Postalkoxysilylation with diethoxydimethylsilane has been carried out on the zeolitic lamellar precursors of various topologies such as MWW, FER, CDO and MCM-47 aiming to construct new crystalline structures with expanded pore apertures between the layers. The silylation process and the crystalline and pore structures of the resulting materials have been investigated with the techniques of XRD, IR, (13)C and (29)Si MAS NMR, ICP, SEM, HRTEM, elemental analyses, and N 2 adsorption. In contrast to forming known three-dimensional zeolite structures after direct calcination of the lamellar precursors, the silylation led to new crystalline structures with opener pores, as evidenced by the shift of layer-related diffractions to the lower-angle region in XRD patterns and the enlarged interlayer pores found by HRTEM images. After optimizing the treatment conditions, particularly the amount of silane agent, a maximum and homogeneous silylation was realized, which guaranteed the phase purity in interlayer expanded zeolites. The expanded structures were well preserved after calcination at 823 K or reflux in water for 1 to 2 weeks, indicating a high thermal stability and also a hydrothermal stability. The interlayer expanded zeolites prepared from the metallosilicate precursors of MWW topology exhibited higher catalytic activities in the redox and solid acid-catalyzed reactions of bulky molecules than that of their counterparts with conventional MWW topology.

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Despite the ubiquity of poorly crystalline ferric hydrous oxides (HFO, or ferrihydrite) in natural environments, stable Fe isotopic fractionation between HFO and other Fe phases remains unclear. In particular, it has been difficult to determine equilibrium Fe isotope fractionation between aqueous Fe(II) and HFO due to fast transformation of the latter to more stable minerals. Here we used HFO stabilized by the presence of dissolved silica (2.14 mM), or a Si-HFO coprecipitate, to determine an equilibrium Fe(II)-HFO fractionation factor using a three-isotope method. Iron isotope exchange between Fe(II) and HFO was rapid and near complete with the Si-HFO coprecipitate, and rapid but incomplete for HFO in the presence of dissolved silica, the latter case likely reflecting blockage of oxide surface sites by sorbed silica. Equilibrium Fe(II)-HFO (56)Fe/(54)Fe fractionation factors of -3.17 ± 0.08 (2σ)‰ and -2.58 ± 0.14 (2σ)‰ were obtained for HFO plus silica and the Si-HFO coprecipitate, respectively. Structural similarity between ferrihydrite and hematite, as suggested by spectroscopic studies, combined with the minor isotopic effect of dissolved silica, imply that the true equilibrium Fe(II)-HFO (56)Fe/(54)Fe fractionation factor in the absence of silica may be ∼-3.2‰. These results provide a critical interpretive context for inferring the stable isotope effects of Fe redox cycling in nature.