In Situ Detection of Active Edge Sites in Single-Layer MoS\(_2\) Catalysts

• Published in: arXiv.org
• Main Authors: Bruix, Albert, Füchtbauer, Henrik G, Tuxen, Anders K, Walton, Alex S, Andersen, Mie, Porsgaard, Søren, Besenbacher, Flemming, Hammer, Bjørk, Lauritsen, Jeppe V
• Format: Paper
• Language: English
• Published: Ithaca Cornell University Library, arXiv.org 13.11.2015
• Subjects: Atomic structure; Catalysis; Catalysts; Density functional theory; Hydrogen evolution; Molybdenum disulfide; Nanoparticles; Photoelectrons; Pressure; Sulfidation; Working conditions; X ray photoelectron spectroscopy
• ISSN: 2331-8422
• DOI: 10.48550/arxiv.1511.04254

MoS2 nanoparticles are proven catalysts for processes such as hydrodesulphurization and hydrogen evolution, but unravelling their atomic-scale structure under catalytic working conditions has remained significantly challenging. Ambient pressure X-ray Photoelectron Spectroscopy (AP-XPS) allows us to follow in-situ the formation of the catalytically relevant MoS2 edge sites in their active state. The XPS fingerprint is described by independent contributions to the Mo3d core level spectrum whose relative intensity is sensitive to the thermodynamic conditions. Density Functional Theory (DFT) is used to model the triangular MoS2 particles on Au(111) and identify the particular sulphidation state of the edge sites. A consistent picture emerges in which the core level shifts for the edge Mo atoms evolve counter-intuitively towards higher binding energies when the active edges are reduced. The shift is explained by a surprising alteration in the metallic character of the edge sites, which is a distinct spectroscopic signature of the MoS2 edges under working conditions.