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      Robust carbon dioxide reduction on molybdenum disulphide edges.

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          Abstract

          Electrochemical reduction of carbon dioxide has been recognized as an efficient way to convert carbon dioxide to energy-rich products. Noble metals (for example, gold and silver) have been demonstrated to reduce carbon dioxide at moderate rates and low overpotentials. Nevertheless, the development of inexpensive systems with an efficient carbon dioxide reduction capability remains a challenge. Here we identify molybdenum disulphide as a promising cost-effective substitute for noble metal catalysts. We uncover that molybdenum disulphide shows superior carbon dioxide reduction performance compared with the noble metals with a high current density and low overpotential (54 mV) in an ionic liquid. Scanning transmission electron microscopy analysis and first principle modelling reveal that the molybdenum-terminated edges of molybdenum disulphide are mainly responsible for its catalytic performance due to their metallic character and a high d-electron density. This is further experimentally supported by the carbon dioxide reduction performance of vertically aligned molybdenum disulphide.

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          Most cited references26

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          Generalized gradient approximation for the exchange-correlation hole of a many-electron system

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            Anomalous Lattice Vibrations of Single and Few-Layer MoS2

            Molybdenum disulfide (MoS2) of single and few-layer thickness was exfoliated on SiO2/Si substrate and characterized by Raman spectroscopy. The number of S-Mo-S layers of the samples was independently determined by contact-mode atomic-force microscopy. Two Raman modes, E12g and A1g, exhibited sensitive thickness dependence, with the frequency of the former decreasing and that of the latter increasing with thickness. The results provide a convenient and reliable means for determining layer thickness with atomic-level precision. The opposite direction of the frequency shifts, which cannot be explained solely by van der Waals interlayer coupling, is attributed to Coulombic interactions and possible stacking-induced changes of the intralayer bonding. This work exemplifies the evolution of structural parameters in layered materials in changing from the 3-dimensional to the 2-dimensional regime.
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              Aqueous CO2 reduction at very low overpotential on oxide-derived Au nanoparticles.

              Carbon dioxide reduction is an essential component of many prospective technologies for the renewable synthesis of carbon-containing fuels. Known catalysts for this reaction generally suffer from low energetic efficiency, poor product selectivity, and rapid deactivation. We show that the reduction of thick Au oxide films results in the formation of Au nanoparticles ("oxide-derived Au") that exhibit highly selective CO(2) reduction to CO in water at overpotentials as low as 140 mV and retain their activity for at least 8 h. Under identical conditions, polycrystalline Au electrodes and several other nanostructured Au electrodes prepared via alternative methods require at least 200 mV of additional overpotential to attain comparable CO(2) reduction activity and rapidly lose their activity. Electrokinetic studies indicate that the improved catalysis is linked to dramatically increased stabilization of the CO(2)(•-) intermediate on the surfaces of the oxide-derived Au electrodes.
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                Author and article information

                Journal
                Nat Commun
                Nature communications
                2041-1723
                2041-1723
                2014
                : 5
                Affiliations
                [1 ] 1] Department of Mechanical and Industrial Engineering, University of Illinois at Chicago, Chicago, Illinois 60607, USA [2].
                [2 ] Department of Mechanical and Industrial Engineering, University of Illinois at Chicago, Chicago, Illinois 60607, USA.
                [3 ] Department of Chemical and Biomolecular Engineering, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
                [4 ] Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, USA.
                [5 ] Department of Physics, University of Illinois at Chicago, Chicago, Illinois 60607, USA.
                [6 ] Dioxide Materials, Champaign, Illinois 61820, USA.
                [7 ] Materials Research Laboratory, University of Illinois at Urbana-Champaign, Urbana, Illinois 61801, USA.
                [8 ] 1] Department of Chemistry, University of Illinois at Chicago, Chicago, Illinois 60607, USA [2] Department of Physics, University of Illinois at Chicago, Chicago, Illinois 60607, USA.
                Article
                ncomms5470
                10.1038/ncomms5470
                25073814
                f3ead402-ddd4-4700-a3b0-8d9d73cccd1b
                History

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