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      Platinum single-atom and cluster catalysis of the hydrogen evolution reaction

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          Abstract

          Platinum-based catalysts have been considered the most effective electrocatalysts for the hydrogen evolution reaction in water splitting. However, platinum utilization in these electrocatalysts is extremely low, as the active sites are only located on the surface of the catalyst particles. Downsizing catalyst nanoparticles to single atoms is highly desirable to maximize their efficiency by utilizing nearly all platinum atoms. Here we report on a practical synthesis method to produce isolated single platinum atoms and clusters using the atomic layer deposition technique. The single platinum atom catalysts are investigated for the hydrogen evolution reaction, where they exhibit significantly enhanced catalytic activity (up to 37 times) and high stability in comparison with the state-of-the-art commercial platinum/carbon catalysts. The X-ray absorption fine structure and density functional theory analyses indicate that the partially unoccupied density of states of the platinum atoms' 5 d orbitals on the nitrogen-doped graphene are responsible for the excellent performance.

          Abstract

          Downsizing platinum based nanocatalysts has the twin advantages of lower platinum usage and increased activity per platinum atom. Here, the authors report an atomic layer deposition technique for single platinum atom catalyst fabrication and assess their hydrogen evolution activity.

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          Most cited references15

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          Atomic layer deposition: an overview.

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            Van der Waals Density Functional for General Geometries

            A scheme within density functional theory is proposed that provides a practical way to generalize to unrestricted geometries the method applied with some success to layered geometries [H. Rydberg, et al., Phys. Rev. Lett. 91, 126402 (2003)]. It includes van der Waals forces in a seamless fashion. By expansion to second order in a carefully chosen quantity contained in the long range part of the correlation functional, the nonlocal correlations are expressed in terms of a density-density interaction formula. It contains a relatively simple parametrized kernel, with parameters determined by the local density and its gradient. The proposed functional is applied to rare gas and benzene dimers, where it is shown to give a realistic description.
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              Ultrathin platinum nanowires grown on single-layered nickel hydroxide with high hydrogen evolution activity.

              Design and synthesis of effective electrocatalysts for hydrogen evolution reaction in alkaline environments is critical to reduce energy losses in alkaline water electrolysis. Here we report a hybrid nanomaterial comprising of one-dimensional ultrathin platinum nanowires grown on two-dimensional single-layered nickel hydroxide. Judicious surface chemistry to generate the fully exfoliated nickel hydroxide single layers is explored to be the key for controllable growth of ultrathin platinum nanowires with diameters of about 1.8 nm. Impressively, this hybrid nanomaterial exhibits superior electrocatalytic activity for hydrogen evolution reaction in alkaline solution, which outperforms currently reported catalysts, and the obviously improved catalytic stability. We believe that this work may lead towards the development of single-layered metal hydroxide-based hybrid materials for applications in catalysis and energy conversion.
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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group
                2041-1723
                30 November 2016
                2016
                : 7
                : 13638
                Affiliations
                [1 ]Department of Mechanical and Materials Engineering, University of Western Ontario , London, Ontario, Canada N6A 5B9
                [2 ]Department of Materials Science and Engineering, McMaster University , Hamilton, Ontario, Canada L8S 4L8
                [3 ]Beijing Computational Science Research Center , Beijing 100193, China
                [4 ]Department of Chemistry, University of Western Ontario , London, Ontario, Canada N6A 5B7
                [5 ]Brockhouse Institute for Materials Research, McMaster University , Hamilton, Ontario, Canada L9S 4M1
                [6 ]Canadian Centre for Electron Microscopy, McMaster University , Hamilton, Ontario, Canada L8S 4M1
                Author notes
                [*]

                These authors contributed equally to this work

                Article
                ncomms13638
                10.1038/ncomms13638
                5141386
                27901129
                b8d578d0-8d4b-45b9-b2d2-6a7e5c48abb0
                Copyright © 2016, The Author(s)

                This work is licensed under a Creative Commons Attribution 4.0 International License. The images or other third party material in this article are included in the article's Creative Commons license, unless indicated otherwise in the credit line; if the material is not included under the Creative Commons license, users will need to obtain permission from the license holder to reproduce the material. To view a copy of this license, visit http://creativecommons.org/licenses/by/4.0/

                History
                : 07 June 2016
                : 14 October 2016
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