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Bimetallic Nickel–Cobalt Nanosized Layers Supported on Polar ZnO Surfaces: Metal–Support Interaction and Alloy Effects Studied by Synchrotron Radiation X-ray Photoelectron Spectroscopy

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† Laboratoire des Matériaux, Surfaces et Procédés pour la Catalyse, CNRS-Université de Strasbourg (UDS) UMR 7515, 25 rue Becquerel, 67087 Strasbourg Cedex 08, France
‡ Sincrotrone Trieste SCpA, Strada statale 14, km 163.5, I-34149 Basovizza-Trieste, Italy
§ Charles University, Faculty of Mathematics and Physics, Department of Surface and Plasma Science, V Holešovičkách 2, CZ-18000 Prague 8, Czech Republic
∥ Institute of Physics, Academy of Sciences of the Czech Republic, Cukrovarnická 10, CZ-16253 Prague 6, Czech Republic
*E-mail: [email protected]
Cite this: J. Phys. Chem. C 2012, 116, 18, 10048–10056
Publication Date (Web):April 21, 2012
https://doi.org/10.1021/jp301219u
Copyright © 2012 American Chemical Society
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    Abstract

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    The interaction of ultrathin bimetallic Ni–Co layers (0.25 and 1.5 nm) supported on polar (0001)Zn–ZnO and (0001̅)O–ZnO substrates was investigated by synchrotron-based photoelectron spectroscopy (PES) under ultrahigh vacuum (UHV) and O2 environments. Monometallic Ni and Co layers were also characterized to highlight the influence of Ni–Co synergetic effects on the metal–support interaction. At room temperature, cobalt is partially oxidized, while nickel is metallic. The effect of ZnO surface termination is minor, while the influence of surface hydroxyl groups is discussed. Annealing at 773 K in UHV promotes oxidation of monometallic Ni and Co layers but has little influence on bimetallic Ni–Co. In addition, significant agglomeration of the Ni–Co overlayer is observed, with a parallel increase in the surface Co concentration. Agglomeration of Ni–Co is more pronounced on O-terminated ZnO. Upon annealing in 1 × 10–6 mbar of O2, both Ni and Co readily oxidize and redisperse over the ZnO substrate. Moreover, cobalt tends to segregate over nickel, creating a concentration gradient between the two alloy constituents (probably a core–shell-like structure). Overall, our results indicate that the interaction at the Ni–Co/ZnO interface is influenced by the synergetic effects between the two metals and to a lesser extent by the substrate termination. Taking into account the substantial progress made in the synthesis of ZnO nanostructures and surfaces, this study can assist in the effort toward improved ZnO-based catalysts with tailored properties.

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    LEED pattern of clean ZnO–Zn (0001) and (0001̅) ZnO–O; PES O 1s spectra recorded with photon energy 590–840 eV; and SEM of 1.5 nm Ni–Co overlayer after annealing in 1 × 10–6 mbar of O2 at 773 K. This material is available free of charge via the Internet at http://pubs.acs.org.

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