Two new polyoxometalate (POM)-based three-dimensional metal organic carbene frameworks, [Ag(trz)(HO)][HPWO] (POMs@MCNCs-1) and [Ag(trz)(HO)][HSiWO] (POMs@MCNCs-2), were hydrothermally synthesized, in which Keggin-type polyoxoanions as templates induce the formation of two different kinds of metal-carbene nanocages (MCNCs) for the first time. Combination of the reversible multielectron redox behavior and electron storage functions of POMs with the good electrical conductivity of the single-walled carbon nanotubes (SWNTs) renders the POMs@MCNCs-1/SWNT composite excellent electrochemical performance and good stability as anode materials of lithium-ion batteries, with up to 2000 mA h g for the first discharge capacity and ca. 859 mA h g for the second cycle at a current density of 100 mA g. The successful fabrication of unprecedented MCNCs into the POM-based three-dimensional metal-organic frameworks in the present work must initiate extensive research interests in diverse fields.
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