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Structure Analysis and Photocatalytic Properties of Spinel Zinc Gallium Oxonitrides

Authors

  • Venkata Bharat Ram Boppana,

    1. Center for Catalytic Science and Technology, Department of Chemical Engineering, University of Delaware, Newark, DE 19716 (USA), Fax: (+1) 302-831-1048
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  • Heather Schmidt,

    1. Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716 (USA)
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  • Prof. Feng Jiao,

    1. Center for Catalytic Science and Technology, Department of Chemical Engineering, University of Delaware, Newark, DE 19716 (USA), Fax: (+1) 302-831-1048
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  • Prof. Douglas J. Doren,

    1. Department of Chemistry and Biochemistry, University of Delaware, Newark, DE 19716 (USA)
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  • Prof. Raul F. Lobo

    Corresponding author
    1. Center for Catalytic Science and Technology, Department of Chemical Engineering, University of Delaware, Newark, DE 19716 (USA), Fax: (+1) 302-831-1048
    • Center for Catalytic Science and Technology, Department of Chemical Engineering, University of Delaware, Newark, DE 19716 (USA), Fax: (+1) 302-831-1048
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Abstract

This report describes a detailed structural, electronic, and catalytic characterization of zinc gallium oxonitride photocatalysts with a spinel crystal structure. The bandgap decreases to less than 3 eV with increasing nitrogen content (<3 wt %) and these photocatalysts are active in visible light (λ>420 nm) for the degradation of cresol and rhodamine B. Density functional theory calculations show that this bandgap reduction is in part associated with hybridization between the dopant N 2p states and Zn 3d orbitals at the top of the valence band. X-ray photoelectron measurements indicate that nitrogen is indeed interacting with the oxide precursor through the formation of both nitride- and oxonitride-type species. The incorporation of nitrogen reduces the uniformity of the local structure of the spinel Zn-Ga-O-N (ZGON) species, as reflected in X-ray absorption spectra and Raman measurements relative to zinc gallate, which suggests the presence of defects. The oxonitrides exhibit faster photocatalytic rates of reaction than the oxide precursor. The degradation mechanisms were determined to be via the attack by hydroxyl radicals and holes for rhodamine B and cresol, respectively. Addition of Pt as a co-catalyst increased the rate of photodegradation, a result attributed to better charge separation.

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