476 DOI: 10.

1017/S1431927604881479

Microsc Microanal 10(Suppl 2), 2004 Copyright 2004 Microscopy Society of America

Magnesium Oxide Nanoparticles as Destructive Sorbent for Toxic Agents

S. Bakardjieva,* J. ubrt*, V. tengl, F. Oplutil**, M. Olanska** * Institute of Inorganic Chemistry ASCR, 25068 e, Czech Republic **Military Technical Institute of Protection, Brno, Veslaska 230, 62800 Brno, Czech Republic Magnesium oxide is an interesting basic oxide that has many applications. For example, magnesium oxide with ultrafine, nanoscale particles and high specific surface area has shown great promise as destructive adsorbent for toxic chemical agents [1]. Magnesium oxide is obtained mainly by thermal decomposition of magnesium hydroxide or carbonate [2] and recently by the sol-gel process [3]. In the present paper sonochemical synthesis followed by supercritical drying was used to prepare MgO nanoparticles from Mg(OCH3)2 and Mg(OC2H5)2.We report the characterization of the morphology (SEM), particle size (XRD and HRTEM), the specific surface area (BET) and DTA behaviour of MgO. The detoxification activities of the MgO samples were evaluated using mustard. Mg(OCH3)2 was dissolved in toluene, whereas Mg(OC2H5)2 was dissolved in methanol. Obtained mixtures were irradiated with ultrasound by employing a direct immersion titanium horn. Ultrasound irradiation was terminated when clear gel solution was obtained. The supercritical drying of hydroxide gels was performed in autoclave [4]. On the basis of DTA results the hydrated MgO precursors obtained from autoclave were heated at temperature range 360-1200C. DTA curve shows that water started to evolve at ~100C and achieves maximum at 139C. Carbon dioxide and H2O from decomposition of residual OCH3 and OC2H5 groups was detected in the gas phase at ~300C and peaked at 396C. The limit of the calcinations temperature was 1200C. At this temperature the final solid produced were found to consist nanoparticles of MgO (periclase). The specific surface area and particle size are shown in Tab.1. The specific surface area decreases and particle size increases with increasing temperature of the annealing of precursors. X-ray diffraction patterns of the precursor Mg15/1 and the samples prepared by there thermal treatment are similar and exhibit characteristic peaks for MgO (periclase ICDD PDF 45 0496)[5]. With increasing annealing temperature the intensity of the peaks has been evolved. No diffraction lines of Mg(OH)2 were detected. SEM micrographs of the selected sample in shown in Fig.1. Precursor particles (Mg15/1) have uniform morphology as periclase particles (Mg15/360, Mg15/400, Mg15/500 and Mg15/800). HRTEM image of MgO crystallites (see Fig.2) obtained at 1200C (sample Mg15/1200) shows one type of domains corresponding to Fm-3m MgO. The face-centered cubic unit cell has been used to index the ED pattern inserted in Fig 2. The particle size from HRTEM is similar to that of the calculated size from X-ray diffraction. The Sherrer equation was applied to estimate a crystalline size (see Tab.1.) The precursors and samples of magnesium oxides were taken for experimental evaluation of their reactivity with mustard. The largest percentage of the conversion mustard into non-toxic products after the elapse of the reaction was 77%. Reference: [1] J. V. Stark and K. J. Klabunde, Chem. Mater. 8 (1996) 1913 [2] M. A. Aramendia et al., J. Mater. Chem. 6 (1996) 1943 [3] S. S. Choi and S. T. Hwang, J. Mater. Res. 15 (2000) 842

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[4] V. Stengl et al., Mater. Lett. 57 (2003) 3998 [5] JCPDS PDF 2, Resease 50, ICDD, Newtown Square, 2000

TABLE 1. Specific surface areas and crystallite sizes of nanoscale MgO samples Sample Mg15/360 Mg15/400 Mg15/500 Mg15/800 Mg15/1000 Mg15/1200 T [C] 360 400 500 800 1000 1200 SBET[m2g-1] 537 377 288 123 78 51 Phase identified by XRD Periclase Periclase Periclase Periclase Periclase Periclase L44,2 [nm] 1,7 2,9 4,2 8,6 14,2 23,5

FIG.1. SEM micrograph of the MgO sample Mg15/500

FIG.2. HRTEM image and ED of a crystallite MgO sample Mg15/1200