Rational Design of a Zr-MOF@Curli-Polyelectrolyte Hybrid Membrane toward Efficient Chemical Protection, Moisture Permeation, and Catalytic Detoxification.

Developing high-performance protective materials is important for soldiers and civilians who are exposed to the atmosphere of highly toxic chemical warfare agents (CWAs). Polyelectrolyte membranes are promising candidates with excellent chemical resistance and moisture permeability, but they cannot efficiently degrade CWAs. Here, we design and prepare a hybrid membrane through growth of catalytically active zirconium-based metal-organic frameworks (Zr-MOFs) on a polyelectrolyte membrane mediated by biofilm-inspired curli nanofibers (CNFs). Superior to the bare polyelectrolyte membrane, the prepared MOF-808@CNF-PQ hybrid membrane exhibits improved rejection of the nerve agent simulant dimethyl methyl phosphonate (DMMP) vapor and permeation of the water vapor by 113 and 45%, respectively. The water/DMMP selectivity of the hybrid membrane reaches 498.6, approximately 13 times that of the commercial polyelectrolyte membrane Nafion 117. In addition, the hybrid membrane possesses appreciable catalytic activity for the hydrolysis of the nerve agent simulant dimethyl 4-nitrophenyl phosphate (DMNP) with a half-life of ∼38 min. Nanomechanical characterization results based on atomic force microscopy (AFM) techniques demonstrate the critical role of CNFs in mediating Zr-MOF nucleation and the dominant effect of electrostatic interactions on self-assembly of CNFs on polyelectrolyte base. It is also confirmed that the Zr-MOF toppings serve as the key components in physically adsorbing and chemically degrading the DMNP molecules through multiple strong intermolecular interactions. Our work offers a rational strategy to develop advanced membranes toward efficient chemical protection, moisture permeation, and catalytic detoxification against CWAs.