High‐Valence Mn MOF Inspired by Laccase Mediators Enables Versatile Nature‐Mimicking Catalysis

Abstract In nature, active Mn 3+ –ligand complexes produced by laccase catalyzed oxidation can act as the low‐molecular mass, diffusible redox mediators to oxidize the phenolic substrates overcoming the limitations of natural enzymes. Learning from the metal–ligand coordination of natural functional units, high‐valence Mn metal–organic framework (Mn MOF) is constructed to simulate the catalysis in natural mediator system. Benefiting from the characteristics of nanoscale size, rich metal coordination unsaturated sites, and mixed valence state dominated by Mn(III), Nano Mn(III)‐TP exhibits superior laccase‐mimicking activity, whose V max (maximal reaction rate) is much higher than that of natural laccase. Referring to natural systems, relevant free radical experiments prove that the material induces the production of active oxygen species with the assistance of carboxylic acid, and active oxygen species further oxidize phenolic substrates. Based on its robust performances, the primary oxidative degradation of an emerging pollutant triclosan (TCS) is creatively applied, an important antiasthmatic medicine terbutaline sulfate (TBT) detection, and the synthesis of non‐toxic and black near‐natural dyes for dyeing. By simulating the essential mediators of natural enzymatic catalysis, an Mn MOF‐based material that demonstrates multiple novel applications is successfully developed, which introduces a new reliable strategy for achieving versatile nature‐mimicking catalysis.