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      A highly active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

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          Abstract

          Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superior activity for hydrogen evolution, achieving current densities of 10 mA cm −2 and 100 mA cm −2 at overpotentials of 48 mV and 109 mV, respectively. Phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation.

          Abstract

          Rational design and synthesis are important for the development of materials for energy applications. Here, the authors sequentially synthesize pyrite structured cobalt phosphosulfide nanoparticles on carbon nanotubes, probing the role of phosphorous substitution on catalyst stability and durability.

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          Generalized Gradient Approximation Made Simple.

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            High-performance electrocatalysis using metallic cobalt pyrite (CoS₂) micro- and nanostructures.

            The development of efficient and robust earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) is an ongoing challenge. We report metallic cobalt pyrite (cobalt disulfide, CoS2) as one such high-activity candidate material and demonstrate that its specific morphology--film, microwire, or nanowire, made available through controlled synthesis--plays a crucial role in determining its overall catalytic efficacy. The increase in effective electrode surface area that accompanies CoS2 micro- and nanostructuring substantially boosts its HER catalytic performance, with CoS2 nanowire electrodes achieving geometric current densities of -10 mA cm(-2) at overpotentials as low as -145 mV vs the reversible hydrogen electrode. Moreover, micro- and nanostructuring of the CoS2 material has the synergistic effect of increasing its operational stability, cyclability, and maximum achievable rate of hydrogen generation by promoting the release of evolved gas bubbles from the electrode surface. The benefits of catalyst micro- and nanostructuring are further demonstrated by the increased electrocatalytic activity of CoS2 nanowire electrodes over planar film electrodes toward polysulfide and triiodide reduction, which suggests a straightforward way to improve the performance of quantum dot- and dye-sensitized solar cells, respectively. Extension of this micro- and nanostructuring strategy to other earth-abundant materials could similarly enable inexpensive electrocatalysts that lack the high intrinsic activity of the noble metals.
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              Enhanced Catalytic Activity in Strained Chemically Exfoliated WS2 Nanosheets for Hydrogen Evolution

              The ability to efficiently evolve hydrogen via electrocatalysis at low overpotentials holds tremendous promise for clean energy. Hydrogen evolution reaction (HER) can be easily achieved from water if a voltage above the thermodynamic potential of the HER is applied. Large overpotentials are energetically inefficient but can be lowered with expensive platinum based catalysts. Replacement of Pt with inexpensive, earth abundant electrocatalysts would be significantly beneficial for clean and efficient hydrogen evolution. Towards this end, promising HER characteristics have been reported using 2H (trigonal prismatic) XS2 (where X = Mo or W) nanoparticles with a high concentration of metallic edges as electrocatalysts. The key challenges for HER with XS2 are increasing the number and catalytic activity of active sites. Here we report atomically thin nanosheets of chemically exfoliated WS2 as efficient catalysts for hydrogen evolution with very low overpotentials. Atomic-resolution transmission electron microscopy and spectroscopy analyses indicate that enhanced electrocatalytic activity of WS2 is associated with high concentration of strained metallic 1T (octahedral) phase in the as-exfoliated nanosheets. Density functional theory calculations reveal that the presence of strain in the 1T phase leads to an enhancement of the density of states at the Fermi level and increases the catalytic activity of the WS2 nanosheet. Our results suggest that chemically exfoliated WS2 nanosheets could be interesting catalysts for hydrogen evolution.
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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group
                2041-1723
                19 February 2016
                2016
                : 7
                : 10771
                Affiliations
                [1 ]Department of Chemistry and Energy Sciences Institute, Yale University , 520 West Campus Drive, West Haven, Connecticut 06511, USA
                [2 ]Chemistry Department, Brookhaven National Laboratory , Upton, New York 11973, USA
                [3 ]Beijing National Laboratory for Molecular Sciences, College of Chemistry and Molecular Engineering, Peking University , Beijing 100871, China
                [4 ]Department of Mechanical Engineering and Materials Science, Yale University , 520 West Campus Drive, West Haven, Connecticut 06511, USA
                [5 ]Department of Chemical and Environmental Engineering, Yale University , 520 West Campus Drive, West Haven, Connecticut 06511, USA
                Author notes
                Author information
                http://orcid.org/0000-0001-8513-518X
                Article
                ncomms10771
                10.1038/ncomms10771
                4762894
                26892437
                1a58457c-e489-4f3b-97ac-20658156ddcf
                Copyright © 2016, Nature Publishing Group, a division of Macmillan Publishers Limited. All Rights Reserved.

                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 November 2015
                : 19 January 2016
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