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Title: Interactions of Organic Solvents at Graphene/α-Al2O3 and Graphene Oxide/α-Al2O3 Interfaces Studied by Sum Frequency Generation

Authors:
; ; ;
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC); Fluid Interface Reactions, Structures and Transport Center (FIRST)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1167808
DOE Contract Number:
ERKCC61
Resource Type:
Journal Article
Resource Relation:
Journal Name: J Phys Chem C; Related Information: FIRST partners with Oak Ridge National Laboratory (lead); Argonne National Laboratory; Drexel University; Georgia State University; Northwestern University; Pennsylvania State University; Suffolk University; Vanderbilt University; University of Virginia
Country of Publication:
United States
Language:
English
Subject:
catalysis (heterogeneous), solar (fuels), energy storage (including batteries and capacitors), hydrogen and fuel cells, electrodes - solar, mechanical behavior, charge transport, materials and chemistry by design, synthesis (novel materials)

Citation Formats

Achtyl, J., Vlassiouk, I., Dai, S., and Geiger, F. Interactions of Organic Solvents at Graphene/α-Al2O3 and Graphene Oxide/α-Al2O3 Interfaces Studied by Sum Frequency Generation. United States: N. p., 2014. Web. doi:10.1021/jp5047547.
Achtyl, J., Vlassiouk, I., Dai, S., & Geiger, F. Interactions of Organic Solvents at Graphene/α-Al2O3 and Graphene Oxide/α-Al2O3 Interfaces Studied by Sum Frequency Generation. United States. doi:10.1021/jp5047547.
Achtyl, J., Vlassiouk, I., Dai, S., and Geiger, F. Thu . "Interactions of Organic Solvents at Graphene/α-Al2O3 and Graphene Oxide/α-Al2O3 Interfaces Studied by Sum Frequency Generation". United States. doi:10.1021/jp5047547.
@article{osti_1167808,
title = {Interactions of Organic Solvents at Graphene/α-Al2O3 and Graphene Oxide/α-Al2O3 Interfaces Studied by Sum Frequency Generation},
author = {Achtyl, J. and Vlassiouk, I. and Dai, S. and Geiger, F.},
abstractNote = {},
doi = {10.1021/jp5047547},
journal = {J Phys Chem C},
number = ,
volume = ,
place = {United States},
year = {Thu Aug 07 00:00:00 EDT 2014},
month = {Thu Aug 07 00:00:00 EDT 2014}
}
  • The adsorption of 1-hexanol from cyclohexane-d12 at single-layer graphene/α-Al2O3 interfaces was probed at mole percent values as low as 0.05 in the C–H stretching region using vibrational sum frequency generation (SFG). The SFG spectra are indiscernible from those obtained in the absence of graphene, and from those obtained in the presence of graphene oxide films prepared via oxygen plasma treatment of pristine single-layer graphene. A Langmuir adsorption model yields observed free adsorption energies of -19.9(5) to -20.9(3) kJ/mol for the three interfaces. The results indicate that the molecular structure of the hexanol alkyl chain is subject to the same orientationmore » distribution when graphene, oxidized or not, is present or absent at the α-Al2O3/cyclohexane-d12 interface. Moreover, it appears that the adsorption of 1-hexanol in this binary mixture is driven by hexanol interactions with the underlying oxide support, and that a single layer of graphene does not influence the extent of this interaction, even when defects are introduced to it. Finally, our structural and quantitative thermodynamic data provide important benchmarks for theoretical calculations and atomistic simulations of liquid/graphene interfaces. We hypothesize that defects emerging in graphene during operation of any device application that relies on layered solvent/graphene/oxide interfaces have little impact on the interfacial structure or thermodynamics, at least for the binary mixture and over the range of defect densities probed in our studies.« less
  • No abstract prepared.
  • Sum frequency generation vibrational spectroscopy (SFG) and quartz crystal microbalance with dissipation monitoring (QCM-D) are employed to study the interfacial structure and adsorbed amount of the amino acids l-lysine and l-proline and their corresponding homopeptides, poly-l-lysine and poly-l-proline, at two liquid-solid interfaces. SFG and QCM-D experiments of these molecules are carried out at the interface between phosphate buffered saline at pH 7.4 (PBS) and the hydrophobic deuterated polystyrene (d{sub 8}-PS) surface as well as the interface between PBS and hydrophilic fused silica (SiO{sub 2}). The SFG spectra of the amino acids studied here are qualitatively similar to their corresponding homopeptides;more » however, the SFG signal from amino acids at the solid/PBS interface is smaller in magnitude relative to their more massive homopeptides at the concentrations studied here. Substantial differences are observed in SFG spectra for each species between the hydrophobic d{sub 8}-PS and the hydrophilic SiO{sub 2} liquid-solid interfaces, suggesting surface-dependent interfacial ordering of the biomolecules. Over the range of concentrations used in this study, QCM-D measurements also indicate that on both surfaces poly-l-lysine adsorbs to a greater extent than its constituent amino acid l-lysine. The opposite trend is demonstrated by poly-l-proline which sticks to both surfaces less extensively than its corresponding amino acid, l-proline. Lastly, we find that the adsorption of the molecules studied here can have a strong influence on interfacial water structure as detected in the SFG spectra.« less