Reactions of VX, GB, GD, and HD with nanosize Al2O3. Formation of aluminophosphonates

Room-temperature reactions of VX, GB, GD, and HD with nanosize Al2O3 (AP-Al 2O3) have been characterized by P-31, C-13, and Al-27 MAS NMR. Nerve agents VX, GB, and GD hydrolyze to yield surface-bound complexes of their corresp onding nontoxic phosphonates. At sufficiently high loadings, discreet alumi nophosphonate complexes, Al[OP(O)(CH3)OR](3), are generated which are ident ical to synthesized model compounds. Thus the reaction with phosphonic acid s is not just surface-limited, but can continue to the core of alumina part icles. HD mainly hydrolyzes at lower loadings to yield thiodiglycol (TG, 71 %) and a minor amount of the CH-TG sulfonium ion (12%), although some elimi nation of HCl is also observed (17%). The reactive capacity for HD is evide ntly exceeded at high loadings, where complete conversion to TG is hindered . However, addition of excess water results in the quantitative hydrolysis of sorbed HD to CH-TG. On AP-Al2O3 dried to remove physisorbed water, C-13 CP-MAS NMR detects a surface alkoxide consistent with that of TG.