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Tailoring the chemical composition of LiMPO4 (M = Mg, Co, Ni) orthophosphates to design new inorganic pigments frommagenta to yellow Hue

Abstract : New inorganic pigments with intense and saturated coloration have been prepared by a solid-state route and exhibit a large color scale from magenta to yellow. Indeed, yellow and magenta are two of the three subtractive model’s colors with wide application in printing or displays as e-book readers. To develop yellow and magenta hue, we focused on cobalt- and nickel-based orthophosphates thanks to the chemical stability, low density, low price, and easy preparation of such a pigment class. All of these orthophosphates crystallize with the well-known olivine-type structure (orthorhombic Pnma space group) where transition metals are stabilized in a distorted octahedral site. This paper deals with the optical absorption properties of various orthophosphates, the correlations with structural features, and their colorimetric parameters (in L*a*b* color space). The LiCo1–xMgxPO4 series show near-magenta color with tunable luminosity, while the LiNiPO4 compound exhibits a frank yellow coloration. Co2+ (4T1) and Ni2+ (4A2) chromophore ions occupy a more or less distorted octahedral site, leading to tuning of the intensity of the d–d electronic transitions in the visible and near-IR ranges and providing a subtractive color scale; i.e., a LiCo1–xNixPO4 solid solution possesses a very rich panel of colors between the two yellow and magenta extremes. It is worth noting that the crystal-field splitting and B Racah parameter have been estimated in a first approximation on the basis of the Tanabe–Sugano diagram and lead to the conclusion of a slightly higher crystal-field splitting of around 0.9 eV for Ni2+ ions and similar β covalent parameters, despite the same crystallographic sites of both of these transition metals.
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Submitted on : Friday, June 14, 2019 - 2:17:02 PM
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Béatrice Serment, Lou Corucho, Alain Demourgues, Georges Hadziioannou, Cyril Brochon, et al.. Tailoring the chemical composition of LiMPO4 (M = Mg, Co, Ni) orthophosphates to design new inorganic pigments frommagenta to yellow Hue. Inorganic Chemistry, American Chemical Society, 2019, 58 (11), pp.7499-7510. ⟨10.1021/acs.inorgchem.9b00715⟩. ⟨hal-02150247⟩

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