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Title: 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 Au 4S 5 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 betweenmore » (100) and (111) surfaces.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Ames Lab., and Iowa State Univ., Ames, IA (United States)
  2. Iowa State Univ., Ames, IA (United States)
Publication Date:
Research Org.:
Ames Laboratory (AMES), 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:  
AC02-07CH11358; CHE-1507223; AC02-05CH11231
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
Country of Publication:
United States
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 States: 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 States. doi:10.1039/C9CP03449H.
Liu, Da -Jiang, Spurgeon, Peter M., Lee, Jiyoung, Windus, Theresa L., Thiel, Patricia A., and Evans, James W. Mon . "Sulfur adsorption on coinage metal(100) surfaces: propensity for metal–sulfur complex formation relative to (111) surfaces". United States. 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 States},
year = {2019},
month = {11}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C9CP03449H

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