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Title: How coverage influences thermodynamic and kinetic isotope effects for H 2 /D 2 dissociative adsorption on transition metals

Abstract

Hydrogen isotope effects are influenced by adsorbate coverage: at high coverages, isotope effects are lower than at low coverages. This helps to rationalize observed isotope effects, allowing more precise elucidation of reaction mechanisms.

Authors:
ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemical and Biological Engineering, University of Wisconsin – Madison, Madison, USA
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1581022
Grant/Contract Number:  
FG02-05ER15731
Resource Type:
Publisher's Accepted Manuscript
Journal Name:
Catalysis Science and Technology
Additional Journal Information:
Journal Name: Catalysis Science and Technology; Journal ID: ISSN 2044-4753
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English

Citation Formats

Chen, Benjamin W. J., and Mavrikakis, Manos. How coverage influences thermodynamic and kinetic isotope effects for H 2 /D 2 dissociative adsorption on transition metals. United Kingdom: N. p., 2020. Web. doi:10.1039/C9CY02338K.
Chen, Benjamin W. J., & Mavrikakis, Manos. How coverage influences thermodynamic and kinetic isotope effects for H 2 /D 2 dissociative adsorption on transition metals. United Kingdom. doi:10.1039/C9CY02338K.
Chen, Benjamin W. J., and Mavrikakis, Manos. Wed . "How coverage influences thermodynamic and kinetic isotope effects for H 2 /D 2 dissociative adsorption on transition metals". United Kingdom. doi:10.1039/C9CY02338K.
@article{osti_1581022,
title = {How coverage influences thermodynamic and kinetic isotope effects for H 2 /D 2 dissociative adsorption on transition metals},
author = {Chen, Benjamin W. J. and Mavrikakis, Manos},
abstractNote = {Hydrogen isotope effects are influenced by adsorbate coverage: at high coverages, isotope effects are lower than at low coverages. This helps to rationalize observed isotope effects, allowing more precise elucidation of reaction mechanisms.},
doi = {10.1039/C9CY02338K},
journal = {Catalysis Science and Technology},
number = ,
volume = ,
place = {United Kingdom},
year = {2020},
month = {1}
}

Journal Article:
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Works referenced in this record:

Quantum tunneling observed without its characteristic large kinetic isotope effects
journal, June 2015

  • Hama, Tetsuya; Ueta, Hirokazu; Kouchi, Akira
  • Proceedings of the National Academy of Sciences, Vol. 112, Issue 24
  • DOI: 10.1073/pnas.1501328112

Interaction of Hydrogen with a Cobalt(0001) Surface
journal, June 2013

  • Huesges, Zita; Christmann, Klaus
  • Zeitschrift für Physikalische Chemie, Vol. 227, Issue 6-7
  • DOI: 10.1524/zpch.2013.0381

Kinetic Isotopic Effects in Oxidative Dehydrogenation of Propane on Vanadium Oxide Catalysts
journal, May 2000

  • Chen, Kaidong; Iglesia, Enrique; Bell, Alexis T.
  • Journal of Catalysis, Vol. 192, Issue 1
  • DOI: 10.1006/jcat.2000.2832

Dissociative adsorption of hydrogen on Cu(100) at low temperatures
journal, May 1993


Projector augmented-wave method
journal, December 1994


Energetics of hydrogen coverage on group VIII transition metal surfaces and a kinetic model for adsorption/desorption
journal, January 2005

  • Faglioni, Francesco; Goddard, William A.
  • The Journal of Chemical Physics, Vol. 122, Issue 1
  • DOI: 10.1063/1.1814938

Adsorbate structure in the H-induced p 4 g reconstruction of the Cu(001) surface
journal, February 1995


Supra-monolayer coverages on small metal clusters and their effects on H 2 chemisorption particle size estimates
journal, February 2018

  • Almithn, Abdulrahman S.; Hibbitts, David D.
  • AIChE Journal, Vol. 64, Issue 8
  • DOI: 10.1002/aic.16110

Computational Thermochemistry: Scale Factor Databases and Scale Factors for Vibrational Frequencies Obtained from Electronic Model Chemistries
journal, August 2010

  • Alecu, I. M.; Zheng, Jingjing; Zhao, Yan
  • Journal of Chemical Theory and Computation, Vol. 6, Issue 9
  • DOI: 10.1021/ct100326h

Binding Isotope Effects
journal, July 2013

  • Świderek, Katarzyna; Paneth, Piotr
  • Chemical Reviews, Vol. 113, Issue 10
  • DOI: 10.1021/cr300515x

Hydrogen-Induced Reconstruction of Cu(100): Two-Dimensional and One-Dimensional Structures of Surface Hydride
journal, July 2014

  • Hellman, A.; Svensson, K.; Andersson, S.
  • The Journal of Physical Chemistry C, Vol. 118, Issue 29
  • DOI: 10.1021/jp5035147

Endothermic dissociative chemisorption of molecular D2 on Ag(111)
journal, September 1995


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


Scaling relationships and theory for vibrational frequencies of adsorbates on transition metal surfaces
journal, November 2017

  • Lansford, Joshua L.; Mironenko, Alexander V.; Vlachos, Dionisios G.
  • Nature Communications, Vol. 8, Issue 1
  • DOI: 10.1038/s41467-017-01983-6

Effects of Catalyst Model and High Adsorbate Coverages in ab Initio Studies of Alkane Hydrogenolysis
journal, May 2018


On the effect of coverage-dependent adsorbate–adsorbate interactions for CO methanation on transition metal surfaces
journal, November 2013


The effects of steps, coupling to substrate vibrations, and surface coverage on surface diffusion rates and kinetic isotope effects: Hydrogen diffusion on Ni
journal, August 1990

  • Truong, Thanh N.; Truhlar, Donald G.
  • The Journal of Chemical Physics, Vol. 93, Issue 3
  • DOI: 10.1063/1.459038

Hydrogen-induced restructuring of close-packed metal surfaces: H/Ni(111) and H/Fe(110)
journal, June 1993


Hydrogen Chemisorption Isotherms on Platinum Particles at Catalytic Temperatures: Langmuir and Two-Dimensional Gas Models Revisited
journal, October 2018

  • García-Diéguez, Mónica; Hibbitts, David D.; Iglesia, Enrique
  • The Journal of Physical Chemistry C, Vol. 123, Issue 13
  • DOI: 10.1021/acs.jpcc.8b10877

Comparison of hydrogen and deuterium adsorption on Pd(100)
journal, January 2010

  • Gladys, M. J.; Kambali, I.; Karolewski, M. A.
  • The Journal of Chemical Physics, Vol. 132, Issue 2
  • DOI: 10.1063/1.3292686

Isotope Effects Reveal an Alternative Mechanism for “Iminium-Ion” Catalysis
journal, June 2018

  • Izzo, Joseph A.; Poulsen, Pernille H.; Intrator, Jeremy A.
  • Journal of the American Chemical Society, Vol. 140, Issue 27
  • DOI: 10.1021/jacs.8b04856

Orbitalwise Coordination Number for Predicting Adsorption Properties of Metal Nanocatalysts
journal, January 2017


Hydrogen adsorption, absorption and diffusion on and in transition metal surfaces: A DFT study
journal, April 2012


Kinetically Relevant Steps and H 2 /D 2 Isotope Effects in Fischer−Tropsch Synthesis on Fe and Co Catalysts
journal, October 2010

  • Ojeda, Manuel; Li, Anwu; Nabar, Rahul
  • The Journal of Physical Chemistry C, Vol. 114, Issue 46
  • DOI: 10.1021/jp1073076

Hydrogen on Ru(001) revisited: vibrational structure, adsorption states, and lateral coupling
journal, July 2004


Structure- and Coverage-Sensitive Mechanism of NO Reduction on Platinum Electrodes
journal, June 2017

  • Katsounaros, Ioannis; Figueiredo, Marta C.; Chen, Xiaoting
  • ACS Catalysis, Vol. 7, Issue 7
  • DOI: 10.1021/acscatal.7b01069

Significant Quantum Effects in Hydrogen Activation
journal, April 2014

  • Kyriakou, Georgios; Davidson, Erlend R. M.; Peng, Guowen
  • ACS Nano, Vol. 8, Issue 5
  • DOI: 10.1021/nn500703k

A climbing image nudged elastic band method for finding saddle points and minimum energy paths
journal, December 2000

  • Henkelman, Graeme; Uberuaga, Blas P.; Jónsson, Hannes
  • The Journal of Chemical Physics, Vol. 113, Issue 22, p. 9901-9904
  • DOI: 10.1063/1.1329672

Factor group splitting and dispersion on internal vibrational modes: A qualitative discussion
journal, December 1984

  • Durman, Ray; Jayasooriya, Upali A.; Kettle, Sidney F. A.
  • The Journal of Chemical Physics, Vol. 81, Issue 12
  • DOI: 10.1063/1.447690

Adsorption energies and ordered structures of hydrogen on Pd(111) from density-functional periodic calculations
journal, October 1998


Dipole correction for surface supercell calculations
journal, May 1999


Benchmark First-Principles Calculations of Adsorbate Free Energies
journal, January 2018


Hydrogen adsorption on palladium and palladium hydride at 1bar
journal, April 2010


H/D Isotope Effects Reveal Factors Controlling Catalytic Activity in Co-Based Oxides for Water Oxidation
journal, January 2019

  • Pasquini, Chiara; Zaharieva, Ivelina; González-Flores, Diego
  • Journal of the American Chemical Society, Vol. 141, Issue 7
  • DOI: 10.1021/jacs.8b10002

The Deuterium Isotope Effect
journal, August 1955


Vibrational spectra of hydrogen on the Rh(111) surface
journal, November 1999


Hydrogen adsorption on Ru(001) studied by scanning tunneling microscopy
journal, January 2008


Dissociative chemisorption of hydrogen on Ir(111): Evidence for terminal site adsorption
journal, November 1999

  • Hagedorn, Christopher J.; Weiss, Michael J.; Weinberg, W. Henry
  • Physical Review B, Vol. 60, Issue 20
  • DOI: 10.1103/PhysRevB.60.R14016

Location of hydrogen adsorbed on Rh(111) studied by low-energy electron diffraction and nuclear reaction analysis
journal, June 2007


Vibrationally assisted sticking, tunneling and isotope effect for hydrogen on Cu surfaces
journal, April 1991


Uncovering the Relationship between the Change in Heat Capacity for Enzyme Catalysis and Vibrational Frequency through Isotope Effect Studies
journal, April 2018

  • Jones, Hannah B. L.; Crean, Rory M.; Matthews, Christopher
  • ACS Catalysis, Vol. 8, Issue 6
  • DOI: 10.1021/acscatal.8b01025

Density Functional Theory Calculations and Analysis of Reaction Pathways for Reduction of Nitric Oxide by Hydrogen on Pt(111)
journal, September 2014

  • Farberow, Carrie A.; Dumesic, James A.; Mavrikakis, Manos
  • ACS Catalysis, Vol. 4, Issue 10
  • DOI: 10.1021/cs500668k

Insights from calculated phonon dispersion curves for an overlayer of H on Pt(111)
journal, August 2005


Adsorption of hydrogen on Pt(111) and Pt(100) surfaces and its role in the HOR
journal, October 2008

  • Strmcnik, D.; Tripkovic, D.; van der Vliet, D.
  • Electrochemistry Communications, Vol. 10, Issue 10, p. 1602-1605
  • DOI: 10.1016/j.elecom.2008.08.019

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


Dynamically Bifurcating Hydride Transfer Mechanism and Origin of Inverse Isotope Effect for Heterodinuclear AgRu-Catalyzed Alkyne Semihydrogenation
journal, February 2019


Hydrogen Adsorption on Co Surfaces: A Density Functional Theory and Temperature Programmed Desorption Study
journal, April 2012

  • van Helden, Pieter; van den Berg, Jan-Albert; Weststrate, Cornelis J.
  • ACS Catalysis, Vol. 2, Issue 6
  • DOI: 10.1021/cs2006586

Adsorption and Coadsorption of CO and H on Ruthenium Surfaces
journal, January 2003

  • Ciobica, I. M.; Kleyn, A. W.; Van Santen, R. A.
  • The Journal of Physical Chemistry B, Vol. 107, Issue 1
  • DOI: 10.1021/jp0201478

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


Special points for Brillouin-zone integrations
journal, June 1976

  • Monkhorst, Hendrik J.; Pack, James D.
  • Physical Review B, Vol. 13, Issue 12, p. 5188-5192
  • DOI: 10.1103/PhysRevB.13.5188

Variational transition state theory. Primary kinetic isotope effects for atom transfer reactions
journal, April 1980

  • Garrett, Bruce C.; Truhlar, Donald G.
  • Journal of the American Chemical Society, Vol. 102, Issue 8
  • DOI: 10.1021/ja00528a008

Chemisorption of hydrogen on the Ag(111) surface
journal, July 1994

  • Lee, Geunseop; Sprunger, P. T.; Okada, M.
  • Journal of Vacuum Science & Technology A: Vacuum, Surfaces, and Films, Vol. 12, Issue 4
  • DOI: 10.1116/1.579147

Hydrogen Isotope Effect on Thermodynamic and Kinetics of Hydrogen/Deuterium Absorption–Desorption in Pd 0.77 Ag 0.10 Cu 0.13 Alloy
journal, April 2015

  • Pati, Subhasis; Jat, Ram A.; Mukerjee, Sapan K.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 19
  • DOI: 10.1021/acs.jpcc.5b03031

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


Density-Functional Analysis of Hydrogen on Pt(111): Electric Field, Solvent, and Coverage Effects
journal, June 2008

  • Hamada, Ikutaro; Morikawa, Yoshitada
  • The Journal of Physical Chemistry C, Vol. 112, Issue 29
  • DOI: 10.1021/jp8028787

Unusual adsorption site of hydrogen on the unreconstructed Ir(100) surface
journal, February 2006


First-principles potential energy surfaces and vibrational states of H∕Rh(111) at 0.25 and 1 monolayer coverages
journal, June 2006

  • Ke, Zhihong; Lai, Wenzhen; Xie, Daiqian
  • Journal of Applied Physics, Vol. 99, Issue 11
  • DOI: 10.1063/1.2199007

The influence of potential energy surface topologies on the dissociation of H 2
journal, August 1990

  • Halstead, D.; Holloway, S.
  • The Journal of Chemical Physics, Vol. 93, Issue 4
  • DOI: 10.1063/1.458871

Effect of hydrogen on the surface relaxation of Pd(100), Rh(100), and Ag(100)
journal, November 2005


Subsurface penetration of chemisorbed hydrogen isotopes into the Ru(0001) crystal surface
journal, September 1985


Dense CO Adlayers as Enablers of CO Hydrogenation Turnovers on Ru Surfaces
journal, August 2017

  • Liu, Jianwei; Hibbitts, David; Iglesia, Enrique
  • Journal of the American Chemical Society, Vol. 139, Issue 34
  • DOI: 10.1021/jacs.7b04606

Accurate and simple analytic representation of the electron-gas correlation energy
journal, June 1992


Ligand Effect in Hydrogen Adsorption on Epitaxial Nickel Films
journal, January 2009

  • Heinz, Klaus; Hammer, Lutz; Gumler, Bernd
  • Zeitschrift für Physikalische Chemie, Vol. 223, Issue 1-2
  • DOI: 10.1524/zpch.2009.6025

Dynamics of the dissociative adsorption of hydrogen on nickel(100)
journal, December 1985

  • Hamza, A. V.; Madix, R. J.
  • The Journal of Physical Chemistry, Vol. 89, Issue 25
  • DOI: 10.1021/j100271a014

CO Chemisorption and Dissociation at High Coverages during CO Hydrogenation on Ru Catalysts
journal, April 2013

  • Loveless, Brett T.; Buda, Corneliu; Neurock, Matthew
  • Journal of the American Chemical Society, Vol. 135, Issue 16
  • DOI: 10.1021/ja311848e

Coverage-dependent hydrogen adsorption site determination on Rh ( 100 ) by high-resolution core-level spectroscopy
journal, September 2004


Origin of Enzymatic Kinetic Isotope Effects in Human Purine Nucleoside Phosphorylase
journal, December 2017


The critical role of water at the gold-titania interface in catalytic CO oxidation
journal, September 2014


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


On the Sequential Hydrogen Dissociative Chemisorption on Small Platinum Clusters: A Density Functional Theory Study
journal, August 2007

  • Zhou, Chenggang; Wu, Jinping; Nie, Aihua
  • The Journal of Physical Chemistry C, Vol. 111, Issue 34
  • DOI: 10.1021/jp073597e

Chemisorption and diffusion of hydrogen on surface and subsurface sites of flat and stepped nickel surfaces
journal, May 2005

  • Bhatia, Bhawna; Sholl, David S.
  • The Journal of Chemical Physics, Vol. 122, Issue 20
  • DOI: 10.1063/1.1902943

Simultaneous Deep Tunneling and Classical Hopping for Hydrogen Diffusion on Metals
journal, September 2017


Density functional theory calculations for the hydrogen evolution reaction in an electrochemical double layer on the Pt(111) electrode
journal, January 2007

  • Skúlason, Egill; Karlberg, Gustav S.; Rossmeisl, Jan
  • Phys. Chem. Chem. Phys., Vol. 9, Issue 25
  • DOI: 10.1039/B700099E

Quantitative determination of hydrogen adsorption site on the Pt(111)-(1×1) surface by low energy ion channeling
journal, July 1999

  • Lui, K. M.; Kim, Y.; Lau, W. M.
  • Applied Physics Letters, Vol. 75, Issue 4
  • DOI: 10.1063/1.124450

Energetic Stability of Absorbed H in Pd and Pt Nanoparticles in a More Realistic Environment
journal, February 2015

  • Kozlov, Sergey M.; Aleksandrov, Hristiyan A.; Neyman, Konstantin M.
  • The Journal of Physical Chemistry C, Vol. 119, Issue 9
  • DOI: 10.1021/jp513022m

Observation of an Inverse Kinetic Isotope Effect in Oxygen Evolution Electrochemistry
journal, August 2016


The deuterium-induced reconstruction of Cu(100): Correlation of surface structures with absolute coverage
journal, June 1994