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Title: First-Principles Study of Alkoxides Adsorbed on Au(111) and Au(110) Surfaces: Assessing the Roles of Noncovalent Interactions and Molecular Structures in Catalysis

Abstract

Microscopic understanding of molecular adsorption on catalytic surfaces is crucial for controlling the activity and selectivity of chemical reactions. However, for complex molecules, the adsorption process is very system-specific and there is a clear need to elaborate systematic understanding of important factors that determine catalytic functionality. Here, we investigate the binding of eight molecules, including seven alkoxides and one carboxylate, on the Au(111) and Au(110) surfaces. Our density-functional theory calculations including long-range van der Waals interactions demonstrate the significant role of these “weak” noncovalent forces on the adsorption structures, energetics, and relative adsorbate stabilities. Interestingly, the binding energy trends are insensitive to the surface structure. Instead, the adsorption stability depends strongly on the structural and chemical characteristics of the molecules: linear vs branching configurations, number of unsaturated C–C bonds, bidentate adsorption, and the presence of electronegative atoms. Our calculations help establish the influence of individual and collective chemical factors that determine the catalytic selectivity of alkoxides.

Authors:
ORCiD logo [1];  [2];  [2]; ORCiD logo [3];  [4]
  1. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195, Berlin, Germany
  2. John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, United States
  3. John A. Paulson School of Engineering and Applied Sciences, Harvard University, Cambridge, Massachusetts 02138, United States; Department of Chemistry and Chemical Biology, Harvard University, Cambridge, Massachusetts 02138, United States
  4. Fritz-Haber-Institut der Max-Planck-Gesellschaft, Faradayweg 4-6, D-14195, Berlin, Germany; Physics and Material Science Research Unit, University of Luxembourg, L-1511 Luxembourg, Luxembourg
Publication Date:
Research Org.:
Oak Ridge National Laboratory, Oak Ridge Leadership Computing Facility (OLCF); Lawrence Berkeley National Laboratory-National Energy Research Scientific Computing Center
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1480511
Grant/Contract Number:  
SC0012573
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. C
Additional Journal Information:
Journal Volume: 121; Journal Issue: 50; Journal ID: ISSN 1932-7447
Country of Publication:
United States
Language:
English

Citation Formats

Cheenicode Kabeer, Fairoja, Chen, Wei, Madix, Robert J., Friend, Cynthia M., and Tkatchenko, Alexandre. First-Principles Study of Alkoxides Adsorbed on Au(111) and Au(110) Surfaces: Assessing the Roles of Noncovalent Interactions and Molecular Structures in Catalysis. United States: N. p., 2017. Web. doi:10.1021/acs.jpcc.7b06641.
Cheenicode Kabeer, Fairoja, Chen, Wei, Madix, Robert J., Friend, Cynthia M., & Tkatchenko, Alexandre. First-Principles Study of Alkoxides Adsorbed on Au(111) and Au(110) Surfaces: Assessing the Roles of Noncovalent Interactions and Molecular Structures in Catalysis. United States. doi:10.1021/acs.jpcc.7b06641.
Cheenicode Kabeer, Fairoja, Chen, Wei, Madix, Robert J., Friend, Cynthia M., and Tkatchenko, Alexandre. Tue . "First-Principles Study of Alkoxides Adsorbed on Au(111) and Au(110) Surfaces: Assessing the Roles of Noncovalent Interactions and Molecular Structures in Catalysis". United States. doi:10.1021/acs.jpcc.7b06641. https://www.osti.gov/servlets/purl/1480511.
@article{osti_1480511,
title = {First-Principles Study of Alkoxides Adsorbed on Au(111) and Au(110) Surfaces: Assessing the Roles of Noncovalent Interactions and Molecular Structures in Catalysis},
author = {Cheenicode Kabeer, Fairoja and Chen, Wei and Madix, Robert J. and Friend, Cynthia M. and Tkatchenko, Alexandre},
abstractNote = {Microscopic understanding of molecular adsorption on catalytic surfaces is crucial for controlling the activity and selectivity of chemical reactions. However, for complex molecules, the adsorption process is very system-specific and there is a clear need to elaborate systematic understanding of important factors that determine catalytic functionality. Here, we investigate the binding of eight molecules, including seven alkoxides and one carboxylate, on the Au(111) and Au(110) surfaces. Our density-functional theory calculations including long-range van der Waals interactions demonstrate the significant role of these “weak” noncovalent forces on the adsorption structures, energetics, and relative adsorbate stabilities. Interestingly, the binding energy trends are insensitive to the surface structure. Instead, the adsorption stability depends strongly on the structural and chemical characteristics of the molecules: linear vs branching configurations, number of unsaturated C–C bonds, bidentate adsorption, and the presence of electronegative atoms. Our calculations help establish the influence of individual and collective chemical factors that determine the catalytic selectivity of alkoxides.},
doi = {10.1021/acs.jpcc.7b06641},
journal = {Journal of Physical Chemistry. C},
number = 50,
volume = 121,
place = {United States},
year = {2017},
month = {12}
}

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