Co₉ S₈ @CN Composites Obtained from Thiacalix[4]arene-Based Coordination Polymers for Supercapacitor Applications

Metal sulfides have been recognized as promising electrodes for electrochemical energy storage owing to their remarkable electrochemical properties. Here, we demonstrate the preparation of Co₉ S₈ nanoparticles anchored on a carbon matrix (denoted as Co₉ S₈ -X@CN (X=1, 2)) from precursor sources, two 1D infinite coordination polymers 1 and 2. The two polymers were assembled by linking Co₄ -TC4A secondary building blocks (SBUs) with ligands L₁ and L₂ , respectively (H₄ TC4A=p-tert-butylthiacalix[4]arene, L₁ =1,4-bis(2H-tetrazol-5-yl)benzene, L₂ =1,3-bis(2H-tetrazol-5-yl)benzene). The composites obtained from 1D polymers showed different morphologies, that is, the Co₉ S₈ nanoparticles of Co₉ S₈ -1@CN are octahedral with a size of ca. 140 nm, while the lamellar Co₉ S₈ nanoparticles in Co₉ S₈ -2@CN possess different sizes (50-150 nm). The Co₉ S₈ -2@CN immobilized on nickel foam (Co₉ S₈ -2@CN/NF) show better supercapacitive performance than that of Co₉ S₈ -1@CN. Co₉ S₈ -2@CN showed exceptionally high activities, combining higher specific capacitances (445.2 F g^-1 at 2 A g^-1 and 393.9 F g^-1 and 5 A g^-1 ), rate capacity (94.5% retention at 2 A g^-1 ), and long-term stability (79.2% retention at 5 A g^-1 over 1000 cycles). The smaller size and larger BET surface area of Co₉ S₈ -2@CN nanoparticles can improve the electrical conductivity and provide facile pathways for charge transport, thus leading to conspicuous electrochemical performance of Co₉ S₈ -2@CN compared with its Co₉ S₈ -1@CN counterpart.