Surface Coordination Modulated Morphological Anisotropic Engineering of Iron-Benzoquinone Frameworks for Lithium-Ion Batteries

Angew Chem Int Ed Engl. 2024 Jul 22;63(30):e202405066. doi: 10.1002/anie.202405066. Epub 2024 Jun 19.

Abstract

Morphological anisotropic engineering is powerful to synthesize metal-organic frameworks (MOFs) with versatile physicochemical properties for diverse applications ranging from gas storage/separation to electrocatalysis and batteries, etc. Herein, we developed a carbon substrate guided strategy to manipulate the facet-dependent coordination for morphology engineering of Fe-THBQ (tetrahydroxy-1,4-benzoquinone) frameworks, which is built with cubic Fe octamer bridged by two parallel THBQ ligands along three orthogonal axes, extending to a three-dimensional (3D) framework with pcu-e network topology. The electronegative O-containing functional groups on carbon surfaces compete with THBQ linkers to selectively interact with the unsaturated coordinated Fe cations on the {111} facets and inhibit crystal growth along the <111> direction. The morphology of Fe-THBQ evolves from thermodynamically favored truncated cube to cuboctahedron depending on the content of O-containing functional groups on the carbon substrate. The Fe-THBQ with varied morphologies exhibits facet-dependent performances for electrochemical lithium storage. This work will shed light on the morphology modulation of MOFs for promising applications.

Keywords: Anisotropy; Coordination chemistry; Lithium-ion batteries; Metal–organic frameworks; Morphological Engineering.