Inorganic Chemistry, Vol.53, No.24, 13220-13226, 2014
A Layered Mixed Zirconium Phosphate/Phosphonate with Exposed Carboxylic and Phosphonic Groups: X-ray Powder Structure and Proton Conductivity Properties
A novel mixed zirconium phosphate/phosphonate based on glyphosine, of formula Zr-2(PO4)H-5(L)(2) center dot H2O [L = (O3PCH2)(2)NCH2COO], was synthesized in mild conditions. The compound has a layered structure that was solved ab initio from laboratory PXRD data. It crystallizes in the monoclinic C2/c space group with the following cell parameters: a = 29.925(3), b = 8.4225(5), c = 9.0985(4) angstrom, and beta = 98.474(6)degrees. Phosphate groups are placed inside the sheets and connect the zirconium atoms in a tetradentate fashion, while uncoordinated carboxylate and P-OH phosphonate groups are exposed on the layer surface. Due to the presence of these acidic groups, the compound showed remarkable proton conductivity properties, which were studied in a wide range of temperature and relative humidity (RH). The conductivity is strongly dependent on RH and reaches 1x 10(-3) S cm(-1) at 140 degrees C and 95% RH. At this RH, the activation energy of conduction is 0.15 eV in the temperature range 80-140 degrees C. The similarities of this structure with related structures already reported in the literature were also discussed.