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Comparative Analysis of Cobalt Oxide Nanoisland Stability and Edge Structures on Three Related Noble Metal Surfaces: Au(111), Pt(111) and Ag(111)

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Abstract

Metal oxide nanostructures and thin films grown on metallic substrates have attracted strong attention as model catalysts and as interesting inverse catalyst systems in their own right. In this study, we investigate the role of metal support in the growth and stabilization of cobalt oxide nanostructures on the three related (111) surfaces of Au, Pt and Ag, as investigated by means of high-resolution scanning tunneling microscopy and DFT calculations. All three substrates promote the growth of crystalline CoOx (x = 1−2) islands under oxidative conditions, but we find several noteworthy differences in the occurrence and stabilization of four distinct cobalt oxide island phases: Co–O bilayers, O–Co–O trilayers, Co–O–Co–O double bilayers and O–Co–O–Co–O multilayers. Using atom-resolved images combined with analysis of defect lines in bilayer islands on Au and Pt, we furthermore unambiguously determine the edge structure. Interestingly, the island shape and abundances of edge types in bilayers change radically from mixed Co/O edge terminations on Au(111) to a predominance of Co terminated edges (~91 %) on Pt(111) which is especially interesting since the Co metal edges are expected to host the most active sites for water dissociation.

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Acknowledgments

The iNANO group gratefully acknowledges support from the Lundbeck Foundation and Villum Foundation. MB, PNP and AV gratefully acknowledge support from the U.S. Department of Energy Office of Basic Energy Science to the SUNCAT Center for Interface Science and Catalysis. AV acknowledges the support from the SLAC National Accelerator Lab LDRD program. MB, PNP and AV would like to acknowledge the use of the computer time allocation for the “Computational search for highly efficient 2d and 3d nano-catalysts for water splitting” at the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. ZS would like to acknowledge the financial support from the Chinese Scholarship Council (CSC).

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Authors and Affiliations

  1. Interdisciplinary Nanoscience Center (iNANO), Aarhus University, 8000, Aarhus C, Denmark

    Jakob Fester, Alex S. Walton, Z. Sun & Jeppe V. Lauritsen

  2. SUNCAT Center for Interface Science and Catalysis, SLAC National Accelerator Laboratory, 2575 Sand Hill Road, Menlo Park, CA, 94025, USA

    Michal Bajdich, Philipp N. Plessow & Aleksandra Vojvodic

  3. School of Chemistry, University of Manchester, Manchester, M13 9PL, UK

    Alex S. Walton

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  1. Jakob Fester
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  7. Jeppe V. Lauritsen
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Correspondence to Jeppe V. Lauritsen.

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Fester, J., Bajdich, M., Walton, A.S. et al. Comparative Analysis of Cobalt Oxide Nanoisland Stability and Edge Structures on Three Related Noble Metal Surfaces: Au(111), Pt(111) and Ag(111). Top Catal 60, 503–512 (2017). https://doi.org/10.1007/s11244-016-0708-6

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