Coordination‐Driven Direct Conversion of Layered Metal Borides Into Borophene/MOF Heterostructures

ABSTRACT Engineering robust two‐dimensional material/metal‐organic framework (MOF) heterostructures with well‐defined interfaces remains challenging, largely because conventional routes depend on sequential etching, exfoliation, and self‐assembly steps that are inefficient, reagent‐consuming, and prone to damage the two‐dimensional components. Exposure to oxygen and aqueous media during these processes often induces surface oxidation and nanosheet fragmentation, severely limiting the functional advantages of the resulting hybrids. Here, we develop a coordination‐driven conversion strategy that enables the single‐step construction of borophene (BP)/MOF heterostructures from layered metal borides. With formic acid serving as a catalytic coordination modulator, the metal layers are selectively reconstructed into MOF domains while the intrinsic boron network is simultaneously exfoliated, enabling a broadly applicable, atom‐efficient transformation with a yield up to 95%. The representative BP/Al‐PMOF heterostructure features a mutually reinforcing interface, where BP improves MOF conductivity and the MOF matrix protects BP from oxidation. This interfacial synergy enables exceptional room‐temperature NO 2 sensing with a strong response and fast detection.