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      Ruthenium-cobalt nanoalloys encapsulated in nitrogen-doped graphene as active electrocatalysts for producing hydrogen in alkaline media

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          Abstract

          The scalable production of hydrogen could conveniently be realized by alkaline water electrolysis. Currently, the major challenge confronting hydrogen evolution reaction (HER) is lacking inexpensive alternatives to platinum-based electrocatalysts. Here we report a high-efficient and stable electrocatalyst composed of ruthenium and cobalt bimetallic nanoalloy encapsulated in nitrogen-doped graphene layers. The catalysts display remarkable performance with low overpotentials of only 28 and 218 mV at 10 and 100 mA cm −2, respectively, and excellent stability of 10,000 cycles. Ruthenium is the cheapest platinum-group metal and its amount in the catalyst is only 3.58 wt.%, showing the catalyst high activity at a very competitive price. Density functional theory calculations reveal that the introduction of ruthenium atoms into cobalt core can improve the efficiency of electron transfer from alloy core to graphene shell, beneficial for enhancing carbon–hydrogen bond, thereby lowing ΔG H* of HER.

          Abstract

          Ruthenium is the cheapest platinum-group metal, yet active hydrogen evolution catalysts with low amounts of ruthenium have yet to be designed. Here, the authors report the preparation of a ruthenium–cobalt nanoalloy and demonstrate its potential as an effective hydrogen evolution catalyst in basic media.

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          Most cited references53

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          Recent Progress in Cobalt-Based Heterogeneous Catalysts for Electrochemical Water Splitting

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            Nanoscale nickel oxide/nickel heterostructures for active hydrogen evolution electrocatalysis.

            Active, stable and cost-effective electrocatalysts are a key to water splitting for hydrogen production through electrolysis or photoelectrochemistry. Here we report nanoscale nickel oxide/nickel heterostructures formed on carbon nanotube sidewalls as highly effective electrocatalysts for hydrogen evolution reaction with activity similar to platinum. Partially reduced nickel interfaced with nickel oxide results from thermal decomposition of nickel hydroxide precursors bonded to carbon nanotube sidewalls. The metal ion-carbon nanotube interactions impede complete reduction and Ostwald ripening of nickel species into the less hydrogen evolution reaction active pure nickel phase. A water electrolyzer that achieves ~20 mA cm(-2) at a voltage of 1.5 V, and which may be operated by a single-cell alkaline battery, is fabricated using cheap, non-precious metal-based electrocatalysts.
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              Raman spectroscopy as a versatile tool for studying the properties of graphene

              Raman spectroscopy is an integral part of graphene research. It is used to determine the number and orientation of layers, the quality and types of edge, and the effects of perturbations, such as electric and magnetic fields, strain, doping, disorder and functional groups. This, in turn, provides insight into all \(sp^2\)-bonded carbon allotropes, because graphene is their fundamental building block. Here we review the state of the art, future directions and open questions in Raman spectroscopy of graphene. We describe essential physical processes whose importance has only recently been recognized, such as the various types of resonance at play, and the role of quantum interference. We update all basic concepts and notations, and propose a terminology that is able to describe any result in literature. We finally highlight the potential of Raman spectroscopy for layered materials other than graphene.
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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group
                2041-1723
                25 April 2017
                2017
                : 8
                : 14969
                Affiliations
                [1 ]Hefei National Laboratory for Physical Science at Microscale, Department of Materials Science & Engineering & Collaborative Innovation Center of Suzhou Nano Science and Technology, University of Science and Technology of China , Hefei 230026, China
                [2 ]High Magnetic Field Laboratory, Hefei Institutes of Physical Science, Chinese Academy of Sciences , Hefei 230031, China
                Author notes
                [*]

                These authors contributed equally to this work.

                Article
                ncomms14969
                10.1038/ncomms14969
                5413983
                28440269
                59e41007-13cf-4988-ac9a-5a5703d7d54a
                Copyright © 2017, 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
                : 04 November 2017
                : 17 February 2017
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