Transient Au–Cl adlayers modulate the surface chemistry of gold nanoparticles during redox reactions
Controlling surface chemistry at the nanoscale is essential for stabilizing structure and tuning function in plasmonic, catalytic and sensing systems, where even trace ligands or ions can reshape surface charge and reactivity. However, probing such dynamic interfaces under operando conditions remains challenging, limiting efforts to engineer nanomaterials with precision. Here, using in situ surface-enhanced Raman spectroscopy, we identify a transient Au-Cl adlayer that forms during electrochemical cycling at gold interfaces. The adlayer exhibits significant charge transfer between gold and chlorine, generating an outward-facing dipole that polarizes neighbouring atoms and modulates the local potential. This dipole stabilizes nanogap interfaces and directs oriented ligand rebinding, enabling reversible reconstruction of subnanometre architectures. It also alters interfacial charge distributions and mediates electron transfer between gold oxidation states, acting as a redox-active intermediate. These findings show how transient surface species shape nanoscale reactivity and stability, offering strategies for designing catalysts, sensors and nanomaterials.
Authors
- Sara Sangtarash (ORCID: https://orcid.org/0000-0003-1152-5673)
- Alexander G. Squires (ORCID: https://orcid.org/0000-0001-6967-3690)
- David O. Scanlon (ORCID: https://orcid.org/0000-0001-9174-8601)
- Tabitha Jones (ORCID: https://orcid.org/0000-0001-7864-2263)
- Bart de Nijs (ORCID: https://orcid.org/0000-0002-8234-723X)
- Nicolas Spiesshofer (ORCID: https://orcid.org/0009-0003-8131-5230)
- Reshma R. Rao (ORCID: https://orcid.org/0000-0002-6655-3105)
- Duncan Graham (ORCID: https://orcid.org/0000-0002-6079-2105)
- Hatef Sadeghi (ORCID: https://orcid.org/0000-0001-5398-8620)
- Oren A. Scherman (ORCID: https://orcid.org/0000-0001-8032-7166)
- Mary P. Ryan (ORCID: https://orcid.org/0000-0001-8582-3003)
- Abdalghani Daaoub (ORCID: https://orcid.org/0000-0002-7476-4770)
- Sarah May Sibug‐Torres (ORCID: https://orcid.org/0000-0002-6015-4090)
- Marika Niihori (ORCID: https://orcid.org/0000-0001-7701-4660)
- Rakesh Arul (ORCID: https://orcid.org/0000-0001-8355-2158)
- Christopher N. Savory (ORCID: https://orcid.org/0000-0002-9052-7484)
- Jeremy J. Baumberg (ORCID: https://orcid.org/0000-0002-9606-9488)
- Elle W. Wyatt (ORCID: https://orcid.org/0009-0002-5372-8217)
Institutions
- University of Strathclyde (GB)
- University of Cambridge (GB)
- University of Warwick (GB)
- Imperial College London (GB)
- University of Birmingham (GB)
Publication Details
- Journal
- Nature Chemistry
- Published
- 2025-11-13
- DOI
- https://doi.org/10.1038/s41557-025-01989-4
- Citations
- 5
- Primary Topic
- Gold and Silver Nanoparticles Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 2.14