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Title: Self-assembly of acetate adsorbates drives atomic rearrangement on the Au(110) surface

Abstract

Weak inter-adsorbate interactions are shown to play a crucial role in determining surface structure, with major implications for its catalytic reactivity. This is exemplified here in the case of acetate bound to Au(110), where the small extra energy of the van der Waals interactions among the surface-bound groups drives massive restructuring of the underlying Au. Acetate is a key intermediate in electro-oxidation of CO2 and a poison in partial oxidation reactions. Metal atom migration originates at surface defects and is likely facilitated by weakened Au–Au interactions due to bonding with the acetate. Even though the acetate is a relatively small molecule, weak intermolecular interaction provides the energy required for molecular self-assembly and reorganization of the metal surface.

Authors:
ORCiD logo [1]; ORCiD logo [1];  [2];  [3];  [4];  [5]
  1. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
  2. Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Science. Dept. of Physics; Univ. of Science and Technology of China, Hefei (China). Synergetic Innovation Center of Quantum Information and Quantum Physics. Hefei National Lab. for Physical Sciences at Microscale. International Center for Quantum Design of Functional Materials (ICQD)
  3. Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Science
  4. Harvard Univ., Cambridge, MA (United States). School of Engineering and Applied Science. Dept. of Physics
  5. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology. School of Engineering and Applied Science
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Harvard Univ., Cambridge, MA (United States); Univ. of Science and Technology of China, Hefei (China); Energy Frontier Research Centers (EFRC) (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); National Natural Science Foundation of China (NNSFC)
OSTI Identifier:
1362265
Grant/Contract Number:  
SC0012573; 11504357
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 7; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Catalysis; Imaging techniques; Surface assembly; Theory and computation

Citation Formats

Hiebel, Fanny, Shong, Bonggeun, Chen, Wei, Madix, Robert J., Kaxiras, Efthimios, and Friend, Cynthia M. Self-assembly of acetate adsorbates drives atomic rearrangement on the Au(110) surface. United States: N. p., 2016. Web. doi:10.1038/ncomms13139.
Hiebel, Fanny, Shong, Bonggeun, Chen, Wei, Madix, Robert J., Kaxiras, Efthimios, & Friend, Cynthia M. Self-assembly of acetate adsorbates drives atomic rearrangement on the Au(110) surface. United States. doi:10.1038/ncomms13139.
Hiebel, Fanny, Shong, Bonggeun, Chen, Wei, Madix, Robert J., Kaxiras, Efthimios, and Friend, Cynthia M. Wed . "Self-assembly of acetate adsorbates drives atomic rearrangement on the Au(110) surface". United States. doi:10.1038/ncomms13139. https://www.osti.gov/servlets/purl/1362265.
@article{osti_1362265,
title = {Self-assembly of acetate adsorbates drives atomic rearrangement on the Au(110) surface},
author = {Hiebel, Fanny and Shong, Bonggeun and Chen, Wei and Madix, Robert J. and Kaxiras, Efthimios and Friend, Cynthia M.},
abstractNote = {Weak inter-adsorbate interactions are shown to play a crucial role in determining surface structure, with major implications for its catalytic reactivity. This is exemplified here in the case of acetate bound to Au(110), where the small extra energy of the van der Waals interactions among the surface-bound groups drives massive restructuring of the underlying Au. Acetate is a key intermediate in electro-oxidation of CO2 and a poison in partial oxidation reactions. Metal atom migration originates at surface defects and is likely facilitated by weakened Au–Au interactions due to bonding with the acetate. Even though the acetate is a relatively small molecule, weak intermolecular interaction provides the energy required for molecular self-assembly and reorganization of the metal surface.},
doi = {10.1038/ncomms13139},
journal = {Nature Communications},
number = ,
volume = 7,
place = {United States},
year = {2016},
month = {10}
}

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Works referenced in this record:

Generalized Gradient Approximation Made Simple
journal, October 1996

  • Perdew, John P.; Burke, Kieron; Ernzerhof, Matthias
  • Physical Review Letters, Vol. 77, Issue 18, p. 3865-3868
  • DOI: 10.1103/PhysRevLett.77.3865

Stabilization and Structure Calculations for Noncovalent Interactions in Extended Molecular Systems Based on Wave Function and Density Functional Theories
journal, September 2010

  • Riley, Kevin E.; Pitoňák, Michal; Jurečka, Petr
  • Chemical Reviews, Vol. 110, Issue 9
  • DOI: 10.1021/cr1000173

Tuning the Stability of Surface Intermediates Using Adsorbed Oxygen: Acetate on Au(111)
journal, March 2014

  • Cremer, Till; Siler, Cassandra G. F.; Rodríguez-Reyes, Juan Carlos F.
  • The Journal of Physical Chemistry Letters, Vol. 5, Issue 7
  • DOI: 10.1021/jz500192k

Mechanism of the CO-induced 1×2→1×1 structural transformation of Pt(110)
journal, September 1989


The adsorption of oxygen on gold
journal, June 1984


Molecule-Driven Substrate Reconstruction in the Two-Dimensional Self-Organization of Fe-Phthalocyanines on Au(110)
journal, February 2012

  • Fortuna, Sara; Gargiani, Pierluigi; Betti, Maria Grazia
  • The Journal of Physical Chemistry C, Vol. 116, Issue 10
  • DOI: 10.1021/jp211036m

From model studies on Au(111) to working conditions with unsupported nanoporous gold catalysts: Oxygen-assisted coupling reactions
journal, December 2013


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


Direct visualization of quasi-ordered oxygen chain structures on Au(110)-(1 × 2)
journal, August 2016


Chance and Necessity: My Encounter with Gold Catalysts
journal, November 2013


Reactivity and deconstruction of the (1×2)-Rh(110) surface studied by scanning tunneling microscopy
journal, April 2002

  • Africh, C.; Esch, F.; Comelli, G.
  • The Journal of Chemical Physics, Vol. 116, Issue 16
  • DOI: 10.1063/1.1465411

The adsorption and oxidation of acetic acid and acetaldehyde on Cu(110)
journal, July 1981


Molecular Architectonic on Metal Surfaces
journal, May 2007


Surface-Mediated Self-Coupling of Ethanol on Gold
journal, April 2009

  • Liu, Xiaoying; Xu, Bingjun; Haubrich, Jan
  • Journal of the American Chemical Society, Vol. 131, Issue 16
  • DOI: 10.1021/ja900822r

Carbon dioxide coordination chemistry: metal complexes and surface-bound species. What relationships?
journal, May 1999


Accurate Molecular Van Der Waals Interactions from Ground-State Electron Density and Free-Atom Reference Data
journal, February 2009


Adsorption of oxygen on gold
journal, September 1978


Utilisation of CO2 as a chemical feedstock: opportunities and challenges
journal, January 2007

  • Aresta, Michele; Dibenedetto, Angela
  • Dalton Transactions, Issue 28
  • DOI: 10.1039/b700658f

Step dynamics on Au(110) studied with a high-temperature, high-speed scanning tunneling microscope
journal, November 1993


The Role of Surface Deconstruction in the Autocatalytic Decomposition of Formate and Acetate on Ni(110)
journal, September 2004

  • Alemozafar, Ali R.; Madix, Robert J.
  • The Journal of Physical Chemistry B, Vol. 108, Issue 38
  • DOI: 10.1021/jp0400061

First-principles calculations of clean Au(110) surfaces and chemisorption of atomic oxygen
journal, January 2009


van der Waals Interactions Determine Selectivity in Catalysis by Metallic Gold
journal, September 2014

  • Rodriguez-Reyes, Juan Carlos F.; Siler, Cassandra G. F.; Liu, Wei
  • Journal of the American Chemical Society, Vol. 136, Issue 38
  • DOI: 10.1021/ja506447y

Update on selective oxidation using gold
journal, January 2012

  • Pina, Cristina Della; Falletta, Ermelinda; Rossi, Michele
  • Chem. Soc. Rev., Vol. 41, Issue 1
  • DOI: 10.1039/C1CS15089H

Adsorption-Induced Step Formation
journal, August 2001


The bonding of simple carboxylic acids on Cu(110)
journal, May 2000

  • Karis, O.; Hasselström, J.; Wassdahl, N.
  • The Journal of Chemical Physics, Vol. 112, Issue 18
  • DOI: 10.1063/1.481415

Chemisorption of oxygen on gold
journal, January 1968


Theory and Application for the Scanning Tunneling Microscope
journal, June 1983


Self-assembly of organic molecules at metal surfaces
journal, April 2009


Catalysis by Unsupported Skeletal Gold Catalysts
journal, November 2013

  • Wittstock, Arne; Bäumer, Marcus
  • Accounts of Chemical Research, Vol. 47, Issue 3
  • DOI: 10.1021/ar400202p

Nano-Gold Catalysis in Fine Chemical Synthesis
journal, November 2011

  • Zhang, Yan; Cui, Xinjiang; Shi, Feng
  • Chemical Reviews, Vol. 112, Issue 4
  • DOI: 10.1021/cr200260m

Role of Surface Elastic Relaxations in an O-Induced Nanopattern on Pt ( 110 ) ( 1 × 2 )
journal, March 2007


Chemisorption of high coverages of atomic oxygen on the Pt(111), Pd(111), and Au(111) surfaces
journal, May 1990

  • Parker, Deborah Holmes; Koel, Bruce E.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 8, Issue 3
  • DOI: 10.1116/1.576675

Step and kink dynamics on Au(110) and Pb(111) studied with a high-speed STM
journal, October 1995


Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set
journal, October 1996


Geometry of the Au(110)-(1×2) missing-row clean surface: A New LEED and DFT study
journal, March 2010


A comparative study of chemisorption by density functional theory, ab initio, and semiempirical methods: carbon monoxide, formate, and acetate on Cu(110)
journal, November 2003


Model Studies with Gold: A Versatile Oxidation and Hydrogenation Catalyst
journal, December 2013

  • Pan, Ming; Gong, Jinlong; Dong, Guangbin
  • Accounts of Chemical Research, Vol. 47, Issue 3
  • DOI: 10.1021/ar400172u

X-RAY PHOTOELECTRON DIFFRACTION STUDY OF A LONG-RANGE-ORDERED ACETATE LAYER ON Ni(110)
journal, February 2000


Unsupported nanoporous gold for heterogeneous catalysis
journal, January 2013

  • Zhang, Xiaomei; Ding, Yi
  • Catalysis Science & Technology, Vol. 3, Issue 11
  • DOI: 10.1039/c3cy00241a

Oxygen-Mediated Coupling of Alcohols over Nanoporous Gold Catalysts at Ambient Pressures
journal, January 2012

  • Kosuda, Kathryn M.; Wittstock, Arne; Friend, Cynthia M.
  • Angewandte Chemie International Edition, Vol. 51, Issue 7
  • DOI: 10.1002/anie.201107178

Direct observation and analysis of kink dynamics
journal, February 2000


Investigation of Ethylene Oxide on Clean and Oxygen-Covered Ag(110) Surfaces
journal, December 2008


Structure and Energetics of Azobenzene on Ag(111): Benchmarking Semiempirical Dispersion Correction Approaches
journal, January 2010


Structure and Surface Chemistry of Gold-Based Model Catalysts
journal, April 2011


Adsorption of oxygen on Au(111) by exposure to ozone
journal, August 1998


Spontaneous and electron-induced adsorption of oxygen on Au( 110 )-(1×2)
journal, June 2002


Switching Selectivity in Oxidation Reactions on Gold: The Mechanism of C–C vs C–H Bond Activation in the Acetate Intermediate on Au(111)
journal, August 2014

  • Siler, Cassandra G. F.; Cremer, Till; Rodriguez-Reyes, Juan Carlos F.
  • ACS Catalysis, Vol. 4, Issue 9
  • DOI: 10.1021/cs500803n

Comparison of van der Waals corrected and sparse-matter density functionals for the metal-free phthalocyanine/gold interface
journal, January 2014


Formation and decomposition of acetate intermediates on the Ag(110) surface
journal, January 1981


CO-induced restructuring of Pt(110)-(1×2): Bridging the pressure gap with high-pressure scanning tunneling microscopy
journal, February 2003

  • Thostrup, P.; Vestergaard, E. Kruse; An, T.
  • The Journal of Chemical Physics, Vol. 118, Issue 8
  • DOI: 10.1063/1.1540611

STM, FTIR and quantum chemical calculation studies of acetate structures on Cu() surfaces
journal, January 2003


    Works referencing / citing this record:

    Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110)
    journal, January 2018

    • O'Connor, Christopher R.; Hiebel, Fanny; Chen, Wei
    • Chemical Science, Vol. 9, Issue 15
    • DOI: 10.1039/c7sc05313d