UiO-66-NH₂ Metal–Organic Framework (MOF) Nucleation on TiO₂, ZnO, and Al₂O₃ Atomic Layer Deposition-Treated Polymer Fibers: Role of Metal Oxide on MOF Growth and Catalytic Hydrolysis of Chemical Warfare Agent Simulants

Metal–organic frameworks (MOFs) chemically bound to polymeric microfibrous textiles show promising performance for many future applications. In particular, Zr-based UiO-66-family MOF-textiles have been shown to catalytically degrade highly toxic chemical warfare agents (CWAs), where favorable MOF/polymer bonding and adhesion are attained by placing a nanoscale metal-oxide layer on the polymer fiber preceding MOF growth. To date, however, the nucleation mechanism of Zr-based MOFs on different metal oxides and how product performance is affected are not well understood. Herein, we provide new insight into how different inorganic nucleation films (i.e., Al₂O₃, ZnO, or TiO₂) conformally coated on polypropylene (PP) nonwoven textiles via atomic layer deposition (ALD) influence the quality, overall surface area, and the fractional yield of UiO-66-NH₂ MOF crystals solvothermally grown on fiber substrates. Of the materials explored, we find that TiO₂ ALD layers lead to the most effective overall MOF/fiber adhesion, uniformity, and a rapid catalytic degradation rate for a CWA simulant, dimethyl p-nitrophenyl phosphate (DMNP) with <i>t</i>_1/2 = 15 min, 580-fold faster than the catalytic performance of untreated PP textiles. Interestingly, compared to ALD TiO₂ and Al₂O₃, ALD ZnO induces a larger MOF yield in solution and mass loading on PP fibrous mats. However, this larger MOF yield is ascribed to chemical instability of the ZnO layer under MOF formation condition, leading to Zn²⁺ ions that promote further homogeneous MOF growth. Insights presented here improve understanding of compatibility between active MOF materials and substrate surfaces, which we believe will help advanced MOF composite materials for a variety of useful functions