Copper Versatility in Hydroxyapatite: Valence States, Clusters, and Optical Absorption Properties

The solid-state reaction between a stoichiometric hydroxyapatite (HA) and CuO at temperatures above 1100 °C produces pure Cu_x-HA phases for x ≤ 0.7 with the general formula Ca₁₀Cu^I_x(PO₄)₆(OH)_2-xO_x. The Cu atoms are located at the center of the hexagonal tunnels between two hydroxyl ligands, as determined by Fourier analysis based on XRD data. During heat treatment, the reduction of Cu²⁺ ions into Cu⁺ is concomitant with the stabilization of copper in HA in the hexagonal tunnel. The incorporation of monovalent copper within the apatite, as revealed by XANES spectroscopy, explains the violet color of the samples. The incorporation of Cu⁺ ions, by substitution of a hydrogen atom by copper(I), results in the formation of linear O-Cu-O chains where the majority of which are isolated for x ≤ 0.3. In addition, the EXAFS investigation showed, thanks to the linear geometry of these clusters that results in multiple diffusion effects, the existence of [CuO]_n chains with n ≥ 2, which only appear clearly for higher copper contents x ≥ 0.5. The strong covalency of the Cu-O bond in such a dumbbell configuration would lead to strong hybridization between the 3d and 4s orbitals of copper and the 2p orbitals of oxygen, as illustrated by ESR signals. In the case of Cu-doped HA prepared by coprecipitation and annealed at a lower temperature (T ≤ 600 °C), copper substitutes calcium according to the theoretical formula Ca_10-xCu_x(PO₄)₆(OH)₂, mainly at the Ca(2) site. This local environment is in line with the Jahn-Teller distortion induced by the Cu²⁺ ion (as evidenced by UV-vis-NIR, XPS, and XANES-EXAFS spectroscopy analyses) and also allows copper-copper interactions from one site to another, as observed by ESR spectroscopy. This versatility of copper in HA gives it optical properties that change from a violet color with near-IR absorption to a blue hue. In all cases, Cu-O-Cu interactions persist whatever the valence state, and heat treatment induces a redox phenomenon, with copper exchanging between two sites close to each other.