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Title: Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110)

Abstract

The relative stability of carboxylates on Au(110) was investigated as part of a comprehensive study of adsorbate binding on Group IB metals that can be used to predict and understand how to control reactivity in heterogeneous catalysis. The binding efficacy of carboxylates is only weakly dependent on alkyl chain length for relatively short-chain molecules, as demonstrated using quantitative temperature-programmed reaction spectroscopy. Corresponding density functional theory (DFT) calculations demonstrated that the bidentate anchoring geometry is rigid and restricts the amount of additional stabilization through adsorbate-surface van der Waals (vdW) interactions which control stability for alkoxides. A combination of scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) shows that carboxylates form dense local islands on Au(110). Complementary DFT calculations demonstrate that adsorbate–adsorbate interactions provide additional stabilization that increases as a function of alkyl chain length for C2 and C3 carboxylates. Hence, overall stability is generally a function of the anchoring group to the surface and the inter-adsorbate interaction. This study demonstrates the importance of these two important factors in describing binding of key catalytic intermediates.

Authors:
ORCiD logo [1];  [1];  [2];  [2];  [3]; ORCiD logo [4]
  1. Department of Chemistry and Chemical Biology, Harvard University, Cambridge, USA
  2. School of Engineering and Applied Sciences, Harvard University, Cambridge, USA, Department of Physics
  3. School of Engineering and Applied Sciences, Harvard University, Cambridge, USA
  4. Department of Chemistry and Chemical Biology, Harvard University, Cambridge, USA, School of Engineering and Applied Sciences
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC), Washington, D.C. (United States). Integrated Mesoscale Architectures for Sustainable Catalysis (IMASC)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1430376
Alternate Identifier(s):
OSTI ID: 1470273
Grant/Contract Number:  
SC0012573
Resource Type:
Published Article
Journal Name:
Chemical Science
Additional Journal Information:
Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 15; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (heterogeneous); mesostructured materials; materials and chemistry by design; synthesis (novel materials)

Citation Formats

O'Connor, Christopher R., Hiebel, Fanny, Chen, Wei, Kaxiras, Efthimios, Madix, Robert J., and Friend, Cynthia M. Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110). United Kingdom: N. p., 2018. Web. doi:10.1039/C7SC05313D.
O'Connor, Christopher R., Hiebel, Fanny, Chen, Wei, Kaxiras, Efthimios, Madix, Robert J., & Friend, Cynthia M. Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110). United Kingdom. https://doi.org/10.1039/C7SC05313D
O'Connor, Christopher R., Hiebel, Fanny, Chen, Wei, Kaxiras, Efthimios, Madix, Robert J., and Friend, Cynthia M. Mon . "Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110)". United Kingdom. https://doi.org/10.1039/C7SC05313D.
@article{osti_1430376,
title = {Identifying key descriptors in surface binding: interplay of surface anchoring and intermolecular interactions for carboxylates on Au(110)},
author = {O'Connor, Christopher R. and Hiebel, Fanny and Chen, Wei and Kaxiras, Efthimios and Madix, Robert J. and Friend, Cynthia M.},
abstractNote = {The relative stability of carboxylates on Au(110) was investigated as part of a comprehensive study of adsorbate binding on Group IB metals that can be used to predict and understand how to control reactivity in heterogeneous catalysis. The binding efficacy of carboxylates is only weakly dependent on alkyl chain length for relatively short-chain molecules, as demonstrated using quantitative temperature-programmed reaction spectroscopy. Corresponding density functional theory (DFT) calculations demonstrated that the bidentate anchoring geometry is rigid and restricts the amount of additional stabilization through adsorbate-surface van der Waals (vdW) interactions which control stability for alkoxides. A combination of scanning tunneling microscopy (STM) and low-energy electron diffraction (LEED) shows that carboxylates form dense local islands on Au(110). Complementary DFT calculations demonstrate that adsorbate–adsorbate interactions provide additional stabilization that increases as a function of alkyl chain length for C2 and C3 carboxylates. Hence, overall stability is generally a function of the anchoring group to the surface and the inter-adsorbate interaction. This study demonstrates the importance of these two important factors in describing binding of key catalytic intermediates.},
doi = {10.1039/C7SC05313D},
journal = {Chemical Science},
number = 15,
volume = 9,
place = {United Kingdom},
year = {Mon Jan 01 00:00:00 EST 2018},
month = {Mon Jan 01 00:00:00 EST 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1039/C7SC05313D

Citation Metrics:
Cited by: 10 works
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Figures / Tables:

Fig. 1 Fig. 1: Temperature programmed experiments show nearly complete displacement of acetate by trifluoroacetic acid on Au(110) at 300 K. (A) The characteristic products for reaction of 0.10 ML of isolated trifluoroacetate (red) decomposed to CF3 and CO2 at 590 K, while 0.10 ML of isolated acetate (blue) decomposed to CO2more » and CH3 at 580 K. (B) The introduction of (i) excess trifluoroacetic acid to acetate and (ii) excess acetic acid to trifluoroacetate yields products characteristic of a majority species trifluoroacetate and a minority species acetate. The deconvolution of the CO2 peak for acetate (blue) and trifluoroacetate (red) is determined by using a selectivity fraction on the CH3 and CF3 peaks. Both orders of adsorption show displacement that favors trifluoroacetate.« less

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Figures/Tables have been extracted from DOE-funded journal article accepted manuscripts.