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Title: General Effect of van der Waals Interactions on the Stability of Alkoxy Intermediates on Metal Surfaces

Abstract

The critical role of noncovalent van der Waals (vdW) interactions in determining the relative thermodynamic stability of alkoxy intermediates has been demonstrated for the Cu(110) surface using a combination of experiment and theory. The results may be significant for the selectivity control of copper-based reactions of alcohols. Previous examination of this effect on Au(110) was also extended to include higher molecular weight alcohols; on Cu(110) and Au(110) the hierarchy for the strength of binding of the alkoxys was found to be the same within experimental accuracy, with alkoxy species of greater chain length being more stable. The equilibrium constants governing the competition of alcohol pairs for binding sites of the alkoxys are also similar on the two surfaces. These results reveal the generality of such vdW effects. In conclusion, this work expands the understanding of the role of vdW interactions on the binding efficacy of key reactive intermediates on metal surfaces, a key factor in the rational design of complex and selective catalytic processes.

Authors:
 [1];  [2];  [2]; ORCiD logo [3];  [4]
  1. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology
  2. Harvard Univ., Cambridge, MA (United States). Dept. of Physics; Harvard Univ., Cambridge, MA (United States). Harvard John A. Paulson School of Engineering and Applied Sciences
  3. Harvard Univ., Cambridge, MA (United States). Dept. of Chemistry and Chemical Biology; Harvard Univ., Cambridge, MA (United States). Harvard John A. Paulson School of Engineering and Applied Sciences
  4. Harvard Univ., Cambridge, MA (United States). Harvard John A. Paulson School of Engineering and Applied Sciences
Publication Date:
Research Org.:
Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Oak Ridge Leadership Computing Facility (OLCF); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); 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)
OSTI Identifier:
1480287
Grant/Contract Number:  
SC0012573
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry
Additional Journal Information:
Journal Volume: 122; Journal Issue: 2; Journal ID: ISSN 1520-6106
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Xu, Yunfei, Chen, Wei, Kaxiras, Efthimios, Friend, Cynthia M., and Madix, Robert J.. General Effect of van der Waals Interactions on the Stability of Alkoxy Intermediates on Metal Surfaces. United States: N. p., 2017. Web. https://doi.org/10.1021/acs.jpcb.7b04952.
Xu, Yunfei, Chen, Wei, Kaxiras, Efthimios, Friend, Cynthia M., & Madix, Robert J.. General Effect of van der Waals Interactions on the Stability of Alkoxy Intermediates on Metal Surfaces. United States. https://doi.org/10.1021/acs.jpcb.7b04952
Xu, Yunfei, Chen, Wei, Kaxiras, Efthimios, Friend, Cynthia M., and Madix, Robert J.. Wed . "General Effect of van der Waals Interactions on the Stability of Alkoxy Intermediates on Metal Surfaces". United States. https://doi.org/10.1021/acs.jpcb.7b04952. https://www.osti.gov/servlets/purl/1480287.
@article{osti_1480287,
title = {General Effect of van der Waals Interactions on the Stability of Alkoxy Intermediates on Metal Surfaces},
author = {Xu, Yunfei and Chen, Wei and Kaxiras, Efthimios and Friend, Cynthia M. and Madix, Robert J.},
abstractNote = {The critical role of noncovalent van der Waals (vdW) interactions in determining the relative thermodynamic stability of alkoxy intermediates has been demonstrated for the Cu(110) surface using a combination of experiment and theory. The results may be significant for the selectivity control of copper-based reactions of alcohols. Previous examination of this effect on Au(110) was also extended to include higher molecular weight alcohols; on Cu(110) and Au(110) the hierarchy for the strength of binding of the alkoxys was found to be the same within experimental accuracy, with alkoxy species of greater chain length being more stable. The equilibrium constants governing the competition of alcohol pairs for binding sites of the alkoxys are also similar on the two surfaces. These results reveal the generality of such vdW effects. In conclusion, this work expands the understanding of the role of vdW interactions on the binding efficacy of key reactive intermediates on metal surfaces, a key factor in the rational design of complex and selective catalytic processes.},
doi = {10.1021/acs.jpcb.7b04952},
journal = {Journal of Physical Chemistry. B, Condensed Matter, Materials, Surfaces, Interfaces and Biophysical Chemistry},
number = 2,
volume = 122,
place = {United States},
year = {2017},
month = {7}
}

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    Direct Correlation between Adsorption Energetics and Nuclear Spin Relaxation in a Liquid-saturated Catalyst Material
    journal, September 2018

    • Robinson, Neil; Robertson, Christopher; Gladden, Lynn F.
    • ChemPhysChem, Vol. 19, Issue 19
    • DOI: 10.1002/cphc.201800836

    Stability of functionalized platform molecules on Au(111)
    journal, December 2018

    • Jasper-Tönnies, Torben; Poltavsky, Igor; Ulrich, Sandra
    • The Journal of Chemical Physics, Vol. 149, Issue 24
    • DOI: 10.1063/1.5059344

    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