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Title: Intercalation-Induced Exfoliation and Thickness-Modulated Electronic Structure of a Layered Ternary Vanadium Oxide

Authors:
; ; ; ; ; ORCiD logo
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
National Science Foundation (NSF)
OSTI Identifier:
1368326
Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemistry of Materials; Journal Volume: 29; Journal Issue: 7
Country of Publication:
United States
Language:
ENGLISH

Citation Formats

Andrews, Justin L., De Jesus, Luis R., Tolhurst, Thomas M., Marley, Peter M., Moewes, Alexander, and Banerjee, Sarbajit. Intercalation-Induced Exfoliation and Thickness-Modulated Electronic Structure of a Layered Ternary Vanadium Oxide. United States: N. p., 2017. Web. doi:10.1021/acs.chemmater.7b00597.
Andrews, Justin L., De Jesus, Luis R., Tolhurst, Thomas M., Marley, Peter M., Moewes, Alexander, & Banerjee, Sarbajit. Intercalation-Induced Exfoliation and Thickness-Modulated Electronic Structure of a Layered Ternary Vanadium Oxide. United States. doi:10.1021/acs.chemmater.7b00597.
Andrews, Justin L., De Jesus, Luis R., Tolhurst, Thomas M., Marley, Peter M., Moewes, Alexander, and Banerjee, Sarbajit. Tue . "Intercalation-Induced Exfoliation and Thickness-Modulated Electronic Structure of a Layered Ternary Vanadium Oxide". United States. doi:10.1021/acs.chemmater.7b00597.
@article{osti_1368326,
title = {Intercalation-Induced Exfoliation and Thickness-Modulated Electronic Structure of a Layered Ternary Vanadium Oxide},
author = {Andrews, Justin L. and De Jesus, Luis R. and Tolhurst, Thomas M. and Marley, Peter M. and Moewes, Alexander and Banerjee, Sarbajit},
abstractNote = {},
doi = {10.1021/acs.chemmater.7b00597},
journal = {Chemistry of Materials},
number = 7,
volume = 29,
place = {United States},
year = {Tue Mar 28 00:00:00 EDT 2017},
month = {Tue Mar 28 00:00:00 EDT 2017}
}
  • The intercalation chemistry of a layered protonic ruthenate, H{sub 0.2}RuO{sub 2.1}.nH{sub 2}O, derived from a layered potassium ruthenate was studied in detail. Three phases with different hydration states were isolated, H{sub 0.2}RuO{sub 2.1}.nH{sub 2}O (n={approx}0, 0.5, 0.9), and its reactivity with tetrabutylammonium ions (TBA{sup +}) was considered. The layered protonic ruthenate mono-hydrate readily reacted with TBA{sup +}, affording direct intercalation of bulky tetrabutylammonium ions into the interlayer gallery. Fine-tuning the reaction conditions allowed exfoliation of the layered ruthenate into elementary nanosheets and thereby a simplified one-step exfoliation was achieved. Microscopic observation by atomic force microscopy and transmission electron microscopy clearlymore » showed the formation of unilamellar sheets with very high two-dimensional anisotropy, a thickness of only 1.3+-0.1 nm. The nanosheets were characterized by two-dimensional crystallites with the oblique cell of a=0.5610(8) nm, b=0.5121(6) nm and gamma=109.4(2){sup o} on the basis of in-plane diffraction analysis. - Graphical abstract: Layered protonic ruthenate derived from a potassium form was directly reacted with bulky tetrabutylammonium ions to trigger exfoliation into nanosheets as long as it is highly hydrated.« less
  • This paper reports on the use of scanning tunneling microscopy to characterize the surface structure of the KHgC{sub 4} (stage 1) and KHgC{sub 8} (stage 2) graphite intercalation compounds. Images of the stage 1 and stage 2 materials exhibit a new commensurate 2x2 superlattice in addition to the centered hexagonal lattice observed in images of pristine graphite. Consideration of intercalant layer structure and previous studies of stage 1 (MC{sub 8}) and stage 2 (MC{sub 24}) alkali metal graphite intercalation compounds (GICs) indicate that the 2x2 superlattice is due to a modulation of the surface carbon layer density of states bymore » the periodic (2x2) potential of the potassium ions. In addition, a new orthorhombic superlattice, a = b = 0.89 nm and« less
  • The utilization of the hydrothermal technique in combination with cationic organic templates has been extensively used in the synthesis of zeolites and molecular sieves. Here, the authors report the hydrothermal synthesis and single-crystal structure of (H{sub 3}N(CH{sub 2}){sub 3}NH{sub 3})[V{sub 4}O{sub 10}], a layered mixed-valence vanadium oxide with organic ammonium cations between the layers. 21 refs., 4 figs.
  • The crystals of an H-form niobate of HCa{sub 2}Nb{sub 3}O{sub 10}.xH{sub 2}O (x=0.5) being tetragonal symmetry (space group P4/mbm) with unit cell parameters a=5.4521(6) and c=14.414(2) A were exfoliated into nanosheets with the triple-layered perovskite structure. The colloid suspension of the nanosheets was put into dialysis membrane tubing and allowed self-assembly in a dilute KCl solution. By this method, a novel layered K-form niobate KCa{sub 2}Nb{sub 3}O{sub 10}.xH{sub 2}O (x=1.3, typically) with bilayer hydrates in the interlayer was produced. The Rieveld refinement and transmission electron microscope (TEM)/selected-area electron diffraction (SAED) observation indicated that the orientations of the a-/b-axis of eachmore » nanosheet as well as the c-axis are uniform, and the self-assembled compound had the same symmetry, tetragonal (P4/mbm) with a=5.453(2) and c=16.876(5) A, as the H-form precursor; the exfoliation/self-assembly process does not markedly affect the two-dimensional lattice of the layer. The large basal spacing resulted from the interlayer K{sup +} ions solvated by two layers of water molecules. The interlayer bilayers-water was gradually changed to monolayer when the temperatures higher than 100 deg. C, and all the water molecules lost when over 600 deg. C. Accompanying the dehydration, the crystal structure transformed from tetragonal to orthorhombic symmetry. Water molecules may take an important role for the layer layered compound to adjust the unit cell to tetragonal symmetry. - Graphical abstract: The structure of layered perovskite niobate KCa{sub 2}Nb{sub 3}O{sub 10}.xH{sub 2}O (x=1.3) having a bilayers-hydrates interlayer, obtained via the exfoliation of an H-form precursor and the self-assembly of Ca{sub 2}Nb{sub 3}O{sub 10}{sup -} nanosheets, was first discussed in detail and determined to be tetragonal symmetry (P4/mbm). The dehydration resulted in the structural transformation to orthorhombic structure.« less
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