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It is of particular significance to unveil the authentic coloration mechanism of the multivalent praseodymium colored ZrSiO4 yellow pigments for advanced decoration applications. We herein adopted a facile strategy to modulate the fluorine‐assisted zircon crystallization and thereby obtained ultrafine Pr‐ZrSiO4 yellow pigments, which have a remarkably narrow size distribution and average diameters within 250–400 nm. By virtue of some cogent combinative spectra of reflection, absorption, excitation, and emission from three types of elaborately‐designed H2‐, air‐, and O2‐based pigments, the coloration mechanism for the Pr‐colored zircon was systematically unveiled: both Pr4+ and Pr3+ coexist invariably in the pigments, while the former contributes primarily to the ligand‐to‐metal charge transfer from O2p to Pr(IV)4f for the blue–violet absorption to generate the yellow hue, and the latter is inclined to discolor the pigments. Therefore, an oxidizing atmosphere is preferable to produce brilliant Pr‐ZrSiO4 pigments with enhanced chromatic properties. The stark spectroscopic distinctions between the wide‐band absorption from the nonluminescent tetravalency and the narrow‐band absorption from the luminescent trivalency can expand our understanding to the rare‐earth‐based inorganic pigments. [ABSTRACT FROM AUTHOR]

Zircon has been widely applied in various traditional and emerging fields due to its distinct physiochemical advantages while monodisperse spherical zircon (MSZ) powders hitherto have not been explored for the tremendous challenges in the control of zircon crystallization and growth. Herein, systematic investigations are presented to reveal the paramount role of halide mineralizers upon the crystallization and growth of MSZ powders synthesized under highly acidic hydrothermal environments (pH <0). A formation mechanism is revealed revolving around the complexation of central Zr4+ with the Lewis basic ligand, fluorine, which forms the F‐containing species of [(OH)1–y·Ry] (R = F, Cl) to replace Zr and generates Zr‐deficient zircons as (ZrO4)1‐xSi[(OH)1‐y·Ry]4x. This finding differs much from conventional views on common fluoro‐hydroxylated hydrothermal zircons, which were generally regarded as Si‐deficient silicates from the substitution of fluoro‐hydroxyls for the [SiO4] tetrahedra. A parameter, Kr=4xy, is first proposed as an index to evaluate the stability of hydrothermal zircons. The MSZ powders demonstrate superb thermal stability at high temperature, superior photo‐reflectance, and thermal insulation over normal zircons, promising attractive prospects to extend zircon applications. [ABSTRACT FROM AUTHOR]

Zircon (ZrSiO 4) is a distinctive material widely investigated and applied for its superb physicochemical advantages. To date, great challenges remain in the synthesis of high-quality zircon powders for their stringent crystallization requirements at elevated temperature and inherent preferential growth along the [200] direction. Herein we, for the first time, present monodisperse spherical zircon (MSZ) powders synthesized via a facile one-step hydrothermolysis at 200 °C by rationally manipulating the Lewis acid–base complexation of zirconium with competitive ions (Lewis basic R ligands) in a Zr–OH–R–F quaternary system. Systematical investigations were revealed encircling the complexation of Zr4+ with the R ligands from various sources, which involve the adjusting acids (HR), Zr/Si reactants and halogen-containing mineralizers. Sufficient acidity from the adjusting acid and weak enough Zr–R affinity are confirmed as two paramount factors modulating the crystallization and growth of high-quality MSZ crystals, which undergo a unique metamorphic morphological transition from monolayered, to multilayered, to donut-shaped and ultimately to micrometer-sized spherical particles. The hydrothermal zircons are first confirmed as Zr-deficient (Zr/Si ratios <1.0) zirconium silicates as (ZrO 4) 1–x Si[(OH) 1–y ·R y ] 4x , rather than the Si-deficient Zr(SiO 4) 1–x [(OH)·R] 4x as initially proposed and hitherto generally accepted. The MSZ powders exhibit fair thermal stability and terrific monodispersity even after calcination at 1100 °C, superior photoreflectance and much lower thermal conductivity (0.18–0.48 W m−1 K−1) over non-spherical zircons. The novel MSZ powders provide arresting prospects to extend the applications of zircon in many traditional and emerging fields. [ABSTRACT FROM AUTHOR]