Journal of the Korean Magnetic Resonance Society (한국자기공명학회논문지)

Korean Magnetic Resonance Society (한국자기공명학회)
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Electron Spin Resonance Study of Manganese Ion Species Incorporated into Novel Aluminosilicate Nanospheres with Solid Core/Mesoporous Shell Structure

  • Back, Gern-Ho (Department of Chemistry, Changwon National University) ;
  • Kim, Ki-Yub (Department of Chemistry, Changwon National University) ;
  • Kim, Yun-Kyung (Department of Advanced Materials Chemistry. BK21 Research Team, Korea University) ;
  • Yu, Jong-Sung (Department of Advanced Materials Chemistry. BK21 Research Team, Korea University)
  • Received : 2010.07.03
  • Accepted : 2010.12.09
  • Published : 2010.12.20
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Abstract

An ion-exchanged reaction of $MnCl_2$ with Al-incorporated solid core/mesoporous shell silica (AlSCMS) followed by calcinations generated manganese species, where average oxidation state of manganese ion is 3+, in the mesoporous materials. Dehydration results in the formation of $Mn^{2+}$ ion species, which can be characterized by electron spin resonance (ESR). The chemical environments of the manganese centers in Mn-AlSCMS were investigated by diffuse reflectance, UV-VIS and ESR spectroscopic methods. Upon drying at 323 K, part of manganese is oxidized to higher oxidation state ($Mn^{3+}$ and $Mn^{4+}$) and further increase in (average) oxidation state takes place upon calcinations at 823 K. It was found that the manganese species on the wall of the Mn-AlSCMS were transformed to tetrahedral $Mn^{3+}$ or $Mn^{4+}$ and further changed to square pyramid by additional coordination to water molecules upon hydration. The oxidized $Mn^{3+}$ or $Mn^{4+}$ species on the surfaces were reversibly reduced to $Mn^{2+}$ or $Mn^{3+}$ species or lower valances by thermal process. Mn(II) species I with a well resolved sextet was observed in calcined, hydrated Mn-AlSCMS, while Mn (II) species II with g = 5.1 and 3.2 observed in dehydrated Mn-AlSCMS. Both species I and II are considered to be non-framework Mn(II).

Keywords

References

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