Tenon‐and‐Mortise Structure‐Inspired MOF/PVDF Composites with Enhanced Piezocatalytic Performance via Dipole‐Engineering Strategy

Abstract Fabricating poly(vinylidene fluoride) (PVDF) and its composite ferroelectrics are essential for the development of next‐generation lightweight, portable, wearable, and implantable intelligent devices. However, integrating and maximizing spontaneous polarization and interfacial electromechanical conversion efficiency remain major challenges in the contemporary PVDF‐based composites field. Herein, inspired by the tenon‐and‐mortise structure associated with ancient Chinese architecture, an amino‐anchored metal–organic framework (MOF)/PVDF piezoelectric composite using a dipole‐engineering strategy to deliver enhanced piezocatalytic performance is constructed. Homogeneous and long‐range ordered hydrogen‐bond networks have been formed with the PVDF matrix after introducing periodically arranged amino anchors into the NH ₂ ‐HU MOF. The NH ₂ ‐HU _10wt% /PVDF composite exhibits a 40% greater β‐phase content and a remnant polarization value more than 550% higher than that of the bare PVDF fibers. These amino anchors synergistically enhance both the local electric field and collaborative dipole alignment resulting in a piezocatalytic bactericidal performance of 97.4% when irradiated under clinical ultrasound conditions. Moreover, the enhanced polarizability within the MOF/PVDF composite simultaneously improves its responsiveness to X‐rays via its periodic amino anchoring networks, thereby doubling CT imaging efficacy for implants at lower voltages. Integrating piezoelectric MOFs and polymer matrices through molecular design presents a viable approach for optimizing ferroelectric properties and expanding piezoelectric‐composite applications.