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Ti(IV)-Exchanged Nano-ZIF-8 and Nano-ZIF-67 for Enhanced Photocatalytic Oxidation of Hydroquinone

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Abstract

The metal centres of nano-zeolitic imidazolate framework-8(Zinc) and 67(Cobalt) [nZIF-8(Zn) and nZIF-67(Co)] were partially exchanged with titanium (Ti) centres to form bimetallic nZIF-8(Zn/Ti) (52% Ti4+) and nZIF-67(Co/Ti) (38% Ti4+) respectively, for enhanced photocatalytic performance. A morphological and structural analysis by scanning electron microscopy, energy dispersive spectroscopy (EDS)-mapping and powder X-ray diffraction showed that the particle size, distribution, and the structural integrity of the Sodalite frameworks of the parent ZIFs were retained during the exchange process to form the new bimetallic Ti-ZIFs. Fourier transform infrared spectroscopy confirmed that no additional chemical bonds were formed during the process. X-ray photoelectron spectroscopy binding energies confirmed the preservation of the Zn(II), Co(II) and Ti(IV) oxidation states, as well as the Ti-content, consistent with inductively coupled plasma-optical emission spectrometry and EDS measurements. The Ti-exchanged ZIFs showed higher activity during the photocatalytic oxidation of hydroquinone in comparison with their parent ZIFs. Their kinetic rates were nearly five times faster than those of the parent ZIFs, with the first-order rate constants k = 0.189 min−1 for nZIF-8(Zn/Ti) and k = 0.139 min−1 for nZIF-67(Co/Ti). These catalysts are efficient, stable, and reusable for three photocatalytic cycles without a significant loss of catalytic activity.

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Acknowledgements

The authors acknowledge the financial assistance by SASOL through the University Collaboration Grant. We also thank Professor E. Erasmus for XPS analysis, the Analytical Chemistry Section for their assistance with the ICP-OES study, Ithemba Labs (Cape Town) for the PXRD analysis, and the Centre for Microscopy (UFS) for the SEM-EDX analyses.

Funding

This study was funded through a SASOL University Collaboration Grant.

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Authors and Affiliations

  1. Department of Chemistry, University of the Free State, Nelson Mandela Drive, P.O. Box 339, Bloemfontein, 9300, South Africa

    Lehlohonolo E. Mphuthi & Ernst H. G. Langner

  2. Department of Chemical and Physical Sciences, Walter Sisulu University, Private Bag XI, Mthatha, 5117, South Africa

    Mametsi R. Maseme

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  1. Lehlohonolo E. Mphuthi
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Mphuthi, L.E., Maseme, M.R. & Langner, E.H.G. Ti(IV)-Exchanged Nano-ZIF-8 and Nano-ZIF-67 for Enhanced Photocatalytic Oxidation of Hydroquinone. J Inorg Organomet Polym 32, 2664–2678 (2022). https://doi.org/10.1007/s10904-022-02327-8

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