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      Graphene aerogel-supported and graphene quantum dots-modified γ-MnOOH nanotubes as a highly efficient electrocatalyst for oxygen reduction reaction

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          Abstract

          In this work, we demonstrate a facile strategy to synthesize a novel three-dimensional (3D) graphene aerogel-supported and graphene quantum dots-modified γ-MnOOH nanotubes as a highly efficient electrocatalyst.

          Abstract

          In this work, we demonstrate a facile strategy to synthesize a novel three-dimensional (3D) graphene aerogel-supported and graphene quantum dots-modified γ-MnOOH nanotubes as a highly efficient electrocatalyst. The structure, morphology, and chemical composition of γ-MnOOH@GA/GQDs are investigated by X-ray diffraction (XRD) spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The electrocatalytic activity of catalysts is discussed by cyclic voltammograms (CV), electrochemical impedance spectroscopy (EIS), and rotating disk electrode (RDE) measurements in O 2-saturated 0.1 M KOH electrolyte. The γ-MnOOH@GA/GQDs hybrid exhibits more positive onset potential and half-wave potential, faster charge transfer, lower Tafel slope than that of γ-MnOOH@GA, GA and γ-MnOOH, and mainly undergoes a direct 4e reaction pathway. Furthermore, its electrocatalytic performance is comparable with the commercial 20 wt% Pt/C, which is attributed to the unique 3D crumpled porous nanostructure of GA with large specific area and fast electron transport, and the synergic covalent coupling between the γ-MnOOH nanotubes and GA. More importantly, the GQDs structural defects can facilitate the adsorption of oxygen and charge transfer. As a highly efficient surface “sensitizer”, GQDs are modified on the γ-MnOOH surfaces to further boost the electrocatalytic property.

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          Exploration of the active center structure of nitrogen-doped graphene-based catalysts for oxygen reduction reaction

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            High oxygen-reduction activity and durability of nitrogen-doped graphene

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              Structure-property relationship of bifunctional MnO2 nanostructures: highly efficient, ultra-stable electrochemical water oxidation and oxygen reduction reaction catalysts identified in alkaline media.

              Manganese oxides of various structures (α-, β-, and δ-MnO2 and amorphous) were synthesized by facile methods. The electrocatalytic properties of these materials were systematically investigated for catalyzing both oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) in alkaline media. Extensive characterization was correlated with the activity study by investigating the crystal structures (XRD, HRTEM), morphologies (SEM), porosities (BET), surfaces (XPS, O2-TPD/MS), and electrochemical properties (Tafel analysis, Koutechy-Levich plots, and constant-current electrolysis). These combined results show that the electrocatalytic activities are strongly dependent on the crystallographic structures, and follow an order of α-MnO2 > AMO > β-MnO2 > δ-MnO2. Both OER studies and ORR studies reveal similar structure-determined activity trends in alkaline media. In the OER studies, α-MnO2 displays an overpotential of 490 mV compared to 380 mV shown by an Ir/C catalyst in reaching 10 mA cm(-2). Meanwhile, α-MnO2 also exhibits stability for 3 h when supplying a constant current density of 5 mA cm(-2). This was further improved by adding Ni(2+) dopants (ca. 8 h). The superior OER activity was attributed to several factors, including abundant di-μ-oxo bridges existing in α-MnO2 as the protonation sites, analogous to the OEC in PS-II of the natural water oxidation system; the mixed valencies (AOS = 3.7); and the lowest charge transfer resistances (91.8 Ω, η = 430 mV) as revealed from in situ electrochemical impedance spectroscopy (EIS). In the ORR studies, when reaching 3 mA cm(-2), α-MnO2 shows 760 mV close to 860 mV for the best ORR catalyst (20% Pt/C). The outstanding ORR activity was due to the strongest O2 adsorption capability of α-MnO2 suggested by temperature-programmed desorption. As a result, this discovery of the structure-related electrocatalytic activities could provide guidance in the further development of easily prepared, scalable, and low-cost catalysts based on metal oxides and their derivatives.
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                Author and article information

                Journal
                RSCACL
                RSC Advances
                RSC Adv.
                Royal Society of Chemistry (RSC)
                2046-2069
                2016
                2016
                : 6
                : 49
                : 43116-43126
                Affiliations
                [1 ]School of Chemistry and Chemical Engineering
                [2 ]Central South University
                [3 ]Changsha 410083
                [4 ]China
                [5 ]Key Laboratory of Hunan Province for Metallurgy and Material Processing of Rare Metals
                [6 ]Department of Chemistry
                [7 ]University College London
                [8 ]UK
                [9 ]Max Planck Institut für Chemische Energiekonversion
                [10 ]D-45470 Mülheim an der Ruhr
                [11 ]Germany
                Article
                10.1039/C6RA04695A
                56f92295-3662-4641-a9b0-b105b3e3d091
                © 2016
                History

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