Nano-TiO2-Catalyzed Dehydrochlorination of 1,1,2,2-Tetrachloroethane: Roles of Crystalline Phase and Exposed Facets

  • Xuguang Li
    Xuguang Li
    College of Environmental Science and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Key Laboratory of Environmental Remediation and Pollution Control, Nankai University, Tianjin 300350, China
    More by Xuguang Li
  • Tong Li
    Tong Li
    College of Environmental Science and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Key Laboratory of Environmental Remediation and Pollution Control, Nankai University, Tianjin 300350, China
    More by Tong Li
  • Tong Zhang
    Tong Zhang
    College of Environmental Science and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Key Laboratory of Environmental Remediation and Pollution Control, Nankai University, Tianjin 300350, China
    More by Tong Zhang
  • Cheng Gu
    Cheng Gu
    State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing, Jiangsu 210023, China
    More by Cheng Gu
  • Shourong Zheng
    Shourong Zheng
    State Key Laboratory of Pollution Control and Resource Reuse, School of the Environment, Nanjing University, Nanjing, Jiangsu 210023, China
  • Haijun Zhang
    Haijun Zhang
    School of Physics and Materials Science, Anhui University, Hefei, Anhui 230039, China
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  • , and 
  • Wei Chen*
    Wei Chen
    College of Environmental Science and Engineering, Ministry of Education Key Laboratory of Pollution Processes and Environmental Criteria, Tianjin Key Laboratory of Environmental Remediation and Pollution Control, Nankai University, Tianjin 300350, China
    *Phone/Fax: 86-22-85358169; e-mail: [email protected]
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Cite this: Environ. Sci. Technol. 2018, 52, 7, 4031–4039
Publication Date (Web):March 19, 2018
https://doi.org/10.1021/acs.est.7b05479
Copyright © 2018 American Chemical Society
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Abstract

Nanoscale titanium dioxide (nTiO2) is one of the most widely used metal oxide nanomaterials. Once released into the environment, nTiO2 may catalyze abiotic transformation of contaminants and consequently affect their fate and effects. Here, we show that the overall catalytic efficiency of nTiO2 for the dehydrochlorination reaction of 1,1,2,2-tetrachloroethane, a commonly used solvent, depends on the crystalline phase and exposed facets of nTiO2, which significantly affect the adsorption capacity and surface catalytic activity of nTiO2. Specifically, under all three pH conditions tested (7.0, 7.5 and 8.0), the overall catalytic efficiency of eight nTiO2 materials (as indicated by the surface-area-normalized reaction kinetic constants) followed the order of rutile > anatase > TiO2(B). For anatase and TiO2(B) materials, the overall catalytic efficiency increased with the increasing percentage of exposed {001} and {010} facets, respectively. Crystalline phase and exposed facets significantly affected adsorption affinities of nTiO2, likely by modulating surface hydrophobicity of nTiO2. Crystalline phase and exposed facets also determined the activity of surface catalytic sites on nTiO2 by dictating the concentration and strength of surface unsaturated Ti atoms, as the deprotonated hydroxyl groups chemisorbed to these reactive Ti atoms served as bases to catalyze the base-promoted reaction.

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The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.est.7b05479.

  • Material synthesis procedures; tables summarizing intensity ratios of XRD, calculated percentage of {001} facets, experimental parameters and fitted kinetic constants, and relative abundance of the weak and strong acid sites; figures showing mass balance data of kinetic experiments, SEM images, XPS spectra, FTIR spectra, pyridine-adsorbed FTIR spectra, and NH3-TPD profiles of nTiO2 materials, Ti5c concentrations, dehydrochlorination kinetics of TeCA, effects of TiO2 content and divalent cations on dehydrochlorination kinetics, adsorption isotherms of TeCA, photographs of water contact angles on surface of nTiO2 materials, schematic illustration of faceted TiO2 surfaces, and effects of acid strength on catalytic efficiencies of nTiO2 materials (PDF)

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