Sulfur adsorption on coinage metal(100) surfaces: propensity for metal–sulfur complex formation relative to (111) surfaces
Abstract
Experimental data from low-temperature Scanning Tunneling Microscopy (LTSTM) studies on coinage metal surfaces with very low coverages of S is providing new insights into metal–S interactions. A previous LTSTM study for Cu(100), and a new analysis reported here for Ag(100), both indicate no metal–sulfur complex formation, but an Au4S5 complex was observed previously on Au(100). In marked contrast, various complexes have been proposed and/or observed on Ag(111) and Cu(111), but not on Au(111). Also, exposure to trace amounts of S appears to enhance mass transport far more dramatically on (111) than on (100) surfaces for Cu and Ag, a feature tied to the propensity for complex formation. Motivated by these observations, we present a comprehensive assessment at the level of DFT to assess the existence and stability of complexes on (100) surfaces, and compare results with previous analyses for (111) surfaces. Consistent with experiment, our DFT analysis finds no stable complexes on Ag(100) and Cu(100), but several exist for Au(100). In addition, we systematically relate stability for adsorbed and gas-phase species within the framework of Hess's law. We thereby provide key insight into the various energetic contributions to stability which in turn elucidates the difference in behavior between (100) andmore »
- Authors:
-
- Ames Laboratory – USDOE, Iowa State University, Ames, USA
- Department of Chemistry, Iowa State University, Ames, USA
- Ames Laboratory – USDOE, Iowa State University, Ames, USA, Department of Chemistry
- Ames Laboratory – USDOE, Iowa State University, Ames, USA, Department of Physics and Astronomy
- Publication Date:
- Research Org.:
- Ames Lab., Ames, IA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division
- OSTI Identifier:
- 1576019
- Alternate Identifier(s):
- OSTI ID: 1577120
- Report Number(s):
- IS-J-10087
Journal ID: ISSN 1463-9076; PPCPFQ
- Grant/Contract Number:
- AC02-05CH11231; AC02-07CH11358; CHE-1507223
- Resource Type:
- Published Article
- Journal Name:
- Physical Chemistry Chemical Physics. PCCP (Print)
- Additional Journal Information:
- Journal Name: Physical Chemistry Chemical Physics. PCCP (Print) Journal Volume: 21 Journal Issue: 48; Journal ID: ISSN 1463-9076
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Liu, Da-Jiang, Spurgeon, Peter M., Lee, Jiyoung, Windus, Theresa L., Thiel, Patricia A., and Evans, James W. Sulfur adsorption on coinage metal(100) surfaces: propensity for metal–sulfur complex formation relative to (111) surfaces. United Kingdom: N. p., 2019.
Web. doi:10.1039/C9CP03449H.
Liu, Da-Jiang, Spurgeon, Peter M., Lee, Jiyoung, Windus, Theresa L., Thiel, Patricia A., & Evans, James W. Sulfur adsorption on coinage metal(100) surfaces: propensity for metal–sulfur complex formation relative to (111) surfaces. United Kingdom. doi:10.1039/C9CP03449H.
Liu, Da-Jiang, Spurgeon, Peter M., Lee, Jiyoung, Windus, Theresa L., Thiel, Patricia A., and Evans, James W. Wed .
"Sulfur adsorption on coinage metal(100) surfaces: propensity for metal–sulfur complex formation relative to (111) surfaces". United Kingdom. doi:10.1039/C9CP03449H.
@article{osti_1576019,
title = {Sulfur adsorption on coinage metal(100) surfaces: propensity for metal–sulfur complex formation relative to (111) surfaces},
author = {Liu, Da-Jiang and Spurgeon, Peter M. and Lee, Jiyoung and Windus, Theresa L. and Thiel, Patricia A. and Evans, James W.},
abstractNote = {Experimental data from low-temperature Scanning Tunneling Microscopy (LTSTM) studies on coinage metal surfaces with very low coverages of S is providing new insights into metal–S interactions. A previous LTSTM study for Cu(100), and a new analysis reported here for Ag(100), both indicate no metal–sulfur complex formation, but an Au4S5 complex was observed previously on Au(100). In marked contrast, various complexes have been proposed and/or observed on Ag(111) and Cu(111), but not on Au(111). Also, exposure to trace amounts of S appears to enhance mass transport far more dramatically on (111) than on (100) surfaces for Cu and Ag, a feature tied to the propensity for complex formation. Motivated by these observations, we present a comprehensive assessment at the level of DFT to assess the existence and stability of complexes on (100) surfaces, and compare results with previous analyses for (111) surfaces. Consistent with experiment, our DFT analysis finds no stable complexes on Ag(100) and Cu(100), but several exist for Au(100). In addition, we systematically relate stability for adsorbed and gas-phase species within the framework of Hess's law. We thereby provide key insight into the various energetic contributions to stability which in turn elucidates the difference in behavior between (100) and (111) surfaces.},
doi = {10.1039/C9CP03449H},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 48,
volume = 21,
place = {United Kingdom},
year = {2019},
month = {12}
}
DOI: 10.1039/C9CP03449H
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