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      Ultrathin metal-organic framework array for efficient electrocatalytic water splitting

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      1 , a , 1 , b , 1
      Nature Communications
      Nature Publishing Group

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          Abstract

          Two-dimensional metal-organic frameworks represent a family of materials with attractive chemical and structural properties, which are usually prepared in the form of bulk powders. Here we show a generic approach to fabricate ultrathin nanosheet array of metal-organic frameworks on different substrates through a dissolution–crystallization mechanism. These materials exhibit intriguing properties for electrocatalysis including highly exposed active molecular metal sites owning to ultra-small thickness of nanosheets, improved electrical conductivity and a combination of hierarchical porosity. We fabricate a nickel-iron-based metal-organic framework array, which demonstrates superior electrocatalytic performance towards oxygen evolution reaction with a small overpotential of 240 mV at 10 mA cm −2, and robust operation for 20,000 s with no detectable activity decay. Remarkably, the turnover frequency of the electrode is 3.8 s −1 at an overpotential of 400 mV. We further demonstrate the promise of these electrodes for other important catalytic reactions including hydrogen evolution reaction and overall water splitting.

          Abstract

          Metal-organic frameworks are generally considered to be inert catalysts for many electrochemical reactions, however this is not always the case. Here the authors fabricate an ultrathin nanosheet array of metal-organic frameworks exhibiting enhanced performance toward electrocatalytic water splitting.

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          Most cited references22

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          Nickel-iron oxyhydroxide oxygen-evolution electrocatalysts: the role of intentional and incidental iron incorporation.

          Fe plays a critical, but not yet understood, role in enhancing the activity of the Ni-based oxygen evolution reaction (OER) electrocatalysts. We report electrochemical, in situ electrical, photoelectron spectroscopy, and X-ray diffraction measurements on Ni(1-x)Fe(x)(OH)2/Ni(1-x)Fe(x)OOH thin films to investigate the changes in electronic properties, OER activity, and structure as a result of Fe inclusion. We developed a simple method for purification of KOH electrolyte that uses precipitated bulk Ni(OH)2 to absorb Fe impurities. Cyclic voltammetry on rigorously Fe-free Ni(OH)2/NiOOH reveals new Ni redox features and no significant OER current until >400 mV overpotential, different from previous reports which were likely affected by Fe impurities. We show through controlled crystallization that β-NiOOH is less active for OER than the disordered γ-NiOOH starting material and that previous reports of increased activity for β-NiOOH are due to incorporation of Fe-impurities during the crystallization process. Through-film in situ conductivity measurements show a >30-fold increase in film conductivity with Fe addition, but this change in conductivity is not sufficient to explain the observed changes in activity. Measurements of activity as a function of film thickness on Au and glassy carbon substrates are consistent with the hypothesis that Fe exerts a partial-charge-transfer activation effect on Ni, similar to that observed for noble-metal electrode surfaces. These results have significant implications for the design and study of Ni(1-x)Fe(x)OOH OER electrocatalysts, which are the fastest measured OER catalysts under basic conditions.
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            Water photolysis at 12.3% efficiency via perovskite photovoltaics and Earth-abundant catalysts.

            Although sunlight-driven water splitting is a promising route to sustainable hydrogen fuel production, widespread implementation is hampered by the expense of the necessary photovoltaic and photoelectrochemical apparatus. Here, we describe a highly efficient and low-cost water-splitting cell combining a state-of-the-art solution-processed perovskite tandem solar cell and a bifunctional Earth-abundant catalyst. The catalyst electrode, a NiFe layered double hydroxide, exhibits high activity toward both the oxygen and hydrogen evolution reactions in alkaline electrolyte. The combination of the two yields a water-splitting photocurrent density of around 10 milliamperes per square centimeter, corresponding to a solar-to-hydrogen efficiency of 12.3%. Currently, the perovskite instability limits the cell lifetime.
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              Conductive MOF electrodes for stable supercapacitors with high areal capacitance

              Using MOFs as active electrodes in electrochemical double layer capacitors has so far proved difficult. An electrically conductive MOF used as an electrode is now shown to exhibit electrochemical performance similar to most carbon-based materials.
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                Author and article information

                Journal
                Nat Commun
                Nat Commun
                Nature Communications
                Nature Publishing Group
                2041-1723
                05 June 2017
                2017
                : 8
                : 15341
                Affiliations
                [1 ]School of Chemistry, Faculty of Science, The University of New South Wales , Sydney, New South Wales 2052, Australia
                Author notes
                Article
                ncomms15341
                10.1038/ncomms15341
                5465318
                28580963
                57357de5-dade-410a-902e-9d4b57b4edff
                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
                : 25 November 2016
                : 10 March 2017
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