Current approaches to create zirconium‐based metal–organic framework (MOF) fabric composites for catalysis, water purification, wound healing, gas sorption, and other applications often rely on toxic solvents, long reaction/post processing times, and batch methods hindering process scalability. Here, a novel mechanism was reported for rapid UiO‐66‐NH2synthesis in common low‐boiling‐point solvents (water, ethanol, and acetic acid) and revealed acid–base chemistry promoting full linker dissolution and vapor‐based crystallization. The mechanism enabled scalable roll‐to‐roll production of mechanically resilient UiO‐66‐NH2fabrics with superior chemical protective capability. Solvent choice and segregated spray delivery of organic linker and metal salt MOF precursor solutions allowed for rapid MOF nucleation on the fiber surface and decreased the energy and time needed for post‐processing, producing an activated composite in less than 165 min, far outpacing conventional MOF‐fabric synthesis approaches. The MOF‐fabric hydrolyzed and blocked permeation of the chemical warfare agent soman, outperforming the protection‐standard activated carbon cloth. This work presents both chemical insights into Zr‐MOF powder and fabric composite formation by a rapid, industrially relevant approach and demonstrates its practicality and affordability for high‐performing personal protective equipment.
Ammonia is a widely used toxic industrial chemical that can cause severe respiratory ailments. Therefore, understanding and developing materials for its efficient capture and controlled release is necessary. One such class of materials is 3D porous metal‐organic frameworks (MOFs) with exceptional surface areas and robust structures, ideal for gas storage/transport applications. Herein, interactions between ammonia and UiO‐67‐X (X: H, NH2, CH3) zirconium MOFs were studied under cryogenic, ultrahigh vacuum (UHV) conditions using temperature‐programmed desorption mass spectrometry (TPD‐MS) and in‐situ temperature‐programmed infrared (TP‐IR) spectroscopy. Ammonia was observed to interact with μ3−OH groups present on the secondary building unit of UiO‐67‐X MOFs via hydrogen bonding. TP‐IR studies revealed that under cryogenic UHV conditions, UiO‐67‐X MOFs are stable towards ammonia sorption. Interestingly, an increase in the intensity of the C−H stretching mode of the MOF linkers was detected upon ammonia exposure, attributed to NH−π interactions with linkers. These same binding interactions were observed in grand canonical Monte Carlo simulations. Based on TPD‐MS, binding strength of ammonia to three MOFs was determined to be approximately 60 kJ mol−1, suggesting physisorption of ammonia to UiO‐67‐X. In addition, missing linker defect sites, consisting of H2O coordinated to Zr4+sites, were detected through the formation of
- NSF-PAR ID:
- 10362335
- Publisher / Repository:
- Wiley Blackwell (John Wiley & Sons)
- Date Published:
- Journal Name:
- ChemSusChem
- Volume:
- 15
- Issue:
- 1
- ISSN:
- 1864-5631
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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