Manganese dioxide nanoparticles-silver-Y zeolite as a nanocomposite catalyst for the decontamination reactions of OS-diethyl methyl phosphonothiolate

  • K. Dastafkan
  • M. Sadeghi
  • A. Obeydavi
Original Paper


The decontamination reactions of O,S-diethyl methyl phosphonothiolate, as an agricultural organo-phosphorous pesticide onto 20 wt% loaded manganese dioxide nanoparticles-silver-Y zeolite as a nanocomposite catalyst in different solvents, were evaluated and monitored by means of gas chromatography–flame ionization detector and gas chromatography–mass spectrometry. Prior to the reaction, the catalyst was synthesized in three steps: at first, sodium-Y zeolite was prepared by hydrothermal method; then, silver-Y zeolite was prepared from sodium-Y zeolite using ion exchange procedure; and finally, manganese dioxide nanoparticles were synthesized by in situ impregnation method by pouring the pre-prepared silver-Y zeolite into manganese(ΙΙ) nitrate solution and loaded as 20 wt% onto silver-Y zeolite structure. The formation of the synthesized units and final nanocomposite catalyst was verified through scanning electron microscopy, X-ray diffraction, atomic absorption spectrometry and Fourier transform-infrared spectroscopy techniques. Gas chromatography chromatograms showed that O,S-diethyl methyl phosphonothiolate was decontaminated perfectly by the catalyst in n-heptane solvent after 8 h, at room temperature, while chloroform and isopropanol solvents and other reaction times gave lower decontamination results. Moreover, gas chromatography–mass spectrometry chromatograms confirmed the formation of ethyl methyl phosphonic acid as a major and final product, which exemplifies the role of hydrolysis reaction during the degradation progress.


Decontamination OS-diethyl methyl phosphonothiolate Manganese dioxide nanoparticles-silver-Y zeolite Nanocomposite catalyst Degradation Ethyl methyl phosphonic acid 



The authors are grateful to Young Researchers and Elite Club, Ahvaz and Karaj branches.


  1. Al-Qurainy F, Abdel-Megeed A (2009) Phytoremediation and detoxification of two organophosphorous pesticides residues in Riyadh area. World Appl Sci J 6:987–998Google Scholar
  2. Auerbach SM, Carrado KA, Dutta PK (2003) Handbook of zeolite science and technology. Marcel Dekker Inc., New YorkCrossRefGoogle Scholar
  3. Bagheri H, Ayazi Z, Aghakhani A, Alipour N (2012) Polypyrrole/polyamide electrospun-based sorbent for microextraction in packed syringe of organophosphorous pesticides from aquatic samples. J Sep Sci 35:114–120CrossRefGoogle Scholar
  4. Barata C, Solayan A, Porte C (2004) Role of B-esterases in assessing toxicity of organophosphorus (chlorpyrifos, malathion) and carbamate (carbofuran) pesticides to Daphnia magna. Aquat Toxicol 66:125–139CrossRefGoogle Scholar
  5. Barlocher CH, Meier WM, Olson DH (2001) Atlas of zeolite framework types, Rev edn. Elsevier, AmsterdamGoogle Scholar
  6. Bartram PW, Wagner GW (2003) Decontamination method for toxic chemical agents. US Patent, No 6, 537, 382Google Scholar
  7. Cao H, Suib SL (1994) Highly efficient heterogeneous photooxidation of 2-propanol to acetone with amorphous manganese oxide catalysts. J Am Chem Soc 116:5334–5342CrossRefGoogle Scholar
  8. Chen D, Wang J, Xu Y, Li D (2012) A pure shear mode ZnO film resonator for the detection of organophosphorous pesticides. Sens Actuators B 171–172:1081–1086CrossRefGoogle Scholar
  9. Diurak L, Kazanicif M (2001) Effect of some organophosphorus insecticides on soil microorganisms. Turk J Biol 25:51–58Google Scholar
  10. Elzey S, Mubayib A, Larsen SC, Grassian VH (2008) FTIR study of the selective catalytic reduction of NO2 with ammonia on nanocrystalline NaY and CuY. J Mol Catal A: Chem 285:48–57CrossRefGoogle Scholar
  11. Feeley JS, Sachtler WMH (1991) Enhanced reductibility of Ni and Ni + Pd in zeolite Y: blocking of small cages with Ca2+ or Mg2+ ions. Catal Lett 9:377–386CrossRefGoogle Scholar
  12. Gupta VK, Nayak A (2012) Cadmium removal and recovery from aqueous solutions by novel adsorbents prepared from orange peel and Fe2O3 nanoparticles. Chem Eng J 180:81–90CrossRefGoogle Scholar
  13. Gupta VK, Jain R, Malathi S, Nayak A (2010a) Adsorption–desorption studies of indigocarmine from industrial effluents by using deoiled mustard and its comparison with charcoal. J Colloid Interface Sci 348:628–633CrossRefGoogle Scholar
  14. Gupta VK, Rastogi A, Nayak A (2010b) Adsorption studies on the removal of hexavalent chromium from aqueous solution using a low cost fertilizer industry waste material. J Colloid Interface Sci 342:135–141CrossRefGoogle Scholar
  15. Gupta VK, Jain R, Nayak A, Agarwal A, Shrivastava M (2011) Removal of the hazardous dye—tartrazine by photodegradation on titanium dioxide surface. Mater Sci Eng C 31:1062–1067CrossRefGoogle Scholar
  16. Gupta VK, Kumar R, Nayak A, Saleh TA, Barakat MA (2013) Adsorptive removal of dyes from aqueous solution onto carbon nanotubes: a review. Adv Colloid Interface Sci 193–194:24–34CrossRefGoogle Scholar
  17. Howard PH, Sage GW, Jarvis WF, Gray DA (1990) Handbook of environmental fate and exposure data for organic chemicals, vol 4. Lewis Publishers Inc, Chelsea, p 578Google Scholar
  18. Huang YY (1974) Adsorption in AgX and AgY zeolites by carbon monoxide and other simple molecules. J Catal 32:482–491CrossRefGoogle Scholar
  19. Jentys A, Lercher JA (2001) Characterization of zeolites. In: van Bekkum H, Flanigen EM, Jacobs PA, Jensen JC (eds) Introduction to zeolite science and practice. Elsevier, Amsterdam, p 345CrossRefGoogle Scholar
  20. Jiao F, Frei H (2010) Nanostructured cobalt and manganese oxide clusters as efficient wateroxidation catalysts. Energy Environ Sci 3:1018–1027Google Scholar
  21. Kanan SM, Tripp CP (2001) An infrared study of adsorbed organophosphonates on silica: a prefiltering strategy for the detection of nerve agents on metal oxide sensors. Langmuir 17:2213–2218CrossRefGoogle Scholar
  22. Khajeh M, Laurent S, Dastafkan K (2013) Nanoadsorbents: classification, preparation, and applications (with emphasis on aqueous media). Chem Rev 113:7728–7768CrossRefGoogle Scholar
  23. Khatamian M, Alaji Z, Khandar AA (2011) Synthesis and characterization of polycrystalline ZnO/HZSM-5 nanocomposites. J Iran Chem Soc 8:44–54CrossRefGoogle Scholar
  24. Kim SO, Park ED, Ko EY (2006) Zeolite and sorbent for desurfurization and method of preparing the same. US Patent, No 016, 25, 57, A1Google Scholar
  25. Koivula R, Pakarinen J, Sivenius M, Sirola K, Harjula R, Paatero E (2009) Use of hydrometallurgical wastewater as a precursor for the synthesis of cryptomelane-type manganese dioxide ion exchange material. Sep Purif Technol 70:53–57  Google Scholar
  26. Knagge K, Johnson M, Grassian VH, Larsen SC (2006) Adsorption and thermal reaction of DMMP in nanocrystalline NaY. Langmuir 22:11077–11084CrossRefGoogle Scholar
  27. Li Q, Wang X, Yuan D (2009) Solid-phase extraction of polar organophosphorous pesticides from aqueous samples with oxidized carbon nanotubes. J Environ Monit 11:439–444CrossRefGoogle Scholar
  28. Liu R, Liua H, Qiang Z, Qu J, Li G, Wang D (2009) Effects of calcium ions on surface characteristics and adsorptive properties of hydrous manganese dioxide. J Colloid Interface Sci 331:275–228Google Scholar
  29. Mahato TH, Prasad GK, Singh B, Batra K, Ganesan K (2010) Mesoporous manganese oxide nanobelts for decontamination of sarin, sulfur mustard and chloro ethyl ethyl sulfide. Microporous Mesoporous Mater 132:15–21CrossRefGoogle Scholar
  30. Mahato TH, Singh B, Srivastava AK, Prasad GK, Srivastava AR, Ganesan K, Vijayaraghavan R (2011) Effect of calcinations temperature of CuO nanoparticle on the kinetics of decontamination and decontamination products of sulphur mustard. J Hazard Mater 192:1890–1895CrossRefGoogle Scholar
  31. Meng Q, Doetschman DC, Rizos AK, Lee MH, Schulte JT, Spyros A, Kanyi CW (2011) Adsorption of organophosphates into microporous and mesoporous NaX zeolites and subsequent chemistry. Environ Sci Technol 453:3000–3005CrossRefGoogle Scholar
  32. Mitchell MB, Sheinker VN, Tesfamichae ENG, Nunley M (2003) Decomposition of dimethyl methylphosphonate (DMMP) on supported cerium and iron co-impregnated oxides at room temperature. J Phys Chem B 107:580–586CrossRefGoogle Scholar
  33. Moussavi G, Hosseini H, Alahabadi A (2013) The investigation of diazinon pesticide removal from contaminated water by adsorption onto NH4Cl-induced activated carbon. Chem Eng J 214:172–179CrossRefGoogle Scholar
  34. Munro NB, Talmage SS, Griffin GD, Waters LC, Watson AP, King JF, Hauschild V (1999) The sources, fate, and toxicity of chemical warfare agent degradation products. Environ Health Perspect 107:933–974CrossRefGoogle Scholar
  35. Oliveira MLM, Miranda AAL, Barbosa CMBM, Cavalcante CL Jr, Azevedo DCS, Rodriguez-Castellon E (2009) Adsorption of thiophene and toluene on NaY zeolites exchanged with Ag(I), Ni(II) and Zn(II). Fuel 88:1885–1892CrossRefGoogle Scholar
  36. Padron-Sanz C, Halko R, Sosa-Ferrera Z, Santana-Rodryguez JJ (2005) Combination of microwave assisted micellar extraction and liquid chromatography for the determination of organophosphorous pesticides in soil samples. J Chromatogr A 1078:13–21CrossRefGoogle Scholar
  37. Patterson A (1939) The Scherrer formula for X-ray particle size determination. Phys Rev 56:978–982CrossRefGoogle Scholar
  38. Patterson HH (2006) Development of a rapid decontamination system for nerve agents. US Army Research, NC OMB, No 0704–0188Google Scholar
  39. Paukku Y, Michalkova A, Leszczynski J (2008) Adsorption of dimethyl methylphosphonate and trimethylphosphate on calcium oxide: an ab initio study. Struct Chem 19:307–320CrossRefGoogle Scholar
  40. Prasad GK (2010) Decontamination of 2-chloro ethyl phenyl sulfide using mixed metal oxide nanocrystals. J Sci Ind Res 69:835–840Google Scholar
  41. Prasad GK, Singh B, Ganesan K, Batra A, Kumeria T, Gutch PK, Vijayaraghavan R (2009) Modified titania nanotubes for decontamination of sulfur mustard. J Hazard Mater 167:1192–1197CrossRefGoogle Scholar
  42. Prasad GK, Ramacharyulu PVRK, Singh B (2011) Nanomaterial based decontaminates against chemical warfare agents. J Sci Ind Res 70:91–104Google Scholar
  43. Qi F, Hirofumi K, Kenta O (1999) Manganese oxide porous crystals. J Mater Chem 9:319–333CrossRefGoogle Scholar
  44. Qi R, Wang Y, Chen J, Li J, Zhu S (2007) Removing thiophenes from n-octane using PDMS–AgY zeolite mixed matrix membranes. J Membr Sci 295:114–120CrossRefGoogle Scholar
  45. Rasouli M, Yaghobi N, Chitsazan S, Sayyar MH (2012a) Adsorptive separation of meta-xylene from C8 aromatics. Microporous Mesoporous Mater 90:1407–1415Google Scholar
  46. Rasouli M, Yaghobi N, Chitsazan S, Sayyar MH (2012b) Effect of nanocrystalline zeolite Na-Y on meta-xylene separation. Microporous Mesoporous Mater 152:141–147CrossRefGoogle Scholar
  47. Richter M, Berndt H, Eckelt R, Schneider M, Fricke R (1999) Zeolite-mediated removal of NOx by NH3 from exhaust streams at low temperature. Catal Today 54:531–545CrossRefGoogle Scholar
  48. Richter M, Trunschke A, Bentrup U, Brzezinka KW, Schreier E, Schneider M, Pohl MM, Fricke R (2002) Selective catalytic reduction of nitric oxide by ammonia over egg-shell MnOx/Na-Y composite catalysts. J Catal 206:98–113CrossRefGoogle Scholar
  49. Rusu CN, Yates JT (2000) Adsorption and decomposition of dimethyl methylphosphonate on TiO2. J Phys Chem B 104:12992–12998Google Scholar
  50. Sambur JB, Doetschman DC, Yang SW, Schulte JT, Jones BR, DeCoste JB (2008) Multiple effects of the presence of water on the nucleophilic substitution reactions of NaX Faujasite zeolite with dimethyl methylphosphonate (DMMP). Microporous Mesoporous Mater 112:116–124CrossRefGoogle Scholar
  51. Seidel A, Kampf G, Schmidt A, Boddenberg B (1998) Zeolite ZnY catalysts prepared by solid-state ion exchange. Catal Lett 51:213–218CrossRefGoogle Scholar
  52. Shen YF, Zerger RP, DeGuzman RN, Suib SL, McCurdy L, Potter DI, O’Young CL (1993) Manganese oxide octahedral molecular sieves: preparation, characterization, and applications. Science 23:511–515CrossRefGoogle Scholar
  53. Shen HY, Zhu Y, Wen XE, Zhuang YM (2007) Preparation of Fe3O4-C18 nano-magnetic composite materials and their cleanup properties for organophosphorous pesticides. Anal Bioanal Chem 387:2227–2237CrossRefGoogle Scholar
  54. Singh R, Gutch PK, Acharya J, Prabha S (2011) Detoxification of O,S-diethyl methylphosphonothiolate (OSDEMP), a simulant of VX, by N,N-dichlorourethane an effective decontamination agent. Indian J Chem B 50:1504–1509Google Scholar
  55. Stout SC, Larsen SC, Grassian VH (2007) Adsorption, desorption and thermal oxidation of 2-CEES on nanocrystalline zeolites. Microporous Mesoporous Mater 100:77–86CrossRefGoogle Scholar
  56. Tang H, Cheng Z, Zhu H, Zuo G, Zhang M (2008) Effect of acid and base sites on the degradation of sulfur mustard over several typical oxides. Appl Catal B 79:323–333CrossRefGoogle Scholar
  57. Tomašević A, Kiss E, Petrović S, Mijin D (2010) Study on the photocatalytic degradation of insecticide methomyl in water. Desalination 262:228–234CrossRefGoogle Scholar
  58. Trouve A, Batonneau-Gener I, Valange S, Bonne M, Mignard S (2012) Tuning the hydrophobicity of mesoporous silica materials for the adsorption of organic pollutant in aqueous solution. J Hazard Mater 201–202:107–114CrossRefGoogle Scholar
  59. Wagner GW, Bartram PW (1999) Reactions of VX, HD, and their simulants with Na-Y and Ag-Y zeolites desulfurization of VX on Ag-Y. Langmuir 15:8113–8118CrossRefGoogle Scholar
  60. Wagner GW, Bartram PW, Koper O, Klabunde KJ (1999) Reactions of VX, GD, and HD with nanosize MgO. J Phys Chem B 103:3225–3228CrossRefGoogle Scholar
  61. Wagner GW, Koper OB, Lucas E, Decker S, Klabunde KJ (2000) Reactions of VC, GC, and HD with nanosize CaO: autocatalytic dehydrohalogenation of HD. J Phys Chem B 107:5118–5123CrossRefGoogle Scholar
  62. Wagner GW, Porcell LR, O’Connor RJ, Munavalli S, Carnes CL, Kapoor PN, Klabunde KJ (2001) Reactions of VX, GB, GD, and HD with nanosize Al2O3. Formation of aluminophosphonates. J Am Chem Soc 123:1636–1644CrossRefGoogle Scholar
  63. Wang AJ, Zhang PP, Li YF, Feng JJ, Dong WJ, Liu XY (2011) Hydrogen peroxide sensor based on glassy carbon electrode modified with β-manganese dioxide nanorods. Microchim Acta 175:31–37Google Scholar
  64. Wong CT, Abdullah AZ, Bhatia S (2008) Catalytic oxidation of butyl acetate over silver-loaded zeolites. J Hazard Mater 157:480–489CrossRefGoogle Scholar
  65. Yan W, Kim JY, Xing W, Donavan KC, Ayvazian T, Penner RM (2012) Lithographically patterned gold/manganese dioxide core/shell nanowires for high capacity, high rate, and high cyclability hybrid electrical energy storage. Chem Mater 24:2382–2390Google Scholar
  66. Yang YC, Bake JA, Ward JR (1992) Decontamination of chemical warfare agents. Chem Rev 92:1729–1743CrossRefGoogle Scholar
  67. Yang SW, Doetschman DC, Schulte JT, Sambur JB, Kanyi CW, Fox JD, Kowenje CO, Jones BR, Sherma ND (2006) Sodium X-type faujasite zeolite decomposition of dimethyl methylphosphonate (DMMP) to methylphosphonate: nucleophilic zeolite reactions I. Microporous Mesoporous Mater 92:56–60CrossRefGoogle Scholar

Copyright information

© Islamic Azad University (IAU) 2014

Authors and Affiliations

  1. 1.Young Researchers and Elite Club, Karaj BranchIslamic Azad UniversityKarajIran
  2. 2.Young Researchers and Elite Club, Ahvaz BranchIslamic Azad UniversityAhvazIran

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