Formation of Layered Proton-Conducting Zirconium and Titanium Organophosphonates by Topotactic Reaction: Physicochemical Properties, Proton Dynamics, and Atomic-Resolution Structure.

A series of new zirconium and titanium phosphates-organophosphonates, in which the organophosphonate moiety is functionalized with a sulfo group, was prepared by a topotactic reaction involving the gamma modification of zirconium or titanium hydrogen phosphate with 2-bis(phosphonomethyl)amino-ethan-1-sulfonic acid (H4TDP). H4TDP represents a new type of functionalizing agent, which can be easily prepared by a Moedritzer-Irani reaction from taurine (2-aminoethanesulfonic acid). The gamma modification of zirconium hydrogen phosphate (γ-ZrP) with H4TDP provides mixed phosphate-organophosphonate compounds with the formula Zr(PO4)(H2PO4)1-2x(H2TDP)x·yH2O, where x = 0.15, 0.34, 0.45, and is controlled by the γ-ZrP/H4TDP ratio in the starting mixture. On the contrary, by the topotactic gamma modification of titanium hydrogen phosphate (γ-TiP) with H4TDP, only one product with the formula Ti(PO4)(H2PO4)1-2z(H2TDP)z·yH2O, where z = 0.41 ± 0.01, was obtained regardless of the composition of the starting mixture. The synthesized compounds were characterized by elemental analysis, thermogravimetric analysis, energy-dispersive X-ray analysis, and infrared spectroscopy. The way the topotactic reaction proceeds and how the grafted organophosphonate groups are bonded to the layers of the host structure were suggested on the basis of the solid-state NMR data. It was found that the grafted moieties are spread evenly in the host layers among the hydrogen phosphate groups. The obtained solids are able to intercalate basic molecules, as was proved by the intercalation reactions of the zirconium series with butylamine. The amount of intercalated butylamine increases with increasing x. It is known that both host compounds, γ-ZrP and γ-TiP, are protonic conductors. It was found that the incorporation of H2TDP increases conductivity of the zirconium compound when x = 0.15, but further incorporation of H2TDP into the γ-ZrP host structure leads to a decrease of conductivity. This behavior is explained on the basis of the 1H MAS and the 1H-1H EXSY NMR data.

Structure determination of two intercalated compounds VOPO4.(CH2)4O and VOPO4.OH-(CH2)2-O-(CH2)2-OH; synchrotron powder diffraction and molecular modelling.

The crystal structures of two intercalated compounds have been determined using a combination of synchrotron powder diffraction and molecular mechanics simulations: (1) vanadyl phosphate intercalated with tetrahydrofuran, VOPO(4).(CH(2))(4)O, and (2) vanadyl phosphate intercalated with diethylene glycol, VOPO(4).HO(CH(2))(2)O(CH(2))(2)OH. Both intercalates preserve the tetragonal space group P4/n, as found in the host structure VOPO(4).2H(2)O. (1): a = 6.208, c = 8.930 A, Z = 2, D(x) = 2.51 g cm(-3); (2): a = 6.223, c = 11.417 A, Z = 2, D(x) = 2.66 g cm(-3). Both intercalates exhibit the same type of orientational disorder in the arrangement of guest molecules, as observed in the same host compound intercalated with water. These two intercalates also exhibit, rather surprisingly, perfect ordering in layer stacking without the displacement disorder, characteristic of many intercalated layered structures. Thanks to this regularity in the arrangement of guests and layers, synchrotron powder diffraction could be used in the present structure determination. The present results also enabled the analysis of the effect of geometrical parameters characterizing the mutual host-guest complementarity and the effect of host-guest and guest-guest interaction on the crystal packing of intercalates.