Organophophorous Ester Degradation by Chromium(III) Terephthalate Metal-Organic Framework (MIL-101) Chelated to N,N-Dimethylaminopyridine and Related Aminopyridines
ARMY NATICK SOLDIER RESEARCH DEVELOPMENT AND ENGINEERING CENTER MA
Pagination or Media Count:
Porous materials based on chromiumIII terephthalate metal organic frameworks MOF MIL-101Cr and their complexes with dialkylaminopyridines DAAP were synthesized via a DAAP-MOF complexation, and tested for hydrolytic degradation of organophosphorous esters such as diethyl 4-nitrophenyl phosphate paraoxon. Elemental analysis, TGA, XRD, FT-IR, TEM, SEM, and nitrogen adsorption measurements indicated that the DAAP units were incorporated into MIL-101 pores by complexation, keeping the parent framework intact. The DAAP-MOF enabled facile paraoxon hydrolysis in wateracetonitrile mixtures under ambient conditions 100 conversion after 24 h at pH 10. The MOF-DAAP complexes showed synergistic effects, being 7-fold and 47-fold more active than the parent MIL-101 or DAAP materials, respectively. The high hydrolysis reaction turnover was realized by simultaneous action of the Lewis acid CrIII center of the MOF as well as the electron-rich nucleophile, DAAP. This study demonstrates a simple and efficient method of generating catalytically active MOF materials for environmental detoxification as well as defensive applications.
- Inorganic Chemistry
- Organic Chemistry
- Physical Chemistry
- Metallurgy and Metallography