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Operando visualization of the hydrogen evolution reaction with atomic-scale precision at different metal–graphene interfaces


The development of catalysts for the hydrogen evolution reaction is pivotal for the hydrogen economy. Thin iron films covered with monolayer graphene exhibit outstanding catalytic activity, surpassing even that of platinum, as demonstrated by a method based on evaluating the noise in the tunnelling current of electrochemical scanning tunnelling microscopy. Using this approach, we mapped with atomic-scale precision the electrochemical activity of the graphene–iron interface, and determined that single iron atoms trapped within carbon vacancies and curved graphene areas on step edges are exceptionally active. Density functional theory calculations confirmed the sequence of activity obtained experimentally. This work exemplifies the potential of electrochemical scanning tunnelling microscopy as the only technique able to determine both the atomic structure and relative catalytic performance of atomically well-defined sites in electrochemical operando conditions and provides a detailed rationale for the design of novel catalysts based on cheap and abundant metals such as iron.

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Fig. 1: Catalytic processes at different interfaces.
Fig. 2: Electrochemistry and morphology of Gr growth on Pt(111).
Fig. 3: Hydrogen intercalation process under Gr on Pt(111).
Fig. 4: Activity towards the hydrogen evolution reaction of Gr/Pt(111) and Pt(111).
Fig. 5: Graphene/iron as a hydrogen evolution catalyst.
Fig. 6: Potentiodynamic EC-STM images during catalytic activity.
Fig. 7: Identification of catalytic active sites and current roughness analysis.

Data availability

The experimental raw data and atomic coordinates of the optimized models that support the findings of this study are available in figshare at


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The computations were run on the supercomputer MARCONI at CINECA, Bologna, Italy. This work has been partially supported by the project ‘MADAM—Metal Activated 2D cArbon-based platforMs’ funded by the Italian MIUR (PRIN 2017), grant 2017NYPHN8, MIUR (PRIN 2015: SMARTNESS, 2015K7FZLH; PRIN 2017: Multi-e, 20179337R7) and the MAECI Italy–China Bilateral Project (GINSENG, PGR00953). The Cariparo Foundation is acknowledged for funding (Project Synergy, Progetti di Eccellenza 2018). The University of Wrocław is also acknowledged for financial support 1010/S/IFD. We thank Alessandro Facchin for technical support with the EC-STM instrumentation.

Author information




Investigation: T.K., A.B., M.L. and D.P. Data analysis: T.K., A.B., M.L., D.P. and H.L. Conceptualization: T.K., S.A. and C.D.V. Draft writing: T.K., A.B., S.A., C.D.V., C.D. and G.G. Supervision, S.A. and G.G. All authors have read and agreed to the published version of the manuscript.

Corresponding author

Correspondence to Stefano Agnoli.

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Peer review information Nature Catalysis thanks the anonymous reviewers for their contribution to the peer review of this work.

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Supplementary information

Supplementary Information

Supplementary Tables 1–4, Figs. 1–22 and notes 1–3.

Supplementary Video 1

Series of potentiodynamic STM images during HER for Gr/Fe (1.8 ML)/Pt(111) system

Supplementary Video 2

Series of potentiodynamic STM images during HER for Gr/Pt(111) system

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Kosmala, T., Baby, A., Lunardon, M. et al. Operando visualization of the hydrogen evolution reaction with atomic-scale precision at different metal–graphene interfaces. Nat Catal 4, 850–859 (2021).

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