Understanding the interaction of organic corrosion inhibitors with copper at the molecular scale: Benzotriazole on Cu(110)

Marco Turano, Marc Walker, Federico Grillo, Chiara Gattinoni, James Edmondson, Omar Adesida, Gregory Hunt, Paul Kirkman, Neville V. Richardson, Christopher J. Baddeley, Angelos Michaelides, Giovanni Costantini*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

9 Citations (Scopus)

Abstract

Benzotriazole (BTAH) has been used for several industrial applications, but most commonly as a corrosion inhibitor for copper, since the 1950s. However, the mechanism of its interaction with copper surfaces at the atomistic scale is still a matter of debate. Here, the adsorption of BTAH onto a clean Cu(110) surface has been investigated by a combination of scanning tunnelling microscopy, X-ray photoelectron spectroscopy, high resolution electron energy loss spectroscopy and density functional theory calculations. Different supramolecular structures have been observed depending on molecular coverage and annealing. In the low coverage regime, flat lying deprotonated species are formed which give way to benzotriazolate molecules in an upright configuration by increasing the BTAH exposure. The ensuing monolayer is self-limiting but, upon annealing above 150 °C, transforms into a highly ordered nano-ridge structure resulting from a significant in-plane and out-of-plane reconstruction of the surface. All structures are characterised by a strong molecule–substrate interaction and the high coverage phases are dominated by the formation of metal–organic complexes between copper adatoms and benzotriazolate species. These findings shed light on the nature and strength of the interaction occurring between BTAH and copper which lies at the basis of the effectiveness of this prototypical corrosion inhibitor.

Original languageEnglish
Article number151206
Number of pages13
JournalApplied Surface Science
Volume570
Early online date8 Sept 2021
DOIs
Publication statusPublished - 30 Dec 2021

Bibliographical note

Funding Information:
O. De Luca is acknowledged for useful discussion on the interpretation of XPS data. M.T. gratefully acknowledges financial support from Lubrizol Limited and, together with J.E., thank the Engineering and Physical Sciences Research Council (EPSRC) grant EP/L015307/1 for the Molecular Analytical Science Centre for Doctoral Training (MAS-CDT). F.G. acknowledges the participation of D. W. Tee in collecting part of the HREELS data and the EaStCHEM Research Computing facility for providing computational resources for the gas phase modelling of HREELS data. C.G acknowledges the Euler cluster managed by the HPC team at ETH Zurich for computational resources and is grateful for computational support from the UK national high performance computing service, ARCHER, for which access was obtained via the UKCP consortium and funded by EPSRC grant EP/P022561/1 .

Publisher Copyright:
© 2021 Elsevier B.V.

Keywords

  • Copper
  • Corrosion inhibitors
  • DFT
  • HREELS
  • STM
  • XPS

ASJC Scopus subject areas

  • General Chemistry
  • Condensed Matter Physics
  • General Physics and Astronomy
  • Surfaces and Interfaces
  • Surfaces, Coatings and Films

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