Covalent Graphene‐Metal–Organic Polyhedra Hybrids: Triboelectric Nanogenerators for Next Generation of Wearable E‐Skin Technologies

Abstract The development of stretchable energy‐harvesting devices that convert mechanical stimuli into electrical energy is crucial for advancing self‐powered electronic skin (e‐skin) technologies. Triboelectric nanogenerators (TENGs) show promise but suffer from low stretchability, limited conductivity, and poor mechanical durability. Here, we report a new generation of TENGs designed via the molecular chemistry of metal–organic polyhedra (MOPs) covalently bonded to functionalized 2D nitrogen‐doped graphene sheets (NG@MOP). The resulting NG@MOP hybrids, featuring aromatic regions and surface amine groups, link to anionic nickel‐based MOPs, [Ni ₈ (HImDC) ₁₂ ] ^8‐ , through amide bonds. This hybrid exhibits a large surface area, hierarchical micro–mesoporous channels, and structural defects, improving mechanical resilience. Incorporating NG@MOP into a polyurethane matrix produces a highly stretchable, biocompatible film withstanding over 500% strain. The composite delivers excellent triboelectric output, generating 417 V and 10.8 µA at 5 wt % loading. Applied as a wearable e‐skin, the device maintains functionality under extreme deformation, demonstrating a strain sensitivity of 13 mV per degree of motion. It efficiently detects subtle body motions such as bending and stretching, showing strong potential for wearable motion sensing and real‐time health monitoring.