Density functional theory study of thermodynamic and kinetic isotope effects of H2/D2 dissociative adsorption on transition metals

doi:10.1039/C8CY00878G

Title: Density functional theory study of thermodynamic and kinetic isotope effects of H ₂/D ₂ dissociative adsorption on transition metals

Abstract

We studied here the thermodynamic isotope effects (TIEs) and kinetic isotope effects (KIEs) for H ₂/D ₂ dissociative adsorption using periodic, density functional theory (DFT)-based calculations. We examined the TIEs on the close-packed, open, and stepped surfaces, of twelve transition metals (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Re, Ir, Pt, and Au), and the KIEs on the surfaces of three noble metals (Cu, Ag, and Au). Both TIEs and KIEs were evaluated at 1/9 ML coverage. We find distinct TIEs on different adsorption sites, indicating that TIEs could be used in conjunction with binding energies to determine the dominant adsorption sites for hydrogen. Additionally, we find that while H ₂ dissociative adsorption may traditionally be considered structure insensitive in terms of reaction rates, it can exhibit structure sensitivity in terms of its KIEs. Complementarily to TIEs, KIEs might therefore be useful for identifying active sites for H ₂ dissociative adsorption on the three noble metal transition metal catalysts studied.

Authors:

Bai, Yunhai ^[1];

^[1]; Peng, Guowen ^[1];

^[1]

Univ. of Wisconsin, Madison, WI (United States). Dept. of Chemical and Biological Engineering

Publication Date:: 2018-06-13

Research Org.:: Univ. of Wisconsin, Madison, WI (United States)

Sponsoring Org.:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23)

OSTI Identifier:: 1494809

Alternate Identifier(s):: OSTI ID: 1454279

Grant/Contract Number:: FG02-05ER15731; AC02-06CH11357; AC02-05CH11231

Resource Type:: Accepted Manuscript

Journal Name:: Catalysis Science and Technology

Additional Journal Information:: Journal Volume: 8; Journal Issue: 13; Journal ID: ISSN 2044-4753

Publisher:: Royal Society of Chemistry

Country of Publication:: United States

Language:: English

Subject:: 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats


                    Bai, Yunhai, Chen, Benjamin W.  J., Peng, Guowen, and Mavrikakis, Manos. Density functional theory study of thermodynamic and kinetic isotope effects of H2/D2 dissociative adsorption on transition metals.  United States: N. p., 2018. 
        Web.  doi:10.1039/C8CY00878G.

Copy to clipboard


                    Bai, Yunhai, Chen, Benjamin W.  J., Peng, Guowen, & Mavrikakis, Manos. Density functional theory study of thermodynamic and kinetic isotope effects of H2/D2 dissociative adsorption on transition metals.  United States.  doi:10.1039/C8CY00878G.

Copy to clipboard


                    Bai, Yunhai, Chen, Benjamin W.  J., Peng, Guowen, and Mavrikakis, Manos. Wed .  
        "Density functional theory study of thermodynamic and kinetic isotope effects of H2/D2 dissociative adsorption on transition metals".  United States.  doi:10.1039/C8CY00878G.  https://www.osti.gov/servlets/purl/1494809.

Copy to clipboard


                    
@article{osti_1494809,

  title        = {Density functional theory study of thermodynamic and kinetic isotope effects of H2/D2 dissociative adsorption on transition metals},

  author       = {Bai, Yunhai and Chen, Benjamin W.  J. and Peng, Guowen and Mavrikakis, Manos},

  abstractNote = {We studied here the thermodynamic isotope effects (TIEs) and kinetic isotope effects (KIEs) for H2/D2 dissociative adsorption using periodic, density functional theory (DFT)-based calculations. We examined the TIEs on the close-packed, open, and stepped surfaces, of twelve transition metals (Fe, Co, Ni, Cu, Ru, Rh, Pd, Ag, Re, Ir, Pt, and Au), and the KIEs on the surfaces of three noble metals (Cu, Ag, and Au). Both TIEs and KIEs were evaluated at 1/9 ML coverage. We find distinct TIEs on different adsorption sites, indicating that TIEs could be used in conjunction with binding energies to determine the dominant adsorption sites for hydrogen. Additionally, we find that while H2 dissociative adsorption may traditionally be considered structure insensitive in terms of reaction rates, it can exhibit structure sensitivity in terms of its KIEs. Complementarily to TIEs, KIEs might therefore be useful for identifying active sites for H2 dissociative adsorption on the three noble metal transition metal catalysts studied.},

  doi          = {10.1039/C8CY00878G},

  journal      = {Catalysis Science and Technology},

  number       = 13,

  volume       = 8,

  place        = {United States},

  year         = {2018},

  month        = {6}

}

Copy to clipboard

Journal Article:

Free Publicly Available Full Text

Accepted Manuscript (DOE)

Publisher's Version of Record

DOI: 10.1039/C8CY00878G

Other availability

Search WorldCat to find libraries that may hold this journal

Citation Metrics:

Cited by: 2 works

Citation information provided by
Web of Science

Save / Share:

Export Metadata

Save to My Library

Works referenced in this record:

Projector augmented-wave method
journal, December 1994

Blöchl, P. E.
Physical Review B, Vol. 50, Issue 24, p. 17953-17979
DOI: 10.1103/PhysRevB.50.17953

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

Kresse, G.; Joubert, D.
Physical Review B, Vol. 59, Issue 3, p. 1758-1775
DOI: 10.1103/PhysRevB.59.1758

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

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

Kresse, G.; Furthmüller, J.
Computational Materials Science, Vol. 6, Issue 1, p. 15-50
DOI: 10.1016/0927-0256(96)00008-0

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

Kresse, G.; Furthmüller, J.
Physical Review B, Vol. 54, Issue 16, p. 11169-11186
DOI: 10.1103/PhysRevB.54.11169

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

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

Perdew, John P.; Wang, Yue
Physical Review B, Vol. 45, Issue 23, p. 13244-13249
DOI: 10.1103/PhysRevB.45.13244

Similar Records in DOE PAGES and OSTI.GOV collections:

Density functional theory study of thermodynamic and kinetic isotope effects of H ₂ /D ₂ dissociative adsorption on transition metals

Journal Article Bai, Yunhai ; Chen, Benjamin W. J. ; Peng, Guowen ; ... - Catalysis Science & Technology

Thermodynamic/kinetic isotope effects for H ₂ /D ₂ dissociative adsorption calculated on metal surfaces offer a means to identify active sites.
Cited by 1
DOI: 10.1039/C8CY00878G
Test of variational transition state theory and multidimensional semiclassical transmission coefficient methods against accurate quantal rate constants for H + H/sub 2//HD, D + H/sub 2/, and O + H/sub 2//D/sub 2//HD, including intra- and intermolecular kinetic isotope effects

Journal Article Garrett, B.C. ; Truhlar, D.G. ; Schatz, G.C. - J. Am. Chem. Soc.; (United States)

Rate constants and kinetic isotope effects for the title reactions have been calculated by using accurate quantum dynamical methods and used to test the accuracy of corresponding rate constants from conventional and variational transition state theory. The quantum dynamical rate constants are estimated to be within 35% of the exact rate constants for the potential surfaces chosen for this comparison. For all the reactions considered, the conventional and variational transition state theory rate constants with unit transmission coefficient are found to be very close to each other (better than 7%) but in poor agreement with the accurate quantum results (offmore »« less
DOI: 10.1021/ja00271a015
Computational study of the transition state for H[sub 2] addition to Vaska-type complexes (trans-Ir(L)[sub 2](CO)X). Substituent effects on the energy barrier and the origin of the small H[sub 2]/D[sub 2] kinetic isotope effect

Journal Article Abu-Hasanayn, F. ; Goldman, A.S. ; Krogh-Jespersen, K. - Journal of Physical Chemistry; (United States)

Ab initio molecular orbital methods have been used to study transition state properties for the concerted addition reaction of H[sub 2] to Vaska-type complexes, trans-Ir(L)[sub 2](CO)X, 1 (L = PH[sub 3] and X = F, Cl, Br, I, CN, or H; L = NH[sub 3] and X = Cl). Stationary points on the reaction path retaining the trans-L[sub 2] arrangement were located at the Hartree-Fock level using relativistic effective core potentials and valence basis sets of double-[zeta] quality. The identities of the stationary points were confirmed by normal mode analysis. Activation energy barriers were calculated with electron correlation effects includedmore »« less
DOI: 10.1021/j100124a019
Exact quantum mechanical study of kinetic isotope effects in the collinear reaction Cl + H$sub 2$ $Yields$ HCl + H. The H$sub 2$/D$sub 2$ and the H$sub 2$/T$sub 2$ isotope effects

Journal Article Persky, A. ; Baer, M. - J. Chem. Phys., v. 60, no. 1, pp. 133-136

Exact quantum mechanical probabilities for the collinear reaction of chlorine atoms with H/sub 2/, D/sub 2/, and T/sub 2/, in their ground and fi rst vibrational excited states, were calculated for a semiempirical LEPS potential energy surface. These probabilites were used to calculate the kinetic isotope effects k/sub Cl + H/sub 2//K/sub Cl + D/sub 2// and K/sub Cl + T/sub 2/ which are compared with experimental data and with results of transition state calculations. The effect of the vibrational excitation of the hydrogen molecules on the rate of other reaction with chlorine atoms was also studied. (auth)
Non-Transition-Metal Catalytic System for N ₂ Reduction to NH ₃: A Density Functional Theory Study of Al-Doped Graphene

Journal Article Tian, Yong-Hui ; Hu, Shuangli ; Sheng, Xiaolan ; ... - Journal of Physical Chemistry Letters

The prevalent catalysts for natural and artificial N ₂ fixation are known to hinge upon transition-metal (TM) elements. In this paper, we demonstrate by density functional theory that Al-doped graphene is a potential non-TM catalyst to convert N ₂ to NH ₃ in the presence of relatively mild proton/electron sources. In the integrated structure of the catalyst, the Al atom serves as a binding site and catalytic center while the graphene framework serves as an electron buffer during the successive proton/electron additions to N ₂ and its various downstream N _xH _y intermediates. The initial hydrogenation of N ₂ canmore »« less
Cited by 4
DOI: 10.1021/acs.jpclett.7b03094

Full Text Available

Similar Records

Title: Density functional theory study of thermodynamic and kinetic isotope effects of H 2/D 2 dissociative adsorption on transition metals

Abstract

Citation Formats

Projector augmented-wave method journal, December 1994

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

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

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

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

Special points for Brillouin-zone integrations journal, June 1976

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

Title: Density functional theory study of thermodynamic and kinetic isotope effects of H ₂/D ₂ dissociative adsorption on transition metals

Projector augmented-wave method
journal, December 1994

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

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

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

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

Special points for Brillouin-zone integrations
journal, June 1976

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