Organic Intercalant-Free Liquid Exfoliation Route to Layered Metal-Oxide Nanosheets via the Control of Electrostatic Interlayer Interaction

Jang Mee Lee, Bohyun Kang, Yun Kyung Jo, Seong Ju Hwang

Research output: Contribution to journalArticle

Abstract

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.

Original languageEnglish
Pages (from-to)12121-12132
Number of pages12
JournalACS Applied Materials and Interfaces
Volume11
Issue number12
DOIs
Publication statusPublished - 2019 Mar 27

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Nanosheets
Coulomb interactions
Oxides
Transition metals
Metals
Liquids
Graphite
Surface charge
Graphene
Alkali Metals
Solvation
Ions
Alkali metals
Zeta potential
Intercalation
Heavy ions
Metal ions
Surface tension
Cations
Hydrogen bonds

All Science Journal Classification (ASJC) codes

  • Materials Science(all)

Cite this

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title = "Organic Intercalant-Free Liquid Exfoliation Route to Layered Metal-Oxide Nanosheets via the Control of Electrostatic Interlayer Interaction",
abstract = "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.",
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Organic Intercalant-Free Liquid Exfoliation Route to Layered Metal-Oxide Nanosheets via the Control of Electrostatic Interlayer Interaction. / Lee, Jang Mee; Kang, Bohyun; Jo, Yun Kyung; Hwang, Seong Ju.

In: ACS Applied Materials and Interfaces, Vol. 11, No. 12, 27.03.2019, p. 12121-12132.

Research output: Contribution to journalArticle

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