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Al/Fe-, Al/Cu- and Al/(Fe-Cu)-pillared clays: Structural features at low Atomic Active Metal Ratios (AMR)

Galeano, Luis-Alejandro Y Gil, A. Y Vicente, M. Angel (2010) Al/Fe-, Al/Cu- and Al/(Fe-Cu)-pillared clays: Structural features at low Atomic Active Metal Ratios (AMR). In: Conference SEA-CSSJ-CMS Trilateral Meeting on Clays, 2010, Sevilla- España.


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A set of Al/Fe-, Al/Cu- and Al/(Fe-Cu)-pillared clays were prepared from a Colombian bentonite in sodium or natural (Ca/Mg) form as starting materials. The effect of the loading of the second metal(s) (Fe and/or Cu) related to Al (AMR) in the intercalating solutions at low range of values ≤ 10%, on the main physicochemical properties was investigated. The insertion of the active metals rose almost linearly with AMR for both binary, Al/Fe- and Al/Cu- mixed metal systems. For the three-metal Al/(Fe-Cu)- mixed system, the stabilization of copper behaved randomly as a function of AMR, while the stabilization of Fe was almost not affected by the presence of Cu. On the basis of the ionic radii of the metals involved, a possible competition of the two active metals for the octahedral sites available in the Al13 polycationic structure is proposed for the three-metal system (ionic radii values: Al3+ = 0.68 Å; Fe3+ = 0.67 Å; Cu2+ = 0.73 Å), but also as a good explanation for the efficiency of stabilization for iron around 15 times higher than copper in the binary metal systems. A clear dependence of the compensation of the cationic exchange capacity by polycations with the AMR value was found only for the system Al/Fe-, which was explained in terms of the opposite changes in the final pH obtained in the intercalating solutions, induced by the active metals in the Keggin-like polycations. The change in the basal spacings obtained in the XRD patterns from oriented glasses as a function of AMR was interpreted in terms of the opposite effect expected on the molecular size of the polycations as higher amounts of Fe or Cu would isomorphically substitute Al into the Al13 framework, allowing to propose that both, iron and copper are able to carry out such a substitution, although in different extent. The hydrogen consumption in the H2-TPR analysis of the materials was mainly distributed between two broad peaks: one from about 250ºC to 580ºC, and a second one from about 750ºC to 950ºC. Despite the several metal oxide species that are possible to form, the first signal in samples modified with the Al/Fe- system may correspond with the sequential overlapped reduction of Fe2O3 in up to three steps: (1) Fe2O3 → Fe3O4; (2) Fe3O4 → FeO; and (3) FeO → Fe, and to two sequential reduction effects in the range of 210-260 ºC for Cu2+→ Cu+ and Cu+→ Cu0 at higher temperatures of ca. 400 ºC to 700 ºC. In the Al/Fe- system two shoulders were observed at around 600ºC and 850ºC, whose intensity grow as the active metal loading increases, seem to be related to two kinds of metal sites repeatedly claimed in the literature as responsible for the high catalytic activity displayed by these materials in Fenton-like reactions; Fe “decorating” Al pillars and true mixed Al/Fe pillars, respectively. The textural analysis of the natural modified samples suggest that at AMR below 5.0 %, a discrete maximum exist for the systems Al/Fe- and Al/Cu- over which the sorption capacity starts to be significantly affected. Simultaneous thermal analysis (DSC/TGA) demonstrated that the addition of a second metal in the intercalating system enhanced more the fraction of physisorbed water and decreased the maximum temperature for such a thermal event than intercalation with simple Al- polycations. SEM micrographs showed significant changes in morphology of the particles as AMR increased from 2.0 to 5.0%; as the amount of iron and/or copper added to the system increased, a greater amount of tiny particles deposited on the clay surface was seen, may be corresponding with external oxide aggregates. Likewise, the ratio Fe/Al obtained from the semi-quantitative surface chemical EDX analysis of the samples modified with the system Al/Fe- indicated that the AMR increasing also leads to higher fraction of the iron inserted represented in intercalated, possibly less aggregated mixed species in the materials. Acknowledgements: Financial support from MEC and FEDER funds (Ref. MAT2007-66439-C02).

Tipo de Elemento: Conferencia o Taller artículo (Poster)
Asunto: Q Ciencias > QD Chemistry
Division: Facultad de Ciencias Exactas y Naturales > Programa de Química > Productividad
Depósito de Usuario: PhD Luis Alejandro Galeano
Fecha Deposito: 07 May 2018 17:50
Ultima Modificación: 07 May 2018 17:50

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