Nerve Agent Degradation with Polyoxoniobates

被引:85
作者
Kinnan, Mark K. [1 ]
Creasy, William R. [2 ]
Fullmer, Lauren B. [3 ]
Schreuder-Gibson, Heidi L. [4 ]
Nyman, May [3 ]
机构
[1] Sandia Natl Labs, Albuquerque, NM 87123 USA
[2] Leidos Corp, Edgewood Chem Biol Ctr, Aberdeen Proving Ground, MD 21010 USA
[3] Oregon State Univ, Dept Chem, Corvallis, OR 97331 USA
[4] US Army Natick Soldier Res Dev & Engn Ctr, Natick, MA 01760 USA
基金
美国能源部;
关键词
Polyoxometalates; Kinetics; Ion pairs; Small-angle X-ray scattering; Nerve agents; CHEMICAL WARFARE AGENTS; DIISOPROPYL FLUOROPHOSPHATE; POTENTIOMETRIC DETECTION; BIOLOGICAL PROTECTION; LINDQVIST ION; BY-PRODUCTS; DECONTAMINATION; NANOPARTICLES; HEXANIOBATE; OXIDATION;
D O I
10.1002/ejic.201400016
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Polyoxoniobates are exceptional amongst polyoxometalates in that they can potentially perform base catalysis in water, a process in which a proton is bonded to an oxo ligand, and a hydroxyl is released. Catalytic decomposition of chemical warfare agents such as organofluorophosphates that were used recently in the infamous civilian attacks in Syria is one opportunity to employ this process. Upon evaluation of the polyoxoniobate Lindqvist ion, [Nb6O19](8-), fast neutralization kinetics was discovered for the breakdown of the nerve agent simulant diisopropyl fluorophosphate (DFP). The polyoxoniobates were also tested against the nerve agents Sarin (GB) and Soman (GD). It was determined that different Lindqvist countercations (Li, K, or Cs) affect the rate of decomposition of the organophosphate compounds in both aqueous media (homogeneous reaction), and in the solid state (heterogeneous reaction). Small-angle X-ray scattering analysis of solutions of the Li, K, and Cs salts of [Nb6O19](8-) for concentrations at which the experiments were performed revealed distinct differences that could be linked to their relative reaction rates. This study represents the first demonstration of exploiting the unique alkaline reactivity of polyoxoniobates for nerve agent decontamination.
引用
收藏
页码:2361 / 2367
页数:7
相关论文
共 44 条
[1]   Multinuclear NMR investigations of the oxygen, water, and hydroxyl environments in sodium hexaniobate [J].
Alam, TM ;
Nyman, M ;
Cherry, BR ;
Segall, JM ;
Lybarger, LE .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (17) :5610-5620
[2]   Lithium polyniobates. A lindqvist-supported lithium-water adamantane cluster and conversion of hexaniobate to a discrete keggin complex [J].
Anderson, Travis M. ;
Thoma, Steven G. ;
Bonhomme, Francois ;
Rodriguez, Mark A. ;
Park, Hyunsoo ;
Parise, John B. ;
Alam, Todd M. ;
Larentzos, James P. ;
Nyman, May .
CRYSTAL GROWTH & DESIGN, 2007, 7 (04) :719-723
[3]  
[Anonymous], 2005, Potential Military Chemical/Biological Agents and Compounds
[4]  
Antonio M.R., 2009, Angew. Chem, V121, P6252, DOI DOI 10.1002/ANGE.200805323
[5]   Direct Observation of Contact Ion-Pair Formation in Aqueous Solution [J].
Antonio, Mark R. ;
Nyman, May ;
Anderson, Travis M. .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (33) :6136-6140
[6]   Reactions of VX, GD, and HD with Zr(OH)4: Near Instantaneous Decontamination of VX [J].
Bandosz, Teresa J. ;
Laskoski, Matt ;
Mahle, John ;
Mogilevsky, Gregory ;
Peterson, Gregory W. ;
Rossin, Joseph A. ;
Wagner, George W. .
JOURNAL OF PHYSICAL CHEMISTRY C, 2012, 116 (21) :11606-11614
[7]   Rates of oxygen exchange between the [HxNb6O19](aq)8-x Lindqvist ion and aqueous solutions [J].
Black, Jay R. ;
Nyman, May ;
Casey, William H. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (45) :14712-14720
[8]  
Bromberg L., 2007, IND ENG CHEM RES, V46, P3296
[9]   Functional organic-inorganic colloids modified by iodoxybenzoic acid [J].
Bromberg, Lev ;
Zhang, Hidan ;
Hatton, T. Alan .
CHEMISTRY OF MATERIALS, 2008, 20 (05) :2001-2008
[10]   Poly(N-vinylguanidine):: Characterization, and catalytic and bactericidal properties [J].
Bromberg, Lev ;
Hatton, T. Alan .
POLYMER, 2007, 48 (26) :7490-7498