solvothermal-synthesis-mil-96-uio-66-nh2-on-atomic-layer-deposited

Solvothermal Synthesis of MIL-96 and UiO-66-NH<sub>2</sub> on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Metal-organic frameworks (MOFs), which contain reactive metal clusters and organic ligands allowing for large porosities and surface areas, have proven ...

North Carolina State University

The threat associated with chemical warfare agents (CWAs) motivates the development of new materials to provide enhanced protection with a reduced burden. Metal-organic frame-works (MOFs) have recently been shown as highly effective catalysts for detoxifying CWAs, but challenges still remain for integrating MOFs into functional filter media and/or protective garments. Herein, we report a series of MOF-nanofiber kebab structures for fast degradation of CWAs. We found TiO coatings deposited via atomic layer deposition (ALD) onto polyamide-6 nanofibers enable the formation of conformal Zr-based MOF thin films including UiO-66, UiO-66-NH , and UiO-67. Cross-sectional TEM images show that these MOF crystals nucleate and grow directly on and around the nanofibers, with strong attachment to the substrates. These MOF-functionalized nanofibers exhibit excellent reactivity for detoxifying CWAs. The half-lives of a CWA simulant compound and nerve agent soman (GD) are as short as 7.3 min and 2.3 min, respectively. These results therefore provide the earliest report of MOF-nanofiber textile composites capable of ultra-fast degradation of CWAs.

Ultra-Fast Degradation of Chemical Warfare Agents Using MOF-Nanofiber Kebabs.

Metal-organic frameworks (MOFs) are chemically functionalized micro- and mesoporous materials with high surface areas and are attractive for multiple applications including filtration, gas storage, and catalysis. Postsynthetic modification (PSM), via solution or vapor-based techniques, is a way to impart additional complexity and functionality into these materials. There is a desire to shift toward vapor-phase methods in order to ensure more controlled modification and more efficient reagent and solvent removal from the modified MOF material. In this work we explore how the metal precursors titanium tetrachloride (TiCl) and trimethylaluminum (TMA), commonly used in atomic layer deposition, react with UiO-66-NH MOF. Using in situ quartz crystal microbalance (QCM) and Fourier transform infrared spectroscopy (FTIR) at 150 and 250 °C, we find that the ALD precursors react with μ-OH hydroxyl and μ-O bridging oxygen groups on Zr nodes, as well as oxygen from carboxylate linker groups. The reactions occur predominantly at the crystal surface at μ-OH hydroxyl sites, with TiCl exhibiting greater diffusion into the MOF subsurface. FTIR analysis suggests that, at 150 °C, both TiCl and TMA reversibly dehydroxylate the hydroxylated UiO-66-NH, which is accompanied by distortion of the zirconium metal clusters. Finally, we show that TiCl is able to react with the dehydroxylated UiO-66-NH structure, suggesting that TiCl is also able to react directly with the bridging oxygens in the metal clusters or carboxylate groups on the organic ligand. A better understanding of chemical and thermally driven MOF dehydroxylation reactions can be important for improved postsynthetic modification of MOFs.

Reversible Low-Temperature Metal Node Distortion during Atomic Layer Deposition of AlO and TiO on UiO-66-NH Metal-Organic Framework Crystal Surfaces.

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., AlO, ZnO, or TiO) 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-NH MOF crystals solvothermally grown on fiber substrates. Of the materials explored, we find that TiO 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 t = 15 min, 580-fold faster than the catalytic performance of untreated PP textiles. Interestingly, compared to ALD TiO and AlO, 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 Zn 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.

UiO-66-NH Metal-Organic Framework (MOF) Nucleation on TiO, ZnO, and AlO Atomic Layer Deposition-Treated Polymer Fibers: Role of Metal Oxide on MOF Growth and Catalytic Hydrolysis of Chemical Warfare Agent Simulants.

Dennis T. Lee

Department of Chemical and Biomolecular Engineering

North Carolina State University

Solvothermal Synthesis of MIL-96 and UiO-66-NH₂ on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Dennis T. Lee

.css-o250i3{font-size:18px;font-family:Open Sans,sans-serif;line-height:21.6px;}Department of Chemical and Biomolecular Engineering

North Carolina State University

Solvothermal Synthesis of MIL-96 and UiO-66-NH2 on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats

Department of Chemical and Biomolecular Engineering

Solvothermal Synthesis of MIL-96 and UiO-66-NH₂ on Atomic Layer Deposited Metal Oxide Coatings on Fiber Mats