ACS Publications. Most Trusted. Most Cited. Most Read
My Activity

Figure 1Loading Img

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

View Author Information
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
Cite this: J. Phys. Chem. C 2012, 116, 18, 10048–10056
Publication Date (Web):April 21, 2012
Copyright © 2012 American Chemical Society

    Article Views





    Read OnlinePDF (3 MB)
    Supporting Info (1)»


    Abstract Image

    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.

    Supporting Information

    Jump To

    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

    Terms & Conditions

    Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system:

    Cited By

    This article is cited by 20 publications.

    1. Adriano H. Braga, Mauro C. Ribeiro, Fábio B. Noronha, Douglas Galante, José M. C. Bueno, João B. O. Santos. Effects of Co Addition to Supported Ni Catalysts on Hydrogen Production from Oxidative Steam Reforming of Ethanol. Energy & Fuels 2018, 32 (12) , 12814-12825.
    2. Wen Luo, Walid Baaziz, Qing Cao, Housseinou Ba, Rachid Baati, Ovidiu Ersen, Cuong Pham-Huu, and Spyridon Zafeiratos . Design and Fabrication of Highly Reducible PtCo Particles Supported on Graphene-Coated ZnO. ACS Applied Materials & Interfaces 2017, 9 (39) , 34256-34268.
    3. Fotios Paloukis, Kalliopi M. Papazisi, Thierry Dintzer, Vasiliki Papaefthimiou, Viktoriia A. Saveleva, Stella P. Balomenou, Dimitrios Tsiplakides, Fabrice Bournel, Jean-Jacques Gallet, and Spyridon Zafeiratos . Insights into the Surface Reactivity of Cermet and Perovskite Electrodes in Oxidizing, Reducing, and Humid Environments. ACS Applied Materials & Interfaces 2017, 9 (30) , 25265-25277.
    4. Wen Luo and Spyridon Zafeiratos . Tuning Morphology and Redox Properties of Cobalt Particles Supported on Oxides by an in between Graphene Layer. The Journal of Physical Chemistry C 2016, 120 (26) , 14130-14139.
    5. Won Hui Doh, Vasiliki Papaefthimiou, Thierry Dintzer, Véronique Dupuis, and Spyridon Zafeiratos . Synchrotron Radiation X-ray Photoelectron Spectroscopy as a Tool To Resolve the Dimensions of Spherical Core/Shell Nanoparticles. The Journal of Physical Chemistry C 2014, 118 (46) , 26621-26628.
    6. Wen Luo, Won Hui Doh, Yeuk T. Law, Fitsum Aweke, Anna Ksiazek-Sobieszek, Andrzej Sobieszek, Leszek Salamacha, Krzysztof Skrzypiec, François Le Normand, Andrzej Machocki, and Spyridon Zafeiratos . Single-Layer Graphene as an Effective Mediator of the Metal–Support Interaction. The Journal of Physical Chemistry Letters 2014, 5 (11) , 1837-1844.
    7. Randima P. Galhenage, Hui Yan, Samuel A. Tenney, Nayoung Park, Graeme Henkelman, Peter Albrecht, David R. Mullins, and Donna A. Chen . Understanding the Nucleation and Growth of Metals on TiO2: Co Compared to Au, Ni, and Pt. The Journal of Physical Chemistry C 2013, 117 (14) , 7191-7201.
    8. Grzegorz Słowik, Magdalena Greluk. The Influence of Active Phase Composition and Reaction Temperature on the Catalytic Properties of K-Promoted Co–Ni/CeO2 Catalysts in the Steam Reforming of Ethanol. Catalysis Letters 2023, 153 (5) , 1505-1526.
    9. Digambar B. Bankar, Kaluram G. Kanade, Ranjit R. Hawaldar, Sudhir S. Arbuj, Manish D. Shinde, Shrikant P. Takle, Dinesh P. Amalnerkar, Santosh T. Shinde. Facile synthesis of nanostructured Ni-Co/ZnO material: An efficient and inexpensive catalyst for Heck reactions under ligand-free conditions. Arabian Journal of Chemistry 2020, 13 (12) , 9005-9018.
    10. Wen Luo, Spyridon Zafeiratos. Graphene at the Metal–Oxide Interface: A New Approach to Modify the Chemistry of Supported Metals. 2019, 45-71.
    11. V.G. Bayev, J.A. Fedotova, J.V. Kasiuk, S.A. Vorobyova, A.A. Sohor, I.V. Komissarov, N.G. Kovalchuk, S.L. Prischepa, N.I. Kargin, M. Andrulevičius, J. Przewoznik, Cz. Kapusta, O.A. Ivashkevich, S.I. Tyutyunnikov, N.N. Kolobylina, P.V. Guryeva. CVD graphene sheets electrochemically decorated with “core-shell” Co/CoO nanoparticles. Applied Surface Science 2018, 440 , 1252-1260.
    12. Beibei Guo, Dongyun Wan, Jiaou Wang, Sixv Zhu, Hongjie Luo, Yanfeng Gao. Mo-Al co-doped VO2(B) thin films: CVD synthesis, thermal sensitive properties, synchrotron radiation photoelectron and absorption spectroscopy study. Journal of Alloys and Compounds 2018, 745 , 247-255.
    13. Wen Luo, Christophe Mélart, Alain Rach, Christophe Sutter, Spyridon Zafeiratos. Interaction of bimetallic PtCo layers with bare and graphene-covered ZnO(0001) supports. Surface Science 2018, 669 , 64-70.
    14. F. Paloukis, K.M. Papazisi, S.P. Balomenou, D. Tsiplakides, F. Bournel, J.-J. Gallet, S. Zafeiratos. In situ X-ray photoelectron spectroscopy study of complex oxides under gas and vacuum environments. Applied Surface Science 2017, 423 , 1176-1181.
    15. Vasiliki Papaefthimiou, Dimitris K. Niakolas, Fotios Paloukis, Thierry Dintzer, Spyridon Zafeiratos. Is Steam an Oxidant or a Reductant for Nickel/Doped‐Ceria Cermets?. ChemPhysChem 2017, 18 (1) , 164-170.
    16. Wen Luo, Spyridon Zafeiratos. Graphene‐Coated ZnO and SiO 2 as Supports for CoO Nanoparticles with Enhanced Reducibility. ChemPhysChem 2016, 17 (19) , 3055-3061.
    17. Sascha Vongehr, Shaochun Tang, Xiangkang Meng. Adapting Nanotech Research as Nano-Micro Hybrids Approach Biological Complexity, A Review. Journal of Materials Science & Technology 2016, 32 (5) , 387-401.
    18. S. Turczyniak, W. Luo, V. Papaefthimiou, N. S. Ramgir, M. Haevecker, A. Machocki, S. Zafeiratos. A Comparative Ambient Pressure X-ray Photoelectron and Absorption Spectroscopy Study of Various Cobalt-Based Catalysts in Reactive Atmospheres. Topics in Catalysis 2016, 59 (5-7) , 532-542.
    19. Mónica Muñoz, Sonia Moreno, Rafael Molina. The effect of the absence of Ni, Co, and Ni–Co catalyst pretreatment on catalytic activity for hydrogen production via oxidative steam reforming of ethanol. International Journal of Hydrogen Energy 2014, 39 (19) , 10074-10089.
    20. Y.T. Law, W.H. Doh, W. Luo, S. Zafeiratos. A comparative study of ethanol reactivity over Ni, Co and NiCo-ZnO model catalysts. Journal of Molecular Catalysis A: Chemical 2014, 381 , 89-98.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    Pair your accounts.

    Export articles to Mendeley

    Get article recommendations from ACS based on references in your Mendeley library.

    You’ve supercharged your research process with ACS and Mendeley!

    STEP 1:
    Click to create an ACS ID

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Please note: If you switch to a different device, you may be asked to login again with only your ACS ID.

    Your Mendeley pairing has expired. Please reconnect