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

doi:10.1039/C9CP03449H

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 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 » (111) surfaces.« less

Authors:

^[1];

^[2]; Lee, Jiyoung ^[3]; Windus, Theresa L. ^[3];

^[3];

^[4]

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:: 2019-12-11

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.

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                    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.

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                    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.

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@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}

}

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

Abstract

Citation Formats

Generalized Gradient Approximation Made Simple journal, October 1996

Accelerated coarsening of Ag adatom islands on Ag(111) due to trace amounts of S: Mass-transport mediated by Ag–S complexes journal, March 2009

Reconstruction of steps on the Cu(111) surface induced by sulfur journal, May 2015

Stability of M3S3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni journal, October 2018

Projector augmented-wave method journal, December 1994

Adsorption and diffusion of sulfur on the (111), (100), (110), and (211) surfaces of FCC metals: Density functional theory calculations journal, November 2018

Additive-enhanced coarsening and smoothening of metal films: Complex mass-flow dynamics underlying nanostructure evolution journal, May 2002

Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions journal, November 2016

Self-organization of S adatoms on Au(111): √3R30° rows at low coverage journal, July 2015

Particle growth in model supported metal catalysts—I. Theory journal, December 1976

Density functional analysis of key energetics in metal homoepitaxy: Quantum size effects in periodic slab calculations journal, January 2010

Adsorbate-enhanced transport of metals on metal surfaces: Oxygen and sulfur on coinage metals journal, November 2010

Formation and Diffusion of S-Decorated Cu Clusters on Cu(111) journal, July 2000

From ultrasoft pseudopotentials to the projector augmented-wave method journal, January 1999

Growth and structure of supported metal catalyst particles journal, January 1995

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium journal, May 1994

Cu 2 S 3 complex on Cu(111) as a candidate for mass transport enhancement journal, January 2015

Communication: Structure, formation, and equilibration of ensembles of Ag-S complexes on an Ag surface journal, February 2013

Comparison of S-adsorption on (111) and (100) facets of Cu nanoclusters journal, October 2016

Revisiting the S−Au(111) Interaction: Static or Dynamic? journal, March 2005

Ab initiomolecular dynamics for liquid metals journal, January 1993

Destabilization of Ag nanoislands on Ag(100) by adsorbed sulfur journal, October 2011

Sintering of Pt Nanoparticles via Volatile PtO 2 : Simulation and Comparison with Experiments journal, September 2016

Enhanced Self-Diffusion on Cu(111) by Trace Amounts of S: Chemical-Reaction-Limited Kinetics journal, October 2004

Adsorbate-induced surface stress, surface strain and surface reconstruction: S on Cu(100) and Ni(100) journal, July 2013

Sulfur-induced mobilization of Au surface atoms on Au(111) studied by real-time STM journal, April 2007

Characteristics of sulfur atoms adsorbed on Ag(100), Ag(110), and Ag(111) as probed with scanning tunneling microscopy: experiment and theory journal, January 2019

Generalized Gradient Approximation Made Simple
journal, October 1996

Accelerated coarsening of Ag adatom islands on Ag(111) due to trace amounts of S: Mass-transport mediated by Ag–S complexes
journal, March 2009

Reconstruction of steps on the Cu(111) surface induced by sulfur
journal, May 2015

Stability of M3S3 complexes on fcc M(111) surfaces: M = Au, Ag, Cu, and Ni
journal, October 2018

Projector augmented-wave method
journal, December 1994

Adsorption and diffusion of sulfur on the (111), (100), (110), and (211) surfaces of FCC metals: Density functional theory calculations
journal, November 2018

Additive-enhanced coarsening and smoothening of metal films: Complex mass-flow dynamics underlying nanostructure evolution
journal, May 2002

Future Challenges in Heterogeneous Catalysis: Understanding Catalysts under Dynamic Reaction Conditions
journal, November 2016

Self-organization of S adatoms on Au(111): √3R30° rows at low coverage
journal, July 2015

Particle growth in model supported metal catalysts—I. Theory
journal, December 1976

Density functional analysis of key energetics in metal homoepitaxy: Quantum size effects in periodic slab calculations
journal, January 2010

Adsorbate-enhanced transport of metals on metal surfaces: Oxygen and sulfur on coinage metals
journal, November 2010

Formation and Diffusion of S-Decorated Cu Clusters on Cu(111)
journal, July 2000

From ultrasoft pseudopotentials to the projector augmented-wave method
journal, January 1999

Growth and structure of supported metal catalyst particles
journal, January 1995

Ab initio molecular-dynamics simulation of the liquid-metal–amorphous-semiconductor transition in germanium
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${Cu}_{2} S_{3}$ complex on Cu(111) as a candidate for mass transport enhancement
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Communication: Structure, formation, and equilibration of ensembles of Ag-S complexes on an Ag surface
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Comparison of S-adsorption on (111) and (100) facets of Cu nanoclusters
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Revisiting the S−Au(111) Interaction: Static or Dynamic?
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