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Structural Studies on Organozeolites
There is currently great interest in hybrid microporous organic-inorganic solids, where the organic groups are bound covalently to the inorganic framework and can be chosen to impart organic functionality to the internal surfaces. Although many interesting materials have been prepared, little detailed characterisation has been performed, and we have little understanding of the role structure plays in determining the way these materials act as catalysts and sorbents. Neutron diffraction, and in particular its sensitivity to light elements such as hydrogen (as deuterium), carbon, nitrogen and oxygen, provides the ideal tool for structural studies of such materials. HRPD has been used to provide detailed information on the methyl group configurations, helping us to understand further the properties of these novel materials. The organozeolite inorganic framework gives these materials thermal and

mechanical stability, whereas the organic groups can be adapted and functionalised by synthetic organic methods. The solids can therefore be tailored in a more controlled way than conventional inorganic molecular sieves to give materials complementary in properties to the widely used zeolites. We have chosen to begin by studying the microporous aluminium methylphosphonate AlMePO-b (chemical formula Al2(PO3CH3)3). In this solid, which was first discovered by Maeda as recently as 1994, Xray diffraction revealed an aluminophosphonate framework and one-

dimensional channels (figure F1.1). The hexagonally-arranged channels are around

Figure F1.1. A view along the organic lined channels of AlMePo-b

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Figure F1.2. A section of the Rietveld refined neutron powder diffraction data collected at 4.6K on HRPD.

6 in free diameter, similar to those of wellknown zeolites such as ZSM-5. Although the overall structure was determined by X-rays, it was not possible to obtain details of the positions of the methyl groups that line the pores, so neutron diffraction measurements were performed to do this. In order to obtain high quality diffraction profiles it was necessary to prepare the AlMePO-b in a fully deuterated form. This also permitted a H NMR study that established the dynamics of the methyl group rotation. Given this information, we chose to examine the structure at 4.6K at HRPD, when the methyl groups would have adopted their lowest energy configuration. Deuterated AlMePO-b gave an extremely high resolution neutron powder diffraction profile (figure F1.2) that permitted the unconstrained refinement of all 156 positional parameters of the structure. The accuracy of the refinement is reflected in chemically reasonable bond lengths and angles. In particular, all six
2

the phosphonate oxygens. Taken together with the NMR, we now have a complete picture of the structure and dynamics of the internal surface of this material. This initial study indicates the potential that combined neutron diffraction / spectroscopy possesses to help understand the properties of this novel class of solids. Future experiments will aim towards an examination of the interaction of surface functional groups with adsorbed molecules important in separation and catalysis.

crystallographically-distinct methylphosphonate groups adopt the configuration in figure F1.3, where the methyl group is staggered with respect to
Figure F1.3. The low energy configuration of the methylphosphonate groups of AlMePo-b

Wright

(University

of

St.

Andrews)

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