Self-templated formation of twin-like metal-organic framework nanobricks as pre-catalysts for efficient water oxidation

Fabrication of single-crystalline metal-organic framework (MOF) hollow nanostructures with two-dimensional (2D) morphologies is a challenging task. Herein, twin-like MOF nanobricks, a quasi-hollow 2D architecture, with multi-metal nodes and replaceable organic ligands, are uniformly and firmly grown on conductive Ni foam through a generic one-pot approach. The formation process of twin-like MOF nanobricks mainly includes selective epitaxial growth of Fe-rich MOF layer and simultaneously dissolution of the pre-formed Ni-rich metal-organic frameworks (MOFs), all of which can be ascribed to a special self-templated mechanism. The fantastic structural merits of twin-like MOF nanobrick arrays, featuring highly exposed active sites, remarkable electrical conductivity, and hierarchical porosities, enable this material for efficient electrocatalysis. Using bimetallic NiFe-MOFs grown on Ni foam as an example, the resultant twin-like nanobrick arrays can be directly utilized as three-dimensional (3D) integrated electrode for high-performance water oxidation in 1 M KOH with a low overpotential, fast reaction kinetics (28.5 mV·dec⁻¹), and superb stability. Interestingly, the unstable NiFe-MOFs were served as an oxygen evolution reaction (OER) pre-catalyst and the single-crystalline NiFe-MOF precursor can be in-situ topochemically regulated into porous and low-crystalline NiFeO_x nanosheets during the OER process. This work extends the hollowing strategy to fabricate hollow MOFs with 2D architectures and highlights their direct utilization for advanced electrocatalysis.