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Ordered LiGa5O8 loaded with redox capable Cu2+, Cr3+ ions to manifest interesting optical, magnetic, and catalytic properties

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Abstract

The crystal structure and associated property changes brought about by substituting Cu2+ and Cr3+ ions for Li+ and Ga3+ ions, respectively, in ordered LiGa5O8 are probed in the present work. The samples were synthesized by a single-step calcination process of epoxide-mediated xerogels rapidly and characterized extensively. Powder X-ray diffraction patterns revealed the preservation of the superstructure of spinel up to 50 mol % Cu2+ with Li+, 20 mol % Cr3+ with Ga3+ and coupled substitution of Cu2+ (25 mol %) and Cr3+ (5 mol %) with Li and Ga, respectively. The structural refinements and electron microscopic analysis (high-resolution transmission electron microscopy and selected area electron diffraction) confirmed the samples’ ordered spinel structure. Raman and FTIR features confirmed the lower symmetry arising from the cation ordering in the samples. UV–visible and electron paramagnetic resonance spectroscopy measurements on Cu- and Cr-containing samples revealed their oxidation state and site preferences. Reversible peaks in DSC heating and cooling traces showed order/disorder phase transition in Cu2+(1069 and 1044 °C)- and Cr3+(1100 and 1038 °C) substituted samples. Photoemission in the red region and antiferromagnetic behavior with a Néel temperature of 8 K were displayed by the Cr-containing LiGa5O8. The Cu2+-substituted samples catalyzed the reduction of the nitroaromatics while Cr3+-containing sample catalyzed the photodegradation of Rh-6G dye solution. The coupled substituted sample (Cu/Cr), being advantageous, could perform both catalytic conversions.

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Acknowledgements

This research work was financially supported by SERB (EMR/2016/006131 and EMR/2016/006762), the Government of India. PY and SU thank UGC and CSIR, Government of India, for providing a research fellowship.

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  1. Priyanka Yadav and Shrishti Uniyal have contributed equally to this work.

Authors and Affiliations

  1. Materials Chemistry Group, Department of Chemistry, University of Delhi, Delhi, 110007, India

    Priyanka Yadav, Shrishti Uniyal, Sitharaman Uma & Rajamani Nagarajan

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  1. Priyanka Yadav
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  2. Shrishti Uniyal
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Correspondence to Rajamani Nagarajan.

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10853_2021_6572_MOESM1_ESM.doc

TG-DSC traces of LGO, LCGO25, LCGO50, and LCGCO, PXRD pattern of 60 mol % Cu-substituted LGO, FESEM image of LCGCO sample. Summary of crystallographic parameters obtained from the Rietveld refinement of LGO, LCGO25, LCGO50, LGCO, and LCGCO. UV spectra, Ct/C0 and ln C0/Ct to reduce 4-NA, 4-NP, and 2,4-DNP using LCGO50 and LCGO25; ln(C0/Ct) plots and PXRD pattern obtained after the use of LCGCO in photodegradation of Rh-6G. (DOC 4113 KB)

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Yadav, P., Uniyal, S., Uma, S. et al. Ordered LiGa5O8 loaded with redox capable Cu2+, Cr3+ ions to manifest interesting optical, magnetic, and catalytic properties. J Mater Sci 56, 20111–20125 (2021). https://doi.org/10.1007/s10853-021-06572-z

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