Modulation of the intercalation properties of copper-zinc mixed-metal phosphonate materials

摘要

New layered mixed divalent metal vinylphosphonates (Cu1-xZnxII)-Zn-II-(O3PC2H3) . H2O have been prepared from a range of pre-formed copper-zinc oxides (Cu1-xZnxO)-Zn-II-O-II obtained by isomorphous substitution of zinc into the tenorite-type structure of (CuO)-O-II. The corresponding mixed divalent copper-zinc vinylphosphonates have been characterised by powder X-ray diffraction, elemental analysis, infrared spectroscopy and thermogravimetric analysis. All compounds have been shown to consist of a single-phase solid solution that crystallises in an monoclinic unit cell, space group P2(1)/c with a = 9.86 - 9.90. b = 7.61 - 7.64, c = 7.32-7.35 Angstrom and beta = 95.9 - 96, with the exception of the pure zinc vinylphosphonate (x-1), the structure of which is comparable to other Zn-II(O3PR) .H2O materials. Studies of the intercalation of n-butylamine into the range of copper-zinc vinylphosphonates have demonstrated that significant modulation of the adsorption properties occurs: whereas one mole of amine is intercalated into the pure zinc vinylphosphonate to give Zn-II(O3PC2H3).(C4H9NH2), for all other members of the series two moles of amine are coordinated to give intercalated compounds of composition Cu-1-x(II), Zn-x(II), (O3PC2H3).[(C3H9NH2)(1-x)(C4H9NH2)(4)](2) from which the amine can be sequentially removed from the different metal sites: this opens up possibilities for further applications of these materials. [References: 41]