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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

Journal Article · · Journal of Physical Chemistry. C
ORCiD logo [1];  [2];  [2]; ORCiD logo [3];  [4]
  1. Fritz-Haber-Inst. der Max-Planck-Gesellschaft, Berlin (Germany)
  2. Harvard Univ., Cambridge, MA (United States). John A. Paulson School of Engineering and Applied Science
  3. Harvard Univ., Cambridge, MA (United States). John A. Paulson School of Engineering and Applied Science, and Dept. of Chemistry and Chemical Biology
  4. Fritz-Haber-Inst. der Max-Planck-Gesellschaft, Berlin (Germany); Univ. of Luxembourg (Luxembourg). Physics and Material Science Research Unit
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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. In this study, 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. Finally, our calculations help establish the influence of individual and collective chemical factors that determine the catalytic selectivity of alkoxides.

Research Organization:
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 Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012573
OSTI ID:
1480511
Journal Information:
Journal of Physical Chemistry. C, Vol. 121, Issue 50; ISSN 1932-7447
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 11 works
Citation information provided by
Web of Science

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Cited By (3)

Non‐covalent Interactions and Charge Transfer between Propene and Neutral Yttrium‐Doped and Pure Gold Clusters journal November 2019
Stability of functionalized platform molecules on Au(111) journal December 2018
Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110) journal January 2018

Figures / Tables (11)

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