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:
-
- Univ. of Maryland, College Park, MD (United States)
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States)
- Publication Date:
- Research Org.:
- Sandia National Lab. (SNL-NM), Albuquerque, NM (United States); Energy Frontier Research Centers (EFRC) (United States). Nanostructures for Electrical Energy Storage (NEES)
- Sponsoring Org.:
- USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1326207
- Report Number(s):
- SAND-2016-5593J
Journal ID: ISSN 1932-7447; 647404; TRN: US1700152
- Grant/Contract Number:
- AC04-94AL85000; SC0001160
- Resource Type:
- 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. https://doi.org/10.1021/acs.jpcc.6b06870
Song, Wentao, Leung, Kevin, Shao, Qian, Gaskell, Karen J., and Reutt-Robey, Janice E. Thu .
"Complexation and phase evolution at dimethylformamide-Ag(111) interfaces". United States. https://doi.org/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 = {Thu Sep 15 00:00:00 EDT 2016},
month = {Thu Sep 15 00:00:00 EDT 2016}
}
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