Heterometallic Titanium-Organic Frameworks as Dual-Metal Catalysts for Synergistic Non-buffered Hydrolysis of Nerve Agent Simulants

Castells-Gil, Javier; Padial, Natalia M.; Almora-Barrios, Neyvis; Gil-San-Millan, Rodrigo; Romero-Angel, Maria; Torres, Virginia; da Silva, Ivan; Vieira, Bruno C. J.; Waerenborgh, Joao C.; Jagiello, Jaciek; Navarro, Jorge A. R.; Tatay, Sergio; Marti-Gastal

Publicación: CHEM
2020
VL / 6 - BP / 3118 - EP / 3131
abstract
Mixed-metal or heterometallic metal-organic frameworks (MOFs) are gaining importance as a route to produce materials with increasing chemical and functional complexities. We report a family of heterometallic titanium frameworks, MUV-101(M), and use them to exemplify the advantages of controlling metal distribution across the framework in heterogeneous catalysis by exploring their activity toward the degradation of a nerve agent simulant of Sarin gas. MUV-101(Fe) is the only pristine MOF capable of catalytic degradation of diisopropyl-fluorophosphate (DIFP) in non-buffered aqueous media, This activity cannot be explained only by the association of two metals, but to their synergistic cooperation, to create a whole that is more efficient than the simple sum of its parts. Our simulations suggest a dual-metal mechanism reminiscent of bimetallic enzymes, where the combination of Ti(IV) Lewis acid and Fe(III)- -OH Bronsted base sites leads to a lower energy barrier for more efficient degradation of DIFP in absence of a base.

Access level

Bronze, Green submitted