Polyoxometalate-Incorporated Metallacalixarene@Graphene Composite Electrodes for High-Performance Supercapacitors

Composites of polyoxometalate (POM)/metallacalixarene/graphene-based electrode materials not only integrate the superiority of the individual components perfectly but also ameliorate the demerits to some extent, providing a promising route to approach high-performance supercapacitors. Herein, first, we report the preparations, structures, and electrochemical performance of two fascinating POM-incorporated metallacalixarene compounds [Ag₅(C₂H₂N₃)₆][H₅ ⊂ SiMo₁₂O₄₀] (1) and [Ag₅(C₂H₂N₃)₆][H₅ ⊂ SiW₁₂O₄₀] (2); (C₂H₂N₃ = 1 H-1,2,4-triazole). Single-crystal X-ray diffraction analyses illustrated that both 1 and 2 possess intriguing POM-sandwiched metallacalix[6]arene frameworks. Nevertheless, our investigations, including the electrochemical cyclic voltammetry, galvanostatic charge-discharge tests, and electrochemical impedance spectroscopy, reveal that the oxidation ability of the Keggin ions is a primary effect in electrochemical performance of these POM-incorporated metallacalixarene compounds. Namely, the electrodes containing Mo as metal atoms in the Keggin POM shows much higher capacitance than the corresponding W-containing ones. Moreover, compound 1@graphene oxide (GO) composite electrodes are fabricated and systematically explored for their supercapacitor performance. Thanks to the synergetic effects of GO and POM-incorporated metallacalixarenes, the compound 1@15%GO-based electrode exhibits the highest specific capacitance of up to 230.2 F g^-1 (current density equal to 0.5 A g^-1), which is superior to majority of the reported POM-based electrode materials.