Design and Fabrication of Hierarchical NiCoP–MOF Heterostructure with Enhanced Pseudocapacitive Properties

Abstract Metal–organic framework (MOF)‐derived heterostructures possessing the merits of each component are thought to display the enhanced energy storage performance due to their synergistic effect. Herein, a functional heterostructure (NiCoP–MOF) composed of nickel/cobalt‐MOF (NiCo–MOF) and phosphide (NiCoP) is designed and fabricated via the localized phosphorization of unusual lamellar brick‐stacked NiCo–MOF assemblies obtained by a hydrothermal method. The experimental and computational analyses reveal that such‐fabricated heterostructures possess the modulated electronic structure, abundant active sites, and hybrid crystalline feature, which is kinetically beneficial for fast electron/ion transport to enhance the charge storage capability. Examined as the supercapacitor electrode, the obtained NiCoP–MOF compared to the NiCo–MOF delivers a high capacity of 728 C g −1 (1.82 C cm −2 ) at 1 A g −1 with a high capacity retention of 430 C g −1 (1.08 C cm −2 ) when increasing the current density to 20 A g −1 . Importantly, the assembled solid‐state NiCoP–MOF‐based hybrid supercapacitor displays superior properties regarding the capacity (226.3 C g −1 ), energy density (50.3 Wh kg −1 ), and durability (≈100% capacity retention over 10 000 cycles). This in situ heterogenization approach sheds light on the electronic structure modulation while maintaining the well‐defined porosity and morphology, holding promise for designing MOF‐based derivatives for high performance energy storage devices.