Title

Sulfur adsorption on coinage metal(100) surfaces: propensity for metal–sulfur complex formation relative to (111) surfaces

Publication Date

2019

Department

Chemistry; Materials Science and Engineering; Physics and Astronomy; Ames Laboratory

Campus Units

Materials Science and Engineering, Physics and Astronomy, Ames Laboratory, Chemistry

OSTI ID+

1576019

Report Number

IS-J 10087

DOI

10.1039/C9CP03449H

Journal Title

Physical Chemistry Chemical Physics

Volume Number

21

Issue Number

48

First Page

26483

Last Page

26491

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) and (111) surfaces.

DOE Contract Number(s)

AC02-07CH11358; CHE-1507223; AC02-05CH11231

Language

en

Department of Energy Subject Categories

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Publisher

Iowa State University Digital Repository, Ames IA (United States)

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