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Title: Complexation and phase evolution at dimethylformamide-Ag(111) interfaces

Abstract

The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF) 2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV-STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF) 2, through the saturation monolayer limit, in which these two chemical species phase separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF) 2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure-composition phase diagram, which allows structure prediction over arbitrary experimental conditions. In conclusion, this work reveals new surface coordination chemistry for an important electrolyte-electrode system, and illustrates how surface pressure can be used to tune monolayer phases.

Authors:
 [1];  [2];  [1];  [1];  [1]
  1. Univ. of Maryland, College Park, MD (United States)
  2. Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA)
OSTI Identifier:
1326207
Report Number(s):
SAND-2016-5593J
Journal ID: ISSN 1932-7447; 647404; TRN: US1700152
Grant/Contract Number:
AC04-94AL85000
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Name: Journal of Physical Chemistry. C; Journal ID: ISSN 1932-7447
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; solvent-electrode interaction; monolayer; 2-D phases; surface pressure; etching; surface coordination compound

Citation Formats

Song, Wentao, Leung, Kevin, Shao, Qian, Gaskell, Karen J., and Reutt-Robey, Janice E. Complexation and phase evolution at dimethylformamide-Ag(111) interfaces. United States: N. p., 2016. Web. doi:10.1021/acs.jpcc.6b06870.
Song, Wentao, Leung, Kevin, Shao, Qian, Gaskell, Karen J., & Reutt-Robey, Janice E. Complexation and phase evolution at dimethylformamide-Ag(111) interfaces. United States. doi:10.1021/acs.jpcc.6b06870.
Song, Wentao, Leung, Kevin, Shao, Qian, Gaskell, Karen J., and Reutt-Robey, Janice E. 2016. "Complexation and phase evolution at dimethylformamide-Ag(111) interfaces". United States. doi:10.1021/acs.jpcc.6b06870. https://www.osti.gov/servlets/purl/1326207.
@article{osti_1326207,
title = {Complexation and phase evolution at dimethylformamide-Ag(111) interfaces},
author = {Song, Wentao and Leung, Kevin and Shao, Qian and Gaskell, Karen J. and Reutt-Robey, Janice E.},
abstractNote = {The interaction of solvent molecules with metallic surfaces impacts many interfacial chemical processes. We investigate the chemical and structure evolution that follows adsorption of the polar solvent dimethylformamide (DMF) on Ag(111). An Ag(DMF)2 coordination complex forms spontaneously by DMF etching of Ag(111), yielding mixed films of the complexes and DMF. Utilizing ultrahigh vacuum scanning tunneling microscopy (UHV-STM), in combination with X-ray photoelectron spectroscopy (XPS) and density functional theory (DFT) computations, we map monolayer phases from the 2-D gas regime, consisting of a binary mixture of DMF and Ag(DMF)2, through the saturation monolayer limit, in which these two chemical species phase separate into ordered islands. Structural models for the near-square DMF phase and the chain-like Ag(DMF)2 phase are presented and supported by DFT computation. Interface evolution is summarized in a surface pressure-composition phase diagram, which allows structure prediction over arbitrary experimental conditions. In conclusion, this work reveals new surface coordination chemistry for an important electrolyte-electrode system, and illustrates how surface pressure can be used to tune monolayer phases.},
doi = {10.1021/acs.jpcc.6b06870},
journal = {Journal of Physical Chemistry. C},
number = ,
volume = ,
place = {United States},
year = 2016,
month = 9
}

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