Enzyme–inspired coordination chemistry in confined and interfacial microenvironments: Insights from MOFs and MXenes

Enzyme-inspired coordination chemistry in functional materials plays a pivotal role in controlling molecular recognition, transport, and reactivity, particularly under spatial confinement. This review examines recent advances and applications of metal-centered coordination environments in confined and interfacial microenvironments that mimic metalloenzyme functions. The central focus is on the roles of primary coordination geometry, secondary coordination spheres, and confinement effects in governing electronic structures, substrate binding, and reactions. Metal–organic frameworks (MOFs) and MXenes are explored to elucidate how ordered porous architectures and conductive, chemically active 2D layers independently regulate mass transport, charge transfer, and active-site behavior. This parallel approach enables clear mechanistic comparisons across material platforms. Key highlights include MOFs, multidimensional confined systems with structurally defined metal nodes and tunable ligands, and the MXene platforms. These platforms feature surface terminations that function as inorganic ligands, enabling dynamic coordination environments and charge-regulated transport at 2D interfaces. The review further explores applications of these bio-inspired systems in catalysis, sensing, and biomedicine. By comparing framework-confined and surface-confined environments, this review clarifies the relationships among coordination design, confinement, and reactivity. While acknowledging the emergent nature of this research field, the review addresses prevailing challenges related to stability under confinement, scalability, and practical implementation.