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Adsorption and Diffusion of 4d and 5d Transition Metal Adatoms on Graphene/Ru(0001) and the Implications for Cluster Nucleation

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Abstract

To explore the possibility of using the graphene moiré superstructure formed on Ru(0001) (g/Ru(0001)) as a template to self-assemble super-lattices of metal nanoparticles as model catalysts, it is desirable to know the minimum-energy adsorption sites, adsorption energies, and diffusion properties of small metal species on this surface. Toward that end, density functional theory calculations have been carried out to investigate the adsorption and diffusion of 18 4d (Y–Ag) and 5d (La–Au) transition metal adatoms on g/Ru(0001), using small surface models representing different regions of the g/Ru(0001) surface. For each adatom, adsorption is the strongest in the fcc region and the weakest in the mound region of the moiré. Diffusion within the fcc region is facile for most adatoms, but an additional barrier is imposed by the corrugation of the graphene moiré for traversing between neighboring fcc regions. Overall, the earlier 4d and 5d metal adatoms have stronger adsorption energies and higher diffusion barriers on g/Ru(0001) than the later ones. The results are then interpreted to provide a better understanding of the conditions necessary to achieve dense super-lattices of monodisperse metal clusters on g/Ru(0001).

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Acknowledgments

We congratulate Prof. Jens K. Nørskov on his 60th birthday, and thank him for the tremendous leadership and inspiration that he has provided to the field of computational catalysis and surface science. This study was supported as part of the Center for Atomic Level Catalyst Design, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, and Office of Basic Energy Sciences under Award Number DE-SC0001058, and used resources of the National Energy Research Scientific Computing Center, which is supported by DOE Office of Science under Contract DE-AC02-05CH11231. Additional computing resources of Oak Ridge National Laboratory and Georgia Institute of Technology were used.

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Authors and Affiliations

  1. Center for Nanophase Materials Sciences, Oak Ridge National Laboratory, Oak Ridge, TN , 37831, USA

    Bradley F. Habenicht, Lymarie Semidey-Flecha & Ye Xu

  2. School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, 30332, USA

    Dieh Teng & David S. Sholl

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  1. Bradley F. Habenicht
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  2. Dieh Teng
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  3. Lymarie Semidey-Flecha
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  4. David S. Sholl
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Correspondence to Ye Xu.

Additional information

Bradley F. Habenicht, Dieh Teng, Lymarie Semidey-Flecha contributed equally to this work.

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Habenicht, B.F., Teng, D., Semidey-Flecha, L. et al. Adsorption and Diffusion of 4d and 5d Transition Metal Adatoms on Graphene/Ru(0001) and the Implications for Cluster Nucleation. Top Catal 57, 69–79 (2014). https://doi.org/10.1007/s11244-013-0163-6

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