Crystal Structure and Properties of Strontium Phosphate Apatite with Oxocuprate Ions in Hexagonal Channels

Abstract

AbstractStrontium phosphate apatites containing different amounts of copper were prepared by a solid state reaction at 1100 °C or by arc melting above 1600 °C in air. The samples were characterized by X‐ray diffraction, ICP analysis, scanning electron microscopy, IR spectroscopy, MAS—1H—NMR, diffuse reflectance spectroscopy, and SQUID magnetometry. X‐ray crystal structure determination was carried out for a single crystal obtained from the melt. The compound is formulated as Sr5(PO4)3(CuO2)1/3 and has an apatite structure (space group P63/m, a = 9.7815(4)Å, c = 7.3018(4)Å, Z = 2) with linear CuO23— ions occupying hexagonal channels. For solid state synthesized samples, Rietveld refinement of powder XRD patterns was performed. The samples obtained at 1100 °C acquire the composition Sr5(PO4)3CuxOHy, with x changing from 0.01 to 0.62 and y < 1—x. The copper content can be increased to x = 0.85 by annealing in argon at 950 °C. The compounds represent a hydroxyapatite in which part of the protons is substituted by Cu+ and Cu2+ ions. The ions form linear O—Cu—O units which are progressively condensed creating the Cu—O—Cu bridges on increasing copper content. IR and NMR data testify existence of OH groups, non‐disturbed and disturbed by neighboring Cu atoms. In the electron spectra, the samples exhibit absorption bands at 7800‐7900, 14200‐14500 and 17500‐17550 cm—1, which were assigned to Cu2+ d‐electron transitions. By annealing the sample with x = 0.1 in oxygen at 800 °C copper is fully oxidized while retaining in channels in unusual for Cu2+ linear coordination.