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

O'Connor, Christopher R.; Hiebel, Fanny; Chen, Wei; Kaxiras, Efthimios; Madix, Robert J.; Friend, Cynthia M.

doi:10.1039/C7SC05313D

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

Journal Article · Mon Jan 01 00:00:00 EST 2018 · Chemical Science

DOI:https://doi.org/10.1039/C7SC05313D· OSTI ID:1430376

^[1]; Hiebel, Fanny ^[1]; Chen, Wei ^[2]; Kaxiras, Efthimios ^[2]; Madix, Robert J. ^[3];

^[4]

Department of Chemistry and Chemical Biology, Harvard University, Cambridge, USA
School of Engineering and Applied Sciences, Harvard University, Cambridge, USA, Department of Physics
School of Engineering and Applied Sciences, Harvard University, Cambridge, USA
Department of Chemistry and Chemical Biology, Harvard University, Cambridge, USA, School of Engineering and Applied Sciences

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.

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Research Organization:: Energy Frontier Research Centers (EFRC), Washington, D.C. (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:: 1430376

Alternate ID(s):: OSTI ID: 1470273

Journal Information:: Chemical Science, Journal Name: Chemical Science Vol. 9 Journal Issue: 15; ISSN 2041-6520

Publisher:: Royal Society of Chemistry (RSC)Copyright Statement

Country of Publication:: United Kingdom

Language:: English

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Cited by: 10 works

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