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Understanding the effects of Cr doping in rutile TiO₂ by DFT calculations and X-ray spectroscopy.

ABSTRACT: The effects of Cr on local environment and electronic structure of rutile TiO₂ are studied combining theoretical and experimental approaches. Neutral and negatively charged substitutional Cr impurities Cr_Ti⁰ and Cr_Ti^1- as well as Cr-oxygen vacancy complex 2Cr_Ti + V_O are studied by the density functional theory (DFT) within the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) functional. Experimental results based on X-Ray absorption spectroscopy (XAS) and X-Ray photoelectron spectroscopy (XPS) performed on Cr doped TiO₂ at the Synchrotron facility were compared to the theoretical results. It is shown that the electrons of the oxygen vacancy tend to be localized at the t_2g states of the Cr ions in order to reach the stable oxidation state of Cr³⁺. Effects of Cr on crystal field (CF) and structural distortions in the rutile TiO₂ cell were analyzed by the DFT calculations and XAS spectra revealing that the CF and tetragonal distortions in TiO₂ are very sensitive to the concentration of Cr.

SUBMITTER: Vasquez GC

PROVIDER: S-EPMC5992178 | biostudies-literature | 2018 Jun

REPOSITORIES: biostudies-literature

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Understanding the effects of Cr doping in rutile TiO2 by DFT calculations and X-ray spectroscopy.

Vásquez G Cristian GC Maestre David D Cremades Ana A Ramírez-Castellanos Julio J Magnano Elena E Nappini Silvia S Karazhanov Smagul Zh SZ

Scientific reports 20180607 1

The effects of Cr on local environment and electronic structure of rutile TiO2 are studied combining theoretical and experimental approaches. Neutral and negatively charged substitutional Cr impurities CrTi0 and CrTi1- as well as Cr-oxygen vacancy complex 2CrTi + VO are studied by the density functional theory (DFT) within the generalized gradient approximation (GGA) of Perdew-Burke-Ernzerhof (PBE) functional. Experimen ...[more]

PMID: 29880895

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Project description:The efficient adsorption and removal of As(III), which is highly toxic, remains difficult. TiO2 shows promise in this field, though the process needs improvement. Herein, how doping regulates As(OH)3 adsorption over TiO2 surfaces is comprehensively investigated by means of the DFT + D3 approach. Doping creates the bidentate mononuclear (Ce doping at the Ti5c site), tridentate (N, S doping at the O2c site), and other new adsorption structures. The extent of structural perturbation correlates with the atomic radius when doping the Ti site (Ce >> Fe, Mn, V >> B), while it correlates with the likelihood of forming more bonds when doping the O site (N > S > F). Doping the O2c, O3c rather than the Ti5c site is more effective in enhancing As(OH)3 adsorption and also causes more structural perturbation and diversity. Similar to the scenario of pristine surfaces, the bidentate binuclear complexes with two Ti-OAs bonds are often the most preferred, except for B doping at the Ti5c site, S doping at the O2c site, and B doping at the O3c site of rutile (110) and Ce, B doping at the Ti5c site, N, S doping at the O2c site, and N, S, B doping at the O3c site of anatase (101). Doping significantly regulates the As(OH)3 adsorption efficacy, and the adsorption energies reach -4.17, -4.13, and -4.67 eV for Mn doping at the Ti5c site and N doping at the O2c and O3c sites of rutile (110) and -1.99, -2.29, and -2.24 eV for Ce doping at the Ti5c site and N doping at the O2c and O3c sites of anatase (101), respectively. As(OH)3 adsorption and removal are crystal-dependent and become apparently more efficient for rutile vs. anatase, whether doped at the Ti5c, O2c, or O3c site. The auto-oxidation of As(III) occurs when the As centers interact directly with the TiO2 surface, and this occurs more frequently for rutile rather than anatase. The multidentate adsorption of As(OH)3 causes electron back-donation and As(V) re-reduction to As(IV). The regulatory effects of doping during As(III) adsorption and the critical roles played by crystal control are further unraveled at the molecular level. Significant insights are provided for As(III) pollution management via the adsorption and rational design of efficient scavengers.

Dataset Information

Understanding the effects of Cr doping in rutile TiO₂ by DFT calculations and X-ray spectroscopy.

Publications

Understanding the effects of Cr doping in rutile TiO<sub>2</sub> by DFT calculations and X-ray spectroscopy.

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