Self-supported microporous zirconium hydroxide nanofibrous with ultrahigh surface area for efficient chemical warfare agent degradation

Benefiting from strong Lewis acidic Zr 4+ sites and abundant surface-active hydroxyl groups, Zr(OH) 4 exhibits excellent degradation performance against chemical warfare agents (CWAs). However, conventional fiber-based composite systems suffer from low loading capacities and inadequate specific surface areas, which limits their application in flexible protective gear. To address this, this study proposes an in situ transformation strategy on ZrO 2 fibers to construct ultra-high surface area Zr(OH) 4 nanofibers. Through the ligand exchange and removal of Zr-MOF precursors under mild conditions, hydroxyl-rich porous Zr(OH) 4 nanoparticles are successfully prepared. The resulting material achieves a remarkably high specific surface area of 819 m 2 g −1 , breaking the surface area bottleneck of traditional precipitation methods. Furthermore, by utilizing ZrO 2 fibers as the substrate, flexible and free-standing Zr(OH) 4 nanofibers (ZHNF) are successfully fabricated via in situ growth, retaining a high specific surface area of 418 m 2 g −1 . This work systematically investigates the heterogeneous nucleation conditions of Zr-MOFs anchored on the fiber surface, alongside the ligand exchange-driven formation mechanism of microporous Zr(OH) 4 , which achieves strong interfacial bonding between the Zr(OH) 4 and the fiber substrate. Owing to the abundant surface hydroxyls and a high specific surface area, ZHNF shortens the degradation half-life against the CWA simulant CEES to approximately 25 min, while exhibiting outstanding stability. Ultimately, this work not only provides a viable approach for integrating Zr(OH) 4 into flexible protective equipment, but also offers valuable guidance for the design of novel Zr-based porous catalytic materials.