A Dynamic Surface Metal‐Organic Framework Electrocatalyst: Potential‐Driven Activation of Atomically Defined Au Sites for the Hydrogen Evolution Reaction
ABSTRACT Surface metal‐organic frameworks (SMOFs) are promising platforms for catalysis, yet their structural response to electrochemical bias is often overlooked. We report the potential‐driven activation of an N‐heterocyclic carbene (NHC)‐based SMOF on Au(111) for the hydrogen evolution reaction (HER). Operando electrochemical scanning tunneling microscopy (EC‐STM) reveals that the framework, initially “frozen” in a strongly interconnected 1D chain morphology at open circuit potential, transitions into a dynamic phase under cathodic bias. This reconfiguration involves a dynamic cycle of metal abstraction and release, generating a high density of undercoordinated sites. DFT calculations confirm that while internal bridging Au nodes are inert (ΔG H* = 0.99 eV), the potential‐induced decoupling of the chains creates terminal Au nodes and lattice vacancies with near‐thermoneutral adsorption energies of 0.05 and 0.07 eV, respectively. This study demonstrates that superior HER performance originates from the SMOF's ability to dynamically transform into a fluxional active state, providing a strategy for designing adaptive interfacial catalysts.
Authors
- Mattia Cattelan (ORCID: https://orcid.org/0000-0001-9314-1475)
- Zisheng Zhang (ORCID: https://orcid.org/0000-0002-4370-4038)
- Francesco Sedona (ORCID: https://orcid.org/0000-0002-7225-9498)
- Cristina Tubaro (ORCID: https://orcid.org/0000-0001-7724-735X)
- Stefano Agnoli (ORCID: https://orcid.org/0000-0001-5204-5460)
- Rafał Lewandków (ORCID: https://orcid.org/0000-0001-9683-1084)
- Fujia Liu (ORCID: https://orcid.org/0009-0005-8242-4281)
- Boyu Qie (ORCID: https://orcid.org/0000-0003-3552-7366)
- Felix R. Fischer (ORCID: https://orcid.org/0000-0003-4723-3111)
- Tomasz Kosmala (ORCID: https://orcid.org/0000-0002-0026-8205)
- Leonardo Cielo
- Paulina Wira
- Dennis Pedersoli
Institutions
- University of Padua (IT)
- Lawrence Berkeley National Laboratory (US)
- University of Wrocław (PL)
- SLAC National Accelerator Laboratory (US)
- Center for Information Technology Research in the Interest of Society (US)
- Institute of Experimental Physics of the Slovak Academy of Sciences (SK)
- Kavli Energy NanoScience Institute (US)
- University of California, Berkeley (US)
- Stanford University (US)
Publication Details
- Journal
- Small
- Published
- 2026-09-12
- DOI
- https://doi.org/10.1002/smll.75601
- Primary Topic
- Surface Chemistry and Catalysis
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Materials Sciences and Engineering Division
- U.S. Department of Energy
- Dipartimenti di Eccellenza
- European Commission
- Università degli Studi di Padova
- Office of Science
- Basic Energy Sciences