Doping Behavior of Zr4+ Ions in Zr4+-Doped TiO2 Nanoparticles

• Published in: Journal of physical chemistry. C Vol. 117; no. 51; pp. 27120 - 27126
• Main Authors: Wang, Jingsheng, Yu, Yanlong, Li, Sha, Guo, Limei, Wang, Enjun, Cao, Yaan
• Format: Journal Article
• Language: English
• Published: Columbus, OH American Chemical Society 27.12.2013
• Subjects: Condensed matter: electronic structure, electrical, magnetic, and optical properties; Condensed matter: structure, mechanical and thermal properties; Cross-disciplinary physics: materials science; rheology; Equations of state, phase equilibria, and phase transitions; Exact sciences and technology; Fullerenes and related materials; Infrared and raman spectra and scattering; Materials science; Nanocrystalline materials; Nanoscale materials and structures: fabrication and characterization; Optical properties and condensed-matter spectroscopy and other interactions of matter with particles and radiation; Physics; Specific phase transitions; Structural transitions in nanoscale materials; Temperature dependence; High performance; Raman spectra; Transition temperature; Anatase; Impurity density; Doping; Annealing temperature; XRD; Electron microscopy; Raman spectroscopy; Phase transitions; Nanoparticles; Photoelectric effect; Transmission electron microscopy; Photoelectric; Thermal annealing; Nanostructured materials; Sol-gel process; X-ray photoelectron spectra
• ISSN: 1932-7447; 1932-7455
• DOI: 10.1021/jp407662d

TiO2 nanoparticles doped with different concentrations of Zr4+ ions were prepared by the sol–gel method and annealed at different temperatures. X-ray diffraction (XRD), Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), and high resolution transmission electron microscopy (HRTEM) techniques were used to investigate the existing states and doping mechanism of dopants as well as the phase transition of the Zr4+-doped TiO2 samples. It was revealed that the doping behavior of introduced Zr4+ ions was closely related to the doping concentration. The Zr4+ ions would replace the lattice Ti4+ ions directly in substitutional mode at a certain annealing temperature. Moreover, if the concentration of doped Zr4+ ions is high enough, excess Zr4+ ions would form ZrTiO4 on the surface of TiO2. In addition, the phase transition temperature from anatase to rutile increases significantly after doping Zr4+ ions, due to their larger electropositivity and radius than those of Ti4+ ions. Our results may afford a better understanding on the doping mechanism and aid in the preparation of Zr-doped TiO2 with high photoelectric performance.