Efficient bifunctional vanadium-doped Ni3S2 nanorod array for overall water splitting
12 Feb 2019-Inorganic chemistry frontiers (The Royal Society of Chemistry)-Vol. 6, Iss: 2, pp 443-450
TL;DR: In this paper, a vanadium-doped Ni3S2 nanorod array electrode was proposed for overall water splitting in alkaline media, achieving a cell voltage of 1.421 V at 10 mA cm−2.
Abstract: Electrochemical water splitting, allowing energy conversion from renewable resources into non-polluting chemical fuels, is vital for future sustainable energy systems, and great efforts have been made for developing efficient and cheap bifunctional electrocatalysts. Herein we report a bifunctional vanadium-doped Ni3S2 nanorod array electrode for overall water splitting in alkaline media. To afford a catalytic current of 10 mA cm−2, the designed V-Ni3S2 electrode only requires overpotentials of 133 mV for hydrogen evolution and 148 mV for oxygen generation, meanwhile showing high long-term stability. The excellent catalytic properties are attributed to the V dopant and geometric advantages of the nanorod array. The V-Ni3S2 electrodes are simultaneously utilized as cathode and anode in one two-electrode cell for overall water splitting, exhibiting a cell voltage of 1.421 V at 10 mA cm−2. The water splitting in this cell can also be feasibly driven by a single-cell AA battery (1.5 V). Our report shows substantial advancement in the exploration of efficient bifunctional electrocatalysts for water splitting.
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TL;DR: In this paper, the authors provide guidelines for the design and fabrication of TMS-based bifunctional electrocatalysts with excellent performance and to accelerate their large-scale practical application in water electrolysis.
Abstract: Hydrogen produced via water electrolysis can act as an ideal clean chemical fuel with superb gravimetric energy density and high energy conversion efficiency, solving the problems of conventional fossil fuel exhaustion and environmental contamination. Transition metal sulfides (TMS) have been extensively explored as effective, widely available alternatives to precious metals in overall water splitting. Herein, recent advances, covering preparation methods, intrinsic electrocatalytic performance, and optimization strategies, relating to TMS-based bifunctional electrocatalysts have been summarized systematically and comprehensively. Firstly, a general introduction to the reaction mechanisms and key parameters of the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is provided. Next, the physicochemical properties of TMS and typical synthesis methods are introduced to give guidance for fabricating TMS materials with well-defined structures, controllable compositions, and excellent performance. Importantly, the intrinsic activities of TMS-based electrocatalysts and several strategies for improving their bifunctional electrocatalytic performance during water electrolysis are discussed in detail. Finally, perspectives covering the challenges and opportunities related to the further development of TMS-based materials with high activity and long-term durability for overall water splitting are given. The aim herein is to provide guidelines for the design and fabrication of TMS-based bifunctional electrocatalysts with excellent performance and to accelerate their large-scale practical application in water electrolysis.
224 citations
TL;DR: In this article, the compositional engineering of recently reported transition-metal-compound-based water-splitting catalysts with multiple anion, cation, and zero-valent-element regulations were summarized.
Abstract: Global environmental and energy crises have attracted wide attention and led to ongoing efforts to search for sustainable energy storage and conversion systems that can meet the energy needs of modern society Electrocatalytic water splitting driven by renewable-energy-resource-derived electricity has been identified as a potential and practical strategy for future energy generation Exploring nonprecious-metal-based electrocatalysts with high activity and tolerance is the prerequisite for the widespread application of this energy storage model Heteroatom-regulated electrocatalysts with controllable components as well as electronic structure have unlimited potential toward the pursuit of high-efficiency electrocatalysts and they have been recognized as the perfect platform for establishing clear structure–property relationships Therefore, in this review, the compositional engineering of recently reported transition-metal-compound-based water-splitting catalysts with multiple anion, cation, and zero-valent-element regulations were summarized Particular emphasis is placed on the unique role of different doping configurations for each doping type in enhancing the electrocatalytic activities and stability of heteroatom-regulated electrocatalysts by exposing the active sites, regulating the electronic structure, and promoting the electrical conductivity Finally, some personal perspectives on the design and development of heteroatom-doped electrocatalysts are shared to indicate the possible prospective development of transition-metal-compound-based electrocatalysts
95 citations
TL;DR: In this article, the authors evaluated synergic effects in OER electro/photocatalytic activity, and their correlation with the electronic and crystalline structure of the materials, as well as on the electrode material design.
Abstract: The frenetic global development is improving the average quality of life in an unprecedented way, but at the expense of increasing pressure on natural resources, environmental pollution and energy demand, which are being exacerbated by population growth and industrialization in developing countries. The energy demand probably is the one contributing the most to such a situation, thus urging the development of clean and renewable alternative energy sources in order to avoid an imminent energy crisis in the near future. A possible solution is a society in which most energy needs are fulfilled by photoinduced or electrochemical water-splitting, storing solar energy as hydrogen and dioxygen gas, and releasing the chemical energy in fuel cells while regenerating water. However, the oxygen evolution reaction (OER) and the oxygen reduction reaction taking place respectively in water-splitting and fuel cells are quite sluggish because of their multielectronic and multiprotonic nature. Catalysts such as IrO2 and RuO2 are being successfully used as state-of-the-art OER electrocatalysts but such noble metal-based materials are severely limited by their scarcity and high cost. Thus, noble metal free electro/photocatalysts are being eagerly pursued to provide more sustainable alternatives. In this context, vanadium-based and vanadium-containing electro and photocatalysts based on hydroxides/oxyhydroxides/oxides, vanadates, chalcogenides and nitrides stand out among the most promising alternatives, and recent advances have demonstrated their key role in enhancing the catalytic activity by strong synergic electronic and structural effects. In fact, such high-performance materials have potential in the fabrication of fuel cells and photosynthetic devices competitive enough in converting chemical energy into electricity and solar energy into solar fuel, enabling large-scale production, storage and usage of the infinite energy of the sun in a more convenient and safe manner. Perspectives are also provided on the preparation, evaluation of synergic effects in OER electro/photocatalytic activity, and their correlation with the electronic and crystalline structure of the materials, as well as on the electrode material design.
83 citations
TL;DR: In this paper, a homogeneous structure composed of Co and Ce dual doped Ni3S2 nanosheets on nickel foam was synthesized by a facile one-step hydrothermal method.
Abstract: Developing efficient and stable oxygen evolution reaction (OER) electrocatalysts via doping strategy has well-documented for electrochemical water splitting. Herein, a homogeneous structure (denoted as Co/Ce-Ni3S2/NF) composed of Co and Ce dual doped Ni3S2 nanosheets on nickel foam was synthesized by a facile one-step hydrothermal method. Co and Ce dopants are distributed inside the host sulfide, thereby raising the active sites and the electrical conductivity. Besides, the CeOx nanoparticles generated by part of the Ce dopants as a cocatalyst further improve the catalytic activity by adding defective sites and enhancing the electron transfer. As a consequence, the obtained Co/Ce-Ni3S2/NF electrode exhibits better electrocatalytic activity than single Co or Ce doped Ni3S2 and pure Ni3S2, with low overpotential (286 mV) at 20 mA-cm−2, a small Tafel slope and excellent long-term durability in strong alkaline solution. These results presented here not only offer a novel platform for designing transition metal and lanthanide dual-doped catalysts, but also supply some guidelines for constructing catalysts in other catalytic applications.
61 citations
Cites background from "Efficient bifunctional vanadium-dop..."
...S3(a) and S3(b) in the ESM) possessed clean and smooth surface of three-dimensional (3D) cross-linked structure [28]....
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TL;DR: In this paper, the application of Ni3S2 and its composites in oxygen evolution reaction (OER) was reviewed and the composition, structure and electrochemical catalytic performance were systematically summarized.
57 citations
References
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TL;DR: The topotactic fabrication of self-supported nanoporous cobalt phosphide nanowire arrays on carbon cloth via low-temperature phosphidation of the corresponding Co(OH)F/CC precursor offers excellent catalytic performance and durability under neutral and basic conditions.
Abstract: In this Communication, we report the topotactic fabrication of self-supported nanoporous cobalt phosphide nanowire arrays on carbon cloth (CoP/CC) via low-temperature phosphidation of the corresponding Co(OH)F/CC precursor. The CoP/CC, as a robust integrated 3D hydrogen-evolving cathode, shows a low onset overpotential of 38 mV and a small Tafel slope of 51 mV dec–1, and it maintains its catalytic activity for at least 80 000 s in acidic media. It needs overpotentials (η) of 67, 100, and 204 mV to attain current densities of 10, 20, and 100 mA cm–2, respectively. Additionally, this electrode offers excellent catalytic performance and durability under neutral and basic conditions.
2,063 citations
TL;DR: Current progress in this field is summarized here, especially highlighting several important bifunctional catalysts, and various approaches to improve or optimize the electrocatalysts are introduced.
Abstract: Water electrolysis is considered as the most promising technology for hydrogen production. Much research has been devoted to developing efficient electrocatalysts for hydrogen production via the hydrogen evolution reaction (HER) and oxygen production via the oxygen evolution reaction (OER). The optimum electrocatalysts can drive down the energy costs needed for water splitting via lowering the overpotential. A number of cobalt (Co)-based materials have been developed over past years as non-noble-metal heterogeneous electrocatalysts for HER and OER. Recent progress in this field is summarized here, especially highlighting several important bifunctional catalysts. Various approaches to improve or optimize the electrocatalysts are introduced. Finally, the current existing challenges and the future working directions for enhancing the performance of Co-implicated electrocatalysts are proposed.
1,963 citations
TL;DR: In this article, the hydrogen (H2) and oxygen (O2) fuel cell is the one with zero carbon emission and water as the only byproduct, which is essential to ensure higher life cycle and less decay in cell efficiency.
Abstract: Increasing demand for finding eco-friendly and everlasting energy sources is now totally depending on fuel cell technology. Though it is an eco-friendly way of producing energy for the urgent requirements, it needs to be improved to make it cheaper and more eco-friendly. Although there are several types of fuel cells, the hydrogen (H2) and oxygen (O2) fuel cell is the one with zero carbon emission and water as the only byproduct. However, supplying fuels in the purest form (at least the H2) is essential to ensure higher life cycles and less decay in cell efficiency. The current large-scale H2 production is largely dependent on steam reforming of fossil fuels, which generates CO2 along with H2 and the source of which is going to be depleted. As an alternate, electrolysis of water has been given greater attention than the steam reforming. The reasons are as follows: the very high purity of the H2 produced, the abundant source, no need for high-temperature, high-pressure reactors, and so on. In earlier days,...
1,757 citations
TL;DR: Experimental results and theoretical calculations indicate that Ni3S2/NF's excellent catalytic activity is mainly due to the synergistic catalytic effects produced in it by its nanosheet arrays and exposed {2̅10} high-index facets.
Abstract: Elaborate design of highly active and stable catalysts from Earth-abundant elements has great potential to produce materials that can replace the noble-metal-based catalysts commonly used in a range of useful (electro)chemical processes. Here we report, for the first time, a synthetic method that leads to in situ growth of {210} high-index faceted Ni3S2 nanosheet arrays on nickel foam (NF). We show that the resulting material, denoted Ni3S2/NF, can serve as a highly active, binder-free, bifunctional electrocatalyst for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Ni3S2/NF is found to give ∼100% Faradaic yield toward both HER and OER and to show remarkable catalytic stability (for >200 h). Experimental results and theoretical calculations indicate that Ni3S2/NF’s excellent catalytic activity is mainly due to the synergistic catalytic effects produced in it by its nanosheet arrays and exposed {210} high-index facets.
1,459 citations
TL;DR: This study demonstrates that the constructed interfaces synergistically favor the chemisorption of hydrogen and oxygen-containing intermediates, thus accelerating the overall electrochemical water splitting.
Abstract: To achieve sustainable production of H2 fuel through water splitting, low-cost electrocatalysts for the hydrogen-evolution reaction (HER) and the oxygen-evolution reaction (OER) are required to replace Pt and IrO2 catalysts. Herein, for the first time, we present the interface engineering of novel MoS2/Ni3S2 heterostructures, in which abundant interfaces are formed. For OER, such MoS2/Ni3S2 heterostructures show an extremely low overpotential of ca. 218 mV at 10 mA cm−2, which is superior to that of the state-of-the-art OER electrocatalysts. Using MoS2/Ni3S2 heterostructures as bifunctional electrocatalysts, an alkali electrolyzer delivers a current density of 10 mA cm−2 at a very low cell voltage of ca. 1.56 V. In combination with DFT calculations, this study demonstrates that the constructed interfaces synergistically favor the chemisorption of hydrogen and oxygen-containing intermediates, thus accelerating the overall electrochemical water splitting.
1,222 citations