A scalable organic intercalant-free liquid exfoliation route to 2D nanosheets (NSs) of layered transition-metal oxides (TMOs) is developed by employing hydronium-intercalated derivatives as precursors. The replacement of interlayer alkali metal ions with larger hydronium ions via acid treatment makes possible the efficient liquid exfoliation of TMOs without any assistance of organic intercalant cations. Not only a weakening of interlayer electrostatic interaction upon hydronium intercalation but also an efficient solvation of deintercalated hydronium ions via hydrogen bonding with polar solvents is mainly responsible for the high efficacy of hydronium-intercalated TMOs as precursors for liquid exfoliation. The nature of the solvent employed also has a profound effect on the exfoliation yield of these TMO NSs; viscosity, surface tension, density, and Hansen solubility parameter as well as the capability to solvate the exfoliated NSs and hydronium ions are crucial factors for determining the exfoliation efficiency of the hydronium-intercalated precursor. All the obtained Ti 1-x O 2 , MnO 2 , and RuO 2 NSs show highly anisotropic 2D morphologies and distinct negative surface charges with a zeta potential of -30 to -50 mV. Such distinct surface charges of these NSs render them versatile hybridization matrices for the synthesis of novel nanohybrids with enhanced functionalities. The hybridization with the liquid-exfoliated TMO NSs is quite effective in improving the photocatalytic activity of CdS and the electrode functionalities of graphene and graphene-layered double hydroxide nanohybrids. The present study underscores the usefulness of the present liquid exfoliation method in synthesizing organic-free TMO NSs and their nanohybrids as well as in widening the application field of exfoliated TMO NSs.
Bibliographical noteFunding Information:
This work was supported by the National Research Foundation of Korea (NRF) grant funded by the Korea government (MSIP) (no. NRF-2017R1A2A1A17069463) and by the Korea government (MSIT) (no. NRF-2017R1A5A1015365). The experiments at PAL were supported in part by MOST and POSTECH.
All Science Journal Classification (ASJC) codes
- Materials Science(all)