Degradation of Glyphosate to Benign N-Formyl Glycine Using MOF-808 Nanocrystals

JHAIR A. PEÑA PRADA; TATIANA A. HUERTAS NAVARRO; STEPHANIE L. CHUA; ALEJANDRO M. GRANADOS; CHIH-WEN PAO; ALEJANDRO M. FRACAROLI; NICHOLAS M. BEDFORD

Angewandte Chemie

WILEY-V C H VERLAG GMBH

Lugar: Weinheim; Año: 2025

1433-7851

Glyphosate (N-phosphonomethyl glycine, GPh) is an industrial herbicide used worldwide in modern agriculturalpractices. With the growing concerns about cumulative environmental and health effects, pathways for catalytic GPhdegradation to benign products are becoming a pressing societal need. This report demonstrates that Zr-based metal–organic framework (MOF-808) with different crystal sizes and designed defect sites can be employed as an efficientheterogeneous catalyst for the complete degradation of GPh at room temperature. Importantly, the degradation mechanismproduces N-formyl glycine and hydroxymethyl-phosphonate, which are largely innocuous chemicals, especially whencompared to more common decomposition products that typically result in GPh degradation. Nanocrystalline MOF-808(nMOF-808) exhibits enhanced reactivity than larger MOF-808 crystals, attributed to the higher coordination of hydroxyland water molecules to the secondary building units (SBU) as determined using a range of X-ray absorption spectroscopy(XAS) techniques. These studies indicate that the crystal size-dependency in GPh degradation is related to structuralmodifications on coordinative unsaturated Zr site that promote the fast exchange of weakly bonded ligands. Taken together,this study demonstrates that GPh degradation can be optimized through ligand field tuning in MOFs, which can helpimprove overall reactivity while also pushing the reaction toward desirable, nontoxic products.