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Instantaneous Hydrolysis of Nerve-Agent Simulants with a Six-Connected Zirconium-Based Metal–Organic Framework
Summary:
The authors from Northwestern University developed a six-connected zirconium-based metal–organic framework (MOF-808) featuring ultra-high catalytic activity and aqueous stability, achieving rapid and complete hydrolysis of nerve-agent simulants (DMNP) within 30 s under ambient conditions.
Background:
1. To address the slow hydrolysis of chemical warfare agents, previous researchers explored activated carbons, metal oxides, Al-porphyrin catalysts and 12-/8-connected Zr-MOFs, achieving half-lives down to 1.5 min, yet throughput, capacity or node accessibility remained limiting.
2. The authors now propose lowering node connectivity to 6, maximizing open Zr sites and aquo/hydroxo ligands, and obtain instantaneous hydrolysis with a reusable plug-flow membrane reactor.
Research Content:
1. Synthesis: MOF-808 was solvothermally assembled from ZrOCl₂, benzene-1,3,5-tricarboxylate (BTC) and formic acid in DMF, followed by activation to remove formate and create Zr₆(µ₃-O)₄(µ₃-OH)₄(H₂O)₆(OH)₆ nodes.
2. Characterizations:
1) BET surface area ~1 800 m² g⁻¹; micro/meso-pores 4.8 & 18 nm.
2) SEM/DLS show 200–350 nm octahedral particles.
3) Variable-temp PXRD (to 250 °C), DRIFTS, ¹H NMR, N₂ isotherms confirm crystallinity, pore integrity and complete formate removal; ICP proves no Zr leaching (<1 ppb).
3. Application: 0.3–1.5 µmol MOF-808 quantitatively hydrolyzes 25 mM DMNP in ≤30 s (t₁/₂ <0.5 min, TOF >1.4 s⁻¹); a 5 mg membrane plug-flow reactor delivers ≥93 % conversion for 10 mL agent solution at 0.1 mL min⁻¹ and is fully regenerable by water wash.
4. Mechanism: High density of labile water/hydroxide ligands on low-connectivity Zr₆ nodes act as Brønsted acids and nucleophile generators, mimicking phosphotriesterase Zn-OH-Zn sites; large 18 nm channels ensure rapid DMNP diffusion to interior nodes, enabling heterogeneous catalysis without linker defects.
Outlook:
This work establishes six-connected Zr-MOFs as the fastest known heterogeneous catalysts for nerve-agent neutralization, provides a scalable filtration-reactor prototype for protective gear, and points toward tuning node hydration/acidity for next-generation detoxification materials.
Instantaneous Hydrolysis of Nerve-Agent Simulants with a Six-Connected Zirconium-Based Metal–Organic Framework
Authors: Su-Young Moon, Yangyang Liu, Joseph T. Hupp, Omar K. Farha
DOI: 10.1002/anie.201502155
Link: https://onlinelibrary.wiley.com/doi/10.1002/anie.201502155
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