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Chromium-doped TiO 2  pigments were synthesized via a solid-state reaction method and studied with X-ray diffraction, SEM, XPS, and UV-VIS-NIR reflectance spectroscopy. The incorporation of Cr 3+  accelerates the transition from the anatase phase to the rutile phase and compresses the crystal lattice. Moreover, the particle morphology, energy gap, and reflectance spectrum of Cr-doped TiO 2  pigments is affected by the crystal structure and doping concentration. For the rutile samples, some of the Cr 3+  ions are oxidized to Cr 4+  after sintering at a high temperature, which leads to a strong near-infrared absorption band due to the  3 A 2  →  3  T 1  electric dipole-allowed transitions of Cr 4+ . And the decrease of the band gap causes an obvious redshift of the optical absorption edges as the doping concentration increases. Thus, the VIS and near-infrared average reflectance of the rutile Ti 1 −  x  Cr  x  O 2  sample decrease by 60.2 and 58%, respectively, when the Cr content increases to  x  = 0.0375. Meanwhile, the color changes to black brown. However, for the anatase Ti 1 −  x  Cr  x  O 2  pigments, only the VIS reflection spectrum is inhibited by forming some characteristic visible light absorption peaks of Cr 3+ . The morphology, band gap, and NIR reflectance are not significantly affected. Finally, a Cr-doped anatase TiO 2  pigment with a brownish-yellow color and 90% near-infrared reflectance can be obtained.

Structural and Visible-Near Infrared Optical Properties of Cr-Doped TiO2 for Colored Cool Pigments