of the precursor through coordination interactions and simultaneously connects the template through the induced dipole–dipole interaction. By this strategy, a series of meso-structured polymers, featuring highly open radial mesopores and dendritic pore walls composed of continuous interwoven nanosheets can be facilely obtained. Further carbonization gave rise to nitrogen-doped hierarchical mesoporous carbon decorated uniformly with ultrafine γ-Mo₂N nanoparticles. Density functional theory proves that nitrogen-doped carbon and γ-Mo₂N can strongly adsorb polyiodide ions, which effectively alleviate polyiodide dissolving in organic electrolytes. Thereby, as the cathode materials for sodium–iodine batteries, the I₂-loaded carbonaceous composite shows a high specific capacity (235 mA h g⁻¹ at 0.5 A g⁻¹), excellent rate performance, and cycle stability. This work will open a new venue for controllable synthesis of new hierarchical mesoporous functional materials, and thus promote their applications toward diverse fields.