Synthesis of a new potassium-substituted lead fluorapatite and its structural characterization

Abstract

Prismatic crystals of partially potassium substituted lead fluorapatite Pb_5.09Ca_3.78K_1.13(PO₄)₆F_0.87 were grown through a solid-state reaction. The structural study conducted by single-crystal X-ray diffraction revealed that the compound crystallizes in the hexagonal P6₃/m space group, with unit cell parameters a = b = 9.7190(5) Å, c = 7.1700(6) Å and V = 587.37(7) ų(Z = 1), as well as final values amounting to R and wR of 0.0309 and 0.0546, respectively. The structural refinement demonstrated that Pb occupies both the (6h) and (4f) structural sites of hexagonal fluorapatite, K occupies the (6h) site, and Ca is placed on the (4f) site. Powder X-ray diffraction study indicated the absence of additional phases or impurities. Chemical analysis using atomic absorption spectrometry and energy-dispersive X-ray spectroscopy confirmed the expected chemical formula. The electrical conductivity measured over a wide temperature range was found to be governed by the ion mobility mechanism in the tunnel along the c axis (probably attributed to the fluorine ion located there). We, therefore, could infer from the analysis of the complex impedance spectra that the electrical conductivity of our apatite depends essentially on the temperature and frequency, which produces a relaxation phenomenon and semiconductor-like behavior. Moreover, the strong absorption in the UV-Visible region was substantiated through studies of the optical properties of the developed sample. Fluorescence spectra exhibited emissions in the orange regions when excited at 375 nm. The findings of the phenomena resulting from the emission and conduction of the apatite in question suggest its potential for application in various technological fields such as photovoltaic cells, optoelectronics, photonics, LED applications, catalysis and batteries.