Issue 15, 2018

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.

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

Supplementary files

Article information

Article type
Edge Article
Submitted
14 дек 2017
Accepted
26 фев 2018
First published
12 мар 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2018,9, 3759-3766

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

C. R. O'Connor, F. Hiebel, W. Chen, E. Kaxiras, R. J. Madix and C. M. Friend, Chem. Sci., 2018, 9, 3759 DOI: 10.1039/C7SC05313D

This article is licensed under a Creative Commons Attribution 3.0 Unported Licence. You can use material from this article in other publications without requesting further permissions from the RSC, provided that the correct acknowledgement is given.

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