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Aqueous and mechanical exfoliation, unique properties, and theoretical understanding of MoO3 nanosheets made from free-standing α-MoO3 crystals: Raman mode softening and absorption edge blue shift

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Abstract

Crystalline α-MoO3 belts consisting of nanosheets stacked along their [010] axes were synthesized via thermal vapor transport of MoO3 powders at elevated temperatures. The MoO3 belts were millimeters in length along their [001] axes and tens to hundreds of micrometers in width along their [100] axes. Mechanical and aqueous exfoliations of the belts to form two-dimensional (2D) nanosheets were processed via the scotch-tape and bovine serum albumin (BSA) assisted methods, respectively. Upon scotch-tape exfoliation, the Raman features of MoO3 exhibited monotonic decreases in intensity as the thickness was gradually fell to approach that of a 2D nanosheet. Most Raman features eventually disappeared when a monolayer nanosheet was produced, except for the Mo–O–Mo stretching mode (Ag) at ~818 cm−1, which was accompanied by mode-softening of up to 5 cm−1. This mode softening, hitherto not reported for 2D α-MoO3 nanosheets, can be attributed to lattice relaxations that are validated here via theoretical density functional perturbation theory calculations. The BSA-assisted exfoliation products exhibited a blueshift in the α-MoO3 nanosheet absorption edge; they also revealed an absorption peak at 3.98 eV that can be attributed to their intrinsic exciton absorptions. These observations, together with the facile synthesis of high-purity α-MoO3 crystals, illuminate the possibility of further 2D α-MoO3 nanosheet production and lattice dynamic studies.

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Acknowledgements

The authors would like to acknowledge B. Li for his setting-up of the tube-furnace and Coryl J. J Lee for collecting the SEM/EDX/XRD data. This research is supported by A*STAR Science and Engineering Research Council Pharos 2D Program (SERC Grant No. 152-70-00012).

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Authors and Affiliations

  1. Institute of Materials Research and Engineering (IMRE), A*STAR (Agency for Science, Technology and Research), 2 Fusionopolis Way, Singapore, 138634, Singapore

    Hongfei Liu, Mingyong Han, Shifeng Guo, Ming Lin, Meng Zhao & Dongzhi Chi

  2. Institute of High Performance Computing (IHPC), A*STAR (Agency for Science, Technology and Research), 1 Fusionopolis Way, Singapore, 138632, Singapore

    Yongqing Cai & Yongwei Zhang

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  1. Hongfei Liu
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Aqueous and mechanical exfoliation, unique properties, and theoretical understanding of MoO3 nanosheets made from free-standing α-MoO3 crystals: Raman mode softening and absorption edge blue shift

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Liu, H., Cai, Y., Han, M. et al. Aqueous and mechanical exfoliation, unique properties, and theoretical understanding of MoO3 nanosheets made from free-standing α-MoO3 crystals: Raman mode softening and absorption edge blue shift. Nano Res. 11, 1193–1203 (2018). https://doi.org/10.1007/s12274-017-1733-x

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