Molecularly Engineered 2D Xene Heterostructures With Implanted Peroxidase-Like Activity for Mimicking Enzyme Functions

As nature's most refined catalysts, enzymes carry out their functions with outstanding efficiency, making them an inspiring blueprint for the design of artificial catalysts. In this context, 2D nanomaterials and heterostructures that emulate enzyme-like functions (viz. 2D nanozymes) have emerged as promising platforms for catalyzing biologically relevant transformations owing to their high surface area and reduced production costs. Here, we apply molecular engineering to endow enzymatic-like activity on an emerging 2D Xene material, such as allyl germanane (2D-Ge), via electropolymerizing a Co(II)-based molecular catalyst. The resulting 2D-Ge@Co heterostructure exhibits sensitive, selective, and robust electrochemical detection of hydrogen peroxide (H2O2), yielding a micromolar detection limit under physiological conditions. Lastly, its practical applicability is demonstrated by monitoring the in situ generation of H2O2 during an enantiospecific enzymatic reaction, confirming its compatibility with biologically relevant environments. Overall, this work provides a general strategy to molecularly program 2D Xenes by immobilizing tailored molecular catalysts, opening up new opportunities to customize 2D nanozymes for task-specific catalytic applications.