A Dynamic Surface Metal-Organic Framework Electrocatalyst: Potential-Driven Activation of Atomically Defined Au Sites for the Hydrogen Evolution Reaction.

Authors

Paulina Wira, Leonardo Cielo, Zisheng Zhang, Mattia Cattelan, Rafał Lewandków, Dennis Pedersoli, Fujia Liu, Boyu Qie, Felix R Fischer, Francesco Sedona, Cristina Tubaro, Tomasz Kosmala, Stefano Agnoli

Published in

Small (Weinheim an der Bergstrasse, Germany). Pages e75601. Sep 12, 2026. Epub Sep 12, 2026.

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.

PMID:
42730479
Bibliographic data and abstract were imported from PubMed on 13 Sep 2026.

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