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      Bifunctional Electrocatalysts Based on Mo-Doped NiCoP Nanosheet Arrays for Overall Water Splitting

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          Highlights

          • Freestanding Mo-doped NiCoP nanosheets are designed as bifunctional electrocatalysts for overall water splitting.

          • Remarkable electrocatalytic performances are achieved by Mo doping, where a low-water-splitting voltage of 1.61 V at 10 mA cm −2 is obtained.

          Electronic supplementary material

          The online version of this article (10.1007/s40820-019-0289-6) contains supplementary material, which is available to authorized users.

          Abstract

          Rational design of efficient bifunctional electrocatalysts is highly imperative but still a challenge for overall water splitting. Herein, we construct novel freestanding Mo-doped NiCoP nanosheet arrays by the hydrothermal and phosphation processes, serving as bifunctional electrocatalysts for overall water splitting. Notably, Mo doping could effectively modulate the electronic structure of NiCoP, leading to the increased electroactive site and improved intrinsic activity of each site. Furthermore, an electrochemical activation strategy is proposed to form Mo-doped (Ni,Co)OOH to fully boost the electrocatalytic activities for oxygen evolution reaction. Benefiting from the unique freestanding structure and Mo doping, Mo-doped NiCoP and (Ni,Co)OOH show the remarkable electrochemical performances, which are competitive among current researches. In addition, an overall water splitting device assembled by both electrodes only requires a cell voltage of 1.61 V to reach a current density of 10 mA cm −2. Therefore, this work opens up new avenues for designing nonprecious bifunctional electrocatalysts by Mo doping and in situ electrochemical activation.

          Electronic supplementary material

          The online version of this article (10.1007/s40820-019-0289-6) contains supplementary material, which is available to authorized users.

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          Most cited references46

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          Computational high-throughput screening of electrocatalytic materials for hydrogen evolution.

          The pace of materials discovery for heterogeneous catalysts and electrocatalysts could, in principle, be accelerated by the development of efficient computational screening methods. This would require an integrated approach, where the catalytic activity and stability of new materials are evaluated and where predictions are benchmarked by careful synthesis and experimental tests. In this contribution, we present a density functional theory-based, high-throughput screening scheme that successfully uses these strategies to identify a new electrocatalyst for the hydrogen evolution reaction (HER). The activity of over 700 binary surface alloys is evaluated theoretically; the stability of each alloy in electrochemical environments is also estimated. BiPt is found to have a predicted activity comparable to, or even better than, pure Pt, the archetypical HER catalyst. This alloy is synthesized and tested experimentally and shows improved HER performance compared with pure Pt, in agreement with the computational screening results.
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            In situ cobalt-cobalt oxide/N-doped carbon hybrids as superior bifunctional electrocatalysts for hydrogen and oxygen evolution.

            Remarkable hydrogen evolution reaction (HER) or superior oxygen evolution reaction (OER) catalyst has been applied in water splitting, however, utilizing a bifunctional catalyst for simultaneously generating H2 and O2 is still a challenging issue, which is crucial for improving the overall efficiency of water electrolysis. Herein, inspired by the superiority of carbon conductivity, the propitious H atom binding energy of metallic cobalt, and better OER activity of cobalt oxide, we synthesized cobalt-cobalt oxide/N-doped carbon hybrids (CoOx@CN) composed of Co(0), CoO, Co3O4 applied to HER and OER by simple one-pot thermal treatment method. CoOx@CN exhibited a small onset potential of 85 mV, low charge-transfer resistance (41 Ω), and considerable stability for HER. Electrocatalytic experiments further indicated the better performance of CoOx@CN for HER can be attributed to the high conductivity of carbon, the synergistic effect of metallic cobalt and cobalt oxide, the stability of carbon-encapsulated Co nanoparticles, and the introduction of electron-rich nitrogen. In addition, when used as catalysts of OER, the CoOx@CN hybrids required 0.26 V overpotential for a current density of 10 mA cm(-2), which is comparable even superior to many other non-noble metal catalysts. More importantly, an alkaline electrolyzer that approached ∼20 mA cm(-2) at a voltage of 1.55 V was fabricated by applying CoOx@CN as cathode and anode electrocatalyst, which opened new possibilities for exploring overall water splitting catalysts.
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              The Hydrogen Evolution Reaction in Alkaline Solution: From Theory, Single Crystal Models, to Practical Electrocatalysts

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                Author and article information

                Contributors
                jlqi@hit.edu.cn
                Journal
                Nanomicro Lett
                Nanomicro Lett
                Nano-Micro Letters
                Springer Singapore (Singapore )
                2311-6706
                2150-5551
                13 July 2019
                13 July 2019
                December 2019
                : 11
                : 55
                Affiliations
                [1 ]ISNI 0000 0001 0193 3564, GRID grid.19373.3f, State Key Laboratory of Advanced Welding and Joining, , Harbin Institute of Technology, ; Harbin, 150001 People’s Republic of China
                [2 ]ISNI 0000 0001 0193 3564, GRID grid.19373.3f, School of Materials Science and Engineering, , Harbin Institute of Technology, ; Harbin, 150001 People’s Republic of China
                [3 ]ISNI 0000 0001 0193 3564, GRID grid.19373.3f, MIIT Key Laboratory of Critical Materials Technology for New Energy Conversion and Storage, State Key Laboratory of Urban Water Resource and Environment, School of Chemistry and Chemical Engineering, , Harbin Institute of Technology, ; Harbin, 150001 People’s Republic of China
                Article
                289
                10.1007/s40820-019-0289-6
                7770736
                60a9c2aa-46f1-45ae-8672-185f5f8ee69f
                © The Author(s) 2019

                Open AccessThis article is distributed under the terms of the Creative Commons Attribution 4.0 International License ( http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution, and reproduction in any medium, provided you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons license, and indicate if changes were made.

                History
                : 17 May 2019
                : 24 June 2019
                Categories
                Article
                Custom metadata
                © The Author(s) 2019

                water splitting,bifunctional electrocatalyst,electronic structure,freestanding,metal phosphides

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