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Title: Atomic and Molecular Adsorption on Cu(111)

Abstract

Here, due to the wide use of copper-based catalysts in industrial chemical processes, fundamental understanding of the interactions between copper surfaces and various reaction intermediates is highly desired. Here, we performed periodic, self-consistent density functional theory (DFT-GGA) calculations to study the adsorption of five atomic species (H, C, N, O, and S), seven molecular species (NH 3, CH 4, N 2, CO, HCN, NO, and HCOOH), and 13 molecular fragments (CH, CH 2, CH 3, NH, NH 2, OH, CN, COH, HCO, COOH, HCOO, NOH, and HNO) on the Cu(111) surface at a coverage of 0.25 monolayer. The preferred binding site, binding energy, and the corresponding surface deformation energy of each species were determined, as well as the estimated diffusion barrier and diffusion pathway. The binding strengths calculated using the PW91 functional decreased in the following order: CH > C > O > S > CN > NH > N > CH 2 > OH > HCOO > COH > H > NH 2 > NOH > COOH > HNO > HCO > CH 3 > NO > CO > NH 3 > HCOOH. No stable binding structures were observed for N 2, HCN, and CH 4. The adsorbate–surface andmore » intramolecular vibrational modes of all the adsorbates at their preferred binding sites were deternined. Using the calculated adsorption energetics, potential energy surfaces were constructed for the direct decomposition of CO, CO 2, NO, N 2, NH 3, and CH 4 and the hydrogen-assisted decomposition of CO, CO 2, and NO.« less

Authors:
 [1];  [1];  [1];  [1]
  1. Univ. of Wisconsin-Madison, Madison, WI (United States)
Publication Date:
Research Org.:
Univ. of Wisconsin-Madison, Madison, WI (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Contributing Org.:
National Energy Research Scientific Computing Center (NERSC); the Center for Nanoscale Materials (CNM) at Argonne National Laboratory (ANL); and the Environmental Molecular Sciences Laboratory (EMSL), a national scientific user facility at Pacific Northwest National Laboratory (PNNL)
OSTI Identifier:
1440993
Grant/Contract Number:  
FG02-05ER15731
Resource Type:
Accepted Manuscript
Journal Name:
Topics in Catalysis
Additional Journal Information:
Journal Volume: June 2018; Journal Issue: 7-8; Journal ID: ISSN 1022-5528
Publisher:
Springer
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Density functional theory; Copper; Adsorption; Catalysis; Thermochemistry

Citation Formats

Xu, Lang, Lin, Joshua, Bai, Yunhai, and Mavrikakis, Manos. Atomic and Molecular Adsorption on Cu(111). United States: N. p., 2018. Web. doi:10.1007/s11244-018-0943-0.
Xu, Lang, Lin, Joshua, Bai, Yunhai, & Mavrikakis, Manos. Atomic and Molecular Adsorption on Cu(111). United States. doi:10.1007/s11244-018-0943-0.
Xu, Lang, Lin, Joshua, Bai, Yunhai, and Mavrikakis, Manos. Tue . "Atomic and Molecular Adsorption on Cu(111)". United States. doi:10.1007/s11244-018-0943-0. https://www.osti.gov/servlets/purl/1440993.
@article{osti_1440993,
title = {Atomic and Molecular Adsorption on Cu(111)},
author = {Xu, Lang and Lin, Joshua and Bai, Yunhai and Mavrikakis, Manos},
abstractNote = {Here, due to the wide use of copper-based catalysts in industrial chemical processes, fundamental understanding of the interactions between copper surfaces and various reaction intermediates is highly desired. Here, we performed periodic, self-consistent density functional theory (DFT-GGA) calculations to study the adsorption of five atomic species (H, C, N, O, and S), seven molecular species (NH3, CH4, N2, CO, HCN, NO, and HCOOH), and 13 molecular fragments (CH, CH2, CH3, NH, NH2, OH, CN, COH, HCO, COOH, HCOO, NOH, and HNO) on the Cu(111) surface at a coverage of 0.25 monolayer. The preferred binding site, binding energy, and the corresponding surface deformation energy of each species were determined, as well as the estimated diffusion barrier and diffusion pathway. The binding strengths calculated using the PW91 functional decreased in the following order: CH > C > O > S > CN > NH > N > CH2 > OH > HCOO > COH > H > NH2 > NOH > COOH > HNO > HCO > CH3 > NO > CO > NH3 > HCOOH. No stable binding structures were observed for N2, HCN, and CH4. The adsorbate–surface and intramolecular vibrational modes of all the adsorbates at their preferred binding sites were deternined. Using the calculated adsorption energetics, potential energy surfaces were constructed for the direct decomposition of CO, CO2, NO, N2, NH3, and CH4 and the hydrogen-assisted decomposition of CO, CO2, and NO.},
doi = {10.1007/s11244-018-0943-0},
journal = {Topics in Catalysis},
number = 7-8,
volume = June 2018,
place = {United States},
year = {2018},
month = {5}
}

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Works referenced in this record:

Interaction of the atoms (H, S, O, C) with the Cu(111) surface
journal, August 2002


Unique Properties of Ceria Nanoparticles Supported on Metals: Novel Inverse Ceria/Copper Catalysts for CO Oxidation and the Water-Gas Shift Reaction
journal, January 2013

  • Senanayake, Sanjaya D.; Stacchiola, Dario; Rodriguez, Jose A.
  • Accounts of Chemical Research, Vol. 46, Issue 8
  • DOI: 10.1021/ar300231p

The bonding mechanism of NO to Cu(111)
journal, January 1993


Study of the interaction of nitric oxide with Cu(100) and Cu(111) surfaces using low energy electron diffraction and electron spectroscopy
journal, January 1979

  • Johnson, David W.; Matloob, Mohammed H.; Roberts, M. Wyn
  • Journal of the Chemical Society, Faraday Transactions 1: Physical Chemistry in Condensed Phases, Vol. 75, Issue 0
  • DOI: 10.1039/f19797502143

Single crystal adsorption microcalorimetry
journal, September 1991


A Review of the Water Gas Shift Reaction Kinetics
journal, June 2010

  • Smith R. J., Byron; Loganathan, Muruganandam; Shantha, Murthy Shekhar
  • International Journal of Chemical Reactor Engineering, Vol. 8, Issue 1
  • DOI: 10.2202/1542-6580.2238

NEXAFS study of 1-butanethiol adsorbed on Cu(111) and \sqrt 7 × \sqrt 7 R19.1° S/Cu(111)
journal, June 2001


Leed and heed studies of the interaction of oxygen with single crystal surfaces of copper
journal, July 1967


Energetics and Dynamics for NO and CO Dissociation on Cu(100) and Cu(111)
journal, January 1996

  • van Daelen, M. A.; Li, Y. S.; Newsam, J. M.
  • The Journal of Physical Chemistry, Vol. 100, Issue 6
  • DOI: 10.1021/jp952319p

Quantitative analysis of desorption and decomposition kinetics of formic acid on Cu(111): The importance of hydrogen bonding between adsorbed species
journal, December 2015

  • Shiozawa, Yuichiro; Koitaya, Takanori; Mukai, Kozo
  • The Journal of Chemical Physics, Vol. 143, Issue 23
  • DOI: 10.1063/1.4937414

The adsorption and decomposition of formic acid on Cu {110}
journal, April 1996


The back-titration of chemisorbed atomic oxygen on copper by carbon monoxide investigated by microcalorimetry and transient kinetics
journal, January 2008

  • Naumann d’Alnoncourt, R.; Graf, B.; Xia, X.
  • Journal of Thermal Analysis and Calorimetry, Vol. 91, Issue 1
  • DOI: 10.1007/s10973-007-8446-4

Scanning tunneling microscopy studies of oxygen adsorption on Cu(111)
journal, January 2001


Two new oxygen induced reconstructions on Cu(111)
journal, May 1992


H2S/Cu(111): A model study of sulfur poisoning of water-gas shift catalysts
journal, April 1987


Catalytic carbon dioxide hydrogenation to methanol: A review of recent studies
journal, November 2014

  • Jadhav, Suhas G.; Vaidya, Prakash D.; Bhanage, Bhalchandra M.
  • Chemical Engineering Research and Design, Vol. 92, Issue 11
  • DOI: 10.1016/j.cherd.2014.03.005

On the structure of CO adlayers on Cu(100) and Cu(111)
journal, January 1979


Embedded Configuration Interaction Description of CO on Cu(111):  Resolution of the Site Preference Conundrum
journal, March 2008

  • Sharifzadeh, Sahar; Huang, Patrick; Carter, Emily
  • The Journal of Physical Chemistry C, Vol. 112, Issue 12
  • DOI: 10.1021/jp710890a

Atomic and molecular adsorption on Pd(111)
journal, November 2012


Electronic structure, properties, and phase stability of inorganic crystals: A pseudopotential plane-wave study
journal, January 2000


An infrared spectroscopic study of CO on Cu(111): The linear, bridging and physisorbed species
journal, June 1985


Hydrogénations et déshydrogénations par catalyse
journal, July 1911


New insights into the kinetics of formic acid decomposition on copper surfaces
journal, July 1986


Methanol–steam reforming on Cu/ZnO/Al2O3. Part 1: the reaction network
journal, April 1999


Temperature programmed desorption study of the adsorption and absorption of hydrogen on and in Cu(111)
journal, October 1997


CO adsorption on Cu(111) and Cu(001) surfaces: Improving site preference in DFT calculations
journal, October 2005


Water-gas shift reaction: finding the mechanistic boundary
journal, January 1995


The interaction of NO and CO with Cu(111)
journal, January 1989


CO adsorption on the Cu(111) surface: A density functional study
journal, March 2006


Dipole correction for surface supercell calculations
journal, May 1999


The dynamics of H absorption in and adsorption on Cu(111)
journal, February 1998


Spatial structure determination of (√3×√3) R 30° and (1.5×1.5) R 18° CO or Cu(111) using angle-resolved photoemission extended fine structure
journal, October 1996


CatApp: A Web Application for Surface Chemistry and Heterogeneous Catalysis
journal, December 2011

  • Hummelshøj, Jens S.; Abild-Pedersen, Frank; Studt, Felix
  • Angewandte Chemie International Edition, Vol. 51, Issue 1
  • DOI: 10.1002/anie.201107947

Water Gas Shift Catalysis
journal, September 2009


Photoelectron diffraction investigation of the local adsorption site of N on Cu(111)
journal, May 2000


Adsorption and reactivity of NO on Cu(111): a synchrotron infrared reflection absorption spectroscopic study
journal, February 1997


Atomic and Molecular Adsorption on Re(0001)
journal, October 2013


Adsorption and dissociation of O2 on Cu(): thermochemistry, reaction barrier and the effect of strain
journal, November 2001


Coverage and structure of deuterium on Cu(111)
journal, June 1996


Nitrogen-induced pseudo-(100) reconstruction of the Cu(111) surface identified by STM
journal, November 1999


Recent advances in catalytic hydrogenation of carbon dioxide
journal, January 2011

  • Wang, Wei; Wang, Shengping; Ma, Xinbin
  • Chemical Society Reviews, Vol. 40, Issue 7
  • DOI: 10.1039/c1cs15008a

Chemisorption of atomic hydrogen on Cu(111)
journal, October 1983


Photodesorption of NO from Ag(111) and Cu(111)
journal, July 1991

  • So, S. K.; Franchy, R.; Ho, W.
  • The Journal of Chemical Physics, Vol. 95, Issue 2
  • DOI: 10.1063/1.461120

Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set
journal, July 1996


Nature of active species in copper-based catalysts and their chemistry of transformation of nitrogen oxides
journal, November 1995


E LECTRONIC S TRUCTURE AND C ATALYSIS ON M ETAL S URFACES
journal, October 2002


Low-temperature adsorption of CO on Cu(111) studied by reflection absorption infrared spectroscopy
journal, November 1999


Adsorbate-substrate resonant interactions observed for CO on Cu(100) in the far infrared
journal, July 1990


Atomic and molecular adsorption on Au(111)
journal, September 2014

  • Santiago-Rodríguez, Yohaselly; Herron, Jeffrey A.; Curet-Arana, María C.
  • Surface Science, Vol. 627
  • DOI: 10.1016/j.susc.2014.04.012

High-resolution electron energy loss spectroscopy study on chemisorption of hydrogen on Cu()
journal, February 2002


UV photostimulated desorption of ammonia from Cu(111)
journal, February 1995

  • Hertel, T.; Wolf, M.; Ertl, G.
  • The Journal of Chemical Physics, Vol. 102, Issue 8
  • DOI: 10.1063/1.469215

NO pairing and transformation to N2O on Cu() and Pt() from first principles
journal, May 2002


Dynamics of atomic adsorbates: hydrogen on Cu(111)
journal, September 1995


Cu-loaded dealuminated Y zeolites active in selective catalytic reduction of nitric oxide with ammonia
journal, March 2006


Geometry, vibrational frequencies and bonding mechanism of NO adsorbed on Cu(111)
journal, April 1996

  • Illas, F.; Ricart, J. M.; Fernández‐García, M.
  • The Journal of Chemical Physics, Vol. 104, Issue 14
  • DOI: 10.1063/1.471773

Molecular and atomic adsorption states of oxygen on Cu(111) at 100–300 K
journal, September 1996


Coadsorption of NO and NH 3 on Cu(111):  The Formation of the Stabilized (2 × 2) Coadlayer
journal, January 1996

  • Sueyoshi, Tsuyoshi; Sasaki, Takehiko; Iwasawa, Yasuhiro
  • The Journal of Physical Chemistry, Vol. 100, Issue 32
  • DOI: 10.1021/jp9606265

Atomic and Molecular Adsorption on Ir(111)
journal, January 2004

  • Krekelberg, William P.; Greeley, Jeff; Mavrikakis, Manos
  • The Journal of Physical Chemistry B, Vol. 108, Issue 3
  • DOI: 10.1021/jp035786c

Trends in Formic Acid Decomposition on Model Transition Metal Surfaces: A Density Functional Theory study
journal, November 2014

  • Herron, Jeffrey A.; Scaranto, Jessica; Ferrin, Peter
  • ACS Catalysis, Vol. 4, Issue 12
  • DOI: 10.1021/cs500737p

Chemisorption and vibration of hydrogen on Cu(111)
journal, April 1993


In situ STM studies of sulfur and thiocyanate adlayers on Cu(1 1 1) in alkaline solution
journal, September 2003


Improved adsorption energetics within density-functional theory using revised Perdew-Burke-Ernzerhof functionals
journal, March 1999


Recent development in catalytic technologies for methanol synthesis from renewable sources: A critical review
journal, April 2015

  • Ali, Khozema Ahmed; Abdullah, Ahmad Zuhairi; Mohamed, Abdul Rahman
  • Renewable and Sustainable Energy Reviews, Vol. 44
  • DOI: 10.1016/j.rser.2015.01.010

Preferential Oxidation of Carbon Monoxide in the Presence of Hydrogen (PROX) over Noble Metals and Transition Metal Oxides: Advantages and Drawbacks
journal, October 2008


Atoms, molecules, solids, and surfaces: Applications of the generalized gradient approximation for exchange and correlation
journal, September 1992


XPS and TPD study of NO interaction with Cu(111): Role of different oxygen species
journal, May 2013


Methanol–steam reforming on Cu/ZnO/Al2O3 catalysts. Part 2. A comprehensive kinetic model
journal, April 1999


Special Points in the Brillouin Zone
journal, December 1973


Soft self-consistent pseudopotentials in a generalized eigenvalue formalism
journal, April 1990


Oxygen chemisorption and cuprous oxide formation on Cu(111): A high resolution EELS study
journal, July 1982


Atomic and molecular adsorption on Ru(0001)
journal, August 2013


Adsorbate-substrate and adsorbate-adsorbate interactions of Na and K adlayers on Al(111)
journal, December 1992


Interactions of CO molecules adsorbed on Cu(111)
journal, January 1979


Chemisorption of CO on differently prepared Cu(111) surfaces
journal, October 1977


Atomic and molecular adsorption on Pt(111)
journal, August 2005


Untersuchung von oberflächenreaktionen mittels beugung langsamer elektronen (LEED)
journal, February 1967


Adsorption Microcalorimetry: Recent Advances in Instrumentation and Application
journal, July 2011


Hydrogenation of CO2 to value-added products—A review and potential future developments
journal, March 2014

  • Saeidi, Samrand; Amin, Nor Aishah Saidina; Rahimpour, Mohammad Reza
  • Journal of CO2 Utilization, Vol. 5
  • DOI: 10.1016/j.jcou.2013.12.005

ANALYSIS OF THE (3 × 3)- H / Cu (111) SYSTEM USING EIKONAL-LEVEL HELIUM ATOM SCATTERING SIMULATIONS
journal, December 2007


Summary Abstract: EELS study of nitric oxide adsorption on Cu(100) and Cu(111) surfaces
journal, March 1982

  • Wendelken, J. F.
  • Journal of Vacuum Science and Technology, Vol. 20, Issue 3
  • DOI: 10.1116/1.571377

The adsorption of oxygen on copper surfaces
journal, June 1982


The CO/Pt(111) Puzzle
journal, May 2001

  • Feibelman, Peter J.; Hammer, B.; Nørskov, J. K.
  • The Journal of Physical Chemistry B, Vol. 105, Issue 18
  • DOI: 10.1021/jp002302t

Catalysts for methanol steam reforming—A review
journal, August 2010


Atomic and molecular adsorption on Rh(111)
journal, October 2002

  • Mavrikakis, M.; Rempel, J.; Greeley, J.
  • The Journal of Chemical Physics, Vol. 117, Issue 14
  • DOI: 10.1063/1.1507104

Mechanism of Methanol Synthesis on Cu through CO 2 and CO Hydrogenation
journal, February 2011

  • Grabow, L. C.; Mavrikakis, M.
  • ACS Catalysis, Vol. 1, Issue 4
  • DOI: 10.1021/cs200055d

Nitrogen induced restructuring of Cu(111) and explosive desorption of N2
journal, September 1998


FT-rairs, eels and leed studies of the adsorption of carbon monoxide on Cu(111)
journal, September 1988


Low-temperature adsorption of CO on Cu(111) studied by RAIRS
journal, July 2002


Hydraulic performance of siphonic turbine in low head sites
journal, March 2015