Nanocrystalline metal oxides as destructive adsorbents for organophosphorus compounds at ambient temperatures.
Nanocrystals of magnesium oxide react with organophosphorus compounds at room temperature by dissociative chemisorption, which we term "destructive adsorption". This process involves cleavage of P-O and P-F bonds (but not P-C bonds) and immobilization of the resultant molecular fragments. These ultrafine powders have unusual crystalline shapes and possess high surface concentrations of reactive edge/corner and defect sites, and thereby display higher surface reactivity, normalized for surface area, than typical polycrystalline material. This high surface reactivity coupled with high surface area allows their use for effective decontamination of chemical warfare agents and related toxic substances. Herein data is presented for paraoxon, diisopropylfluorophosphate (DFP), and (CH3CH2O)2P(O)CH2-SC6H5 (DEPTMP). Solid-state NMR and IR spectroscopy indicate that all OR and F groups dissociate; this leaves bound -PO4, -F, and -OR groups for paraoxon, DFP, and DEPTMP, respectively. For paraoxon, it was shown that one monolayer reacts. For DEPTMP, the OR groups dissociate, but not the P-CH2SC6H5 group. The nanocrystalline MgO reacts much faster and in higher capacity than typical activated carbon samples, which physisorb but do not destructively adsorb these phosphorous compounds.
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Shyamala
S
Rajagopalan
Olga
O
Koper
Shawn
S
Decker
Kenneth J
KJ
Klabunde
D000327:Adsorption; D002800:Cholinesterase Inhibitors / Q000737:chemistry / Q000493:pharmacokinetics; D003460:Crystallization; D004787:Environmental Pollution / Q000517:prevention & control; D007306:Insecticides / Q000737:chemistry / Q000493:pharmacokinetics; D007531:Isoflurophate / Q000737:chemistry / Q000493:pharmacokinetics; D008277:Magnesium Oxide / Q000737:chemistry*; D036103:Nanotechnology; D009943:Organophosphorus Compounds / Q000737:chemistry* / Q000493:pharmacokinetics; D010261:Paraoxon / Q000737:chemistry / Q000493:pharmacokinetics; D013696:Temperature
D002800:Cholinesterase Inhibitors; D007306:Insecticides; D009943:Organophosphorus Compounds; D007531:Isoflurophate; D008277:Magnesium Oxide; D010261:Paraoxon