Catalytic Activity of Defect-Engineered Transition Me tal Dichalcogenides Mapped with Atomic-Scale Precision by Electrochemical Scanning Tunneling Microscopy

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Volume Title
A1 Alkuperäisartikkeli tieteellisessä aikakauslehdessä
Date
2023-01-16
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Mcode
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Language
en
Pages
9
972-980
Series
ACS Energy Letters, Volume 8, issue 2
Abstract
Unraveling structure-activity relationships is a key objective of catalysis. Unfortunately, the intrinsic complexity and structural heterogeneity of materials stand in the way of this goal, mainly because the activity measurements are area-averaged and therefore contain information coming from different surface sites. This limitation can be surpassed by the analysis of the noise in the current of electrochemical scanning tunneling microscopy (EC-STM). Herein, we apply this strategy to investigate the catalytic activity toward the hydrogen evolution reaction of monolayer films of MoSe2. Thanks to atomically resolved potentiodynamic experiments, we can evaluate individually the catalytic activity of the MoSe2 basal plane, selenium vacancies, and different point defects produced by the intersections of metallic twin boundaries. The activity trend deduced by EC-STM is independently confirmed by density functional theory calculations, which also indicate that, on the metallic twin boundary crossings, the hydrogen adsorption energy is almost thermoneutral. The micro- and macroscopic measurements are combined to extract the turnover frequency of different sites, obtaining for the most active ones a value of 30 s-1 at −136 mV vs RHE.
Description
Funding Information: This work has been partially supported by the MIUR (PRIN 2017: Multi-e, 20179337R7) and the Cariparo Foundation (project Synergy, Progetti di Eccellenza 2018). M.B. acknowledges support from the U.S. National Science Foundation under award 2140038. The National Science Centre, Poland, is acknowledged for funding (grant no. 2021/43/D/ST3/02873). The University of Padova is acknowledged for support through the grant P-Disc 2022 (MUSYCA). The “Excellence Initiative – Research University” program is acknowledged for support. Publisher Copyright: © 2023 The Authors. Published by American Chemical Society.
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Citation
Lunardon, M, Kosmala, T, Ghorbani-Asl, M, Krasheninnikov, A V, Kolekar, S, Durante, C, Batzill, M, Agnoli, S & Granozzi, G 2023, ' Catalytic Activity of Defect-Engineered Transition Me tal Dichalcogenides Mapped with Atomic-Scale Precision by Electrochemical Scanning Tunneling Microscopy ', ACS Energy Letters, vol. 8, no. 2, pp. 972-980 . https://doi.org/10.1021/acsenergylett.2c02599