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      Phase and composition controlled synthesis of cobalt sulfide hollow nanospheres for electrocatalytic water splitting

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          Abstract

          This work demonstrates the controllable synthesis of cobalt sulfide hollow nanospheres and the phase-dependent catalytic properties for the OER and HER.

          Abstract

          Developing cheap, highly efficient and stable electrocatalysts for both oxygen and hydrogen evolution reactions (OER and HER) is extremely meaningful to realize large-scale implementation of water splitting technology. Herein, we report the phase and composition controlled synthesis of cobalt sulfide (CoS x) hollow nanospheres (HNSs) and their catalytic efficiencies for hydrogen and oxygen evolution reactions in alkaline media. Three CoS x compounds, i.e., Co 9S 8, Co 3S 4, and CoS 2 HNSs, were precisely synthesized by simply adjusting the molar ratio of carbon disulfide to cobalt acetate using a facile solution-based strategy. Electrochemical results reveal that the as-prepared CoS 2 HNSs exhibit superior OER and HER catalytic performance to Co 9S 8 and Co 3S 4 HNSs in 1.0 M KOH, with overpotentials of 290 mV for the OER and 193 mV for the HER at 10 mA cm −2, and the corresponding Tafel slopes of 57 and 100 mV dec −1, respectively. In addition, the CoS 2 HNSs exhibit remarkable long-term catalytic durability, which is even superior to precious metal catalysts of RuO 2 and Pt/C. Moreover, an alkaline electrolyzer assembled using CoS 2 HNSs as both anode and cathode materials can achieve 10 mA cm −2 at a low cell voltage of 1.54 V at 60 °C with a faradaic efficiency of 100% for overall water splitting. Further analysis demonstrates that the surface morphology, crystallographic structure and coordination environment of Co n+ active sites in combination determine the HER/OER activities in the synthesized binary CoS x series, which would provide insight into the rational design of transition metal chalcogenides for highly efficient hydrogen and oxygen-involved electrocatalysis.

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          Solar water splitting cells.

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            Noble metal-free hydrogen evolution catalysts for water splitting.

            Sustainable hydrogen production is an essential prerequisite of a future hydrogen economy. Water electrolysis driven by renewable resource-derived electricity and direct solar-to-hydrogen conversion based on photochemical and photoelectrochemical water splitting are promising pathways for sustainable hydrogen production. All these techniques require, among many things, highly active noble metal-free hydrogen evolution catalysts to make the water splitting process more energy-efficient and economical. In this review, we highlight the recent research efforts toward the synthesis of noble metal-free electrocatalysts, especially at the nanoscale, and their catalytic properties for the hydrogen evolution reaction (HER). We review several important kinds of heterogeneous non-precious metal electrocatalysts, including metal sulfides, metal selenides, metal carbides, metal nitrides, metal phosphides, and heteroatom-doped nanocarbons. In the discussion, emphasis is given to the synthetic methods of these HER electrocatalysts, the strategies of performance improvement, and the structure/composition-catalytic activity relationship. We also summarize some important examples showing that non-Pt HER electrocatalysts could serve as efficient cocatalysts for promoting direct solar-to-hydrogen conversion in both photochemical and photoelectrochemical water splitting systems, when combined with suitable semiconductor photocatalysts.
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              Controllable disorder engineering in oxygen-incorporated MoS2 ultrathin nanosheets for efficient hydrogen evolution.

              Molybdenum disulfide (MoS2) has emerged as a promising electrocatalyst for catalyzing protons to hydrogen via the so-called hydrogen evolution reaction (HER). In order to enhance the HER activity, tremendous effort has been made to engineer MoS2 catalysts with either more active sites or higher conductivity. However, at present, synergistically structural and electronic modulations for HER still remain challenging. In this work, we demonstrate the successfully synergistic regulations of both structural and electronic benefits by controllable disorder engineering and simultaneous oxygen incorporation in MoS2 catalysts, leading to the dramatically enhanced HER activity. The disordered structure can offer abundant unsaturated sulfur atoms as active sites for HER, while the oxygen incorporation can effectively regulate the electronic structure and further improve the intrinsic conductivity. By means of controllable disorder engineering and oxygen incorporation, an optimized catalyst with a moderate degree of disorder was developed, exhibiting superior activity for electrocatalytic hydrogen evolution. In general, the optimized catalyst exhibits onset overpotential as low as 120 mV, accompanied by extremely large cathodic current density and excellent stability. This work will pave a new pathway for improving the electrocatalytic activity by synergistically structural and electronic modulations.
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                Author and article information

                Contributors
                Journal
                NANOHL
                Nanoscale
                Nanoscale
                Royal Society of Chemistry (RSC)
                2040-3364
                2040-3372
                2018
                2018
                : 10
                : 10
                : 4816-4824
                Affiliations
                [1 ]Tianjin Key Laboratory of Composite and Functional Materials
                [2 ]Key Laboratory of Advanced Ceramics and Machining Technology (Ministry of Education)
                [3 ]School of Materials Science and Engineering
                [4 ]Tianjin University
                [5 ]Tianjin 300072
                Article
                10.1039/C7NR09424H
                d03aff02-78bc-4c1a-8434-227d5ee3b1ac
                © 2018

                http://rsc.li/journals-terms-of-use

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