A highly efficient Ni–Mo bimetallic hydrogen evolution catalyst derived from a molybdate incorporated Ni-MOF
15 May 2018-Journal of Materials Chemistry (The Royal Society of Chemistry)-Vol. 6, Iss: 19, pp 9228-9235
TL;DR: In this paper, a Ni-Mo bimetallic catalyst for the hydrogen evolution reaction can be obtained from a molybdate incorporated Ni-MOF by thermal decomposition in NH3.
Abstract: A highly efficient Ni–Mo bimetallic catalyst for the hydrogen evolution reaction can be obtained from a molybdate incorporated Ni-MOF by thermal decomposition in NH3. The catalyst is composed of crystalline Ni nanoparticles doped with amorphous low valence Mo oxide encapsulated in thin N-doped carbon layers, showing excellent HER performance, featuring a very low overpotential for the HER (η20 = 58 mV), low Tafel slope (57 mV dec−1) and excellent long term stability. The catalyst apparently outperforms N-doped carbon encapsulated Ni catalysts without Mo doping, emphasizing the critical synergetic effect of Mo doping and the surface N-doped carbon thin layer on promoting the performance of Ni based HER catalysts.
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TL;DR: This review first briefly summarizes this background of MOF nanoparticle catalysis and then comprehensively reviews the fast-growing literature reported during the last years.
Abstract: Metal-organic framework (MOF) nanoparticles, also called porous coordination polymers, are a major part of nanomaterials science, and their role in catalysis is becoming central. The extraordinary variability and richness of their structures afford engineering synergies between the metal nodes, functional linkers, encapsulated substrates, or nanoparticles for multiple and selective heterogeneous interactions and activations in these MOF-based nanocatalysts. Pyrolysis of MOF-nanoparticle composites forms highly porous N- or P-doped graphitized MOF-derived nanomaterials that are increasingly used as efficient catalysts especially in electro- and photocatalysis. This review first briefly summarizes this background of MOF nanoparticle catalysis and then comprehensively reviews the fast-growing literature reported during the last years. The major parts are catalysis of organic and molecular reactions, electrocatalysis, photocatalysis, and views of prospects. Major challenges of our society are addressed using these well-defined heterogeneous catalysts in the fields of synthesis, energy, and environment. In spite of the many achievements, enormous progress is still necessary to improve our understanding of the processes involved beyond the proof-of-concept, particularly for selective methane oxidation, hydrogen production, water splitting, CO2 reduction to methanol, nitrogen fixation, and water depollution.
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TL;DR: In this paper, a series of different nanostructure of (Zn-)Co9S8@CF has been synthesized by accurately varying the ratio of Zn2+ to Co2+.
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82 citations
TL;DR: In this paper, in-plane intergrowth CoS2/MoS2 ultrathin nanosheets have been achieved via a one-step pyrolytic sulfurization of a small-sized Co/Mo-MOF precursor.
Abstract: The alkaline hydrogen evolution reaction (HER) is an extremely important reaction in energy conversion and electrolytic industries. Pristine MoS2 exhibits poor alkaline HER activity due to weak water adsorption and dissociation. Precisely manipulating active water dissociation components to form a functional interface with MoS2 would be an effective strategy. Herein, in-plane intergrowth CoS2/MoS2 ultrathin nanosheets have been achieved via a one-step pyrolytic sulfurization of a small-sized Co/Mo-MOF precursor. The in-plane intergrowth structure produced abundant interfaces and modulated the interfacial electronic structure, demonstrating an accelerated water dissociation process. Ultralow overpotentials at both onset (16 mV) and 10 mA cm−2 (75 mV) have been obtained, which surpass those of most top-rated MoS2-based materials and are even proximate to those of commercial Pt/C (0 mV at onset and 60 mV at 10 mA cm−2, respectively). Under a large current density of 400 mA cm−2, the intergrowth nanosheet exhibited long-term stability, showing potential for applications in alkaline water splitting devices.
54 citations
TL;DR: In this paper, the Mo-doped Ni-MOF nanosheets (M-NMN) are encapsulated in the holes of the Ni-MoF frame structure by self-assembly.
51 citations
References
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TL;DR: A standard protocol is used as a primary screen for evaluating the activity, short-term (2 h) stability, and electrochemically active surface area (ECSA) of 18 and 26 electrocatalysts for the hydrogen evolution reaction (HER and OER) under conditions relevant to an integrated solar water-splitting device in aqueous acidic or alkaline solution.
Abstract: Objective comparisons of electrocatalyst activity and stability using standard methods under identical conditions are necessary to evaluate the viability of existing electrocatalysts for integration into solar-fuel devices as well as to help inform the development of new catalytic systems. Herein, we use a standard protocol as a primary screen for evaluating the activity, short-term (2 h) stability, and electrochemically active surface area (ECSA) of 18 electrocatalysts for the hydrogen evolution reaction (HER) and 26 electrocatalysts for the oxygen evolution reaction (OER) under conditions relevant to an integrated solar water-splitting device in aqueous acidic or alkaline solution. Our primary figure of merit is the overpotential necessary to achieve a magnitude current density of 10 mA cm–2 per geometric area, the approximate current density expected for a 10% efficient solar-to-fuels conversion device under 1 sun illumination. The specific activity per ECSA of each material is also reported. Among HER...
2,877 citations
TL;DR: An overview of recent developments in the non-noble metal catalysts for electrochemical hydrogen evolution reaction (HER) is presented, with emphasis on the nanostructuring of industrially relevant hydrotreating catalysts as potential HER electrocatalysts.
Abstract: Progress in catalysis is driven by society's needs. The development of new electrocatalysts to make renewable and clean fuels from abundant and easily accessible resources is among the most challenging and demanding tasks for today's scientists and engineers. The electrochemical splitting of water into hydrogen and oxygen has been known for over 200 years, but in the last decade and motivated by the perspective of solar hydrogen production, new catalysts made of earth-abundant materials have emerged. Here we present an overview of recent developments in the non-noble metal catalysts for electrochemical hydrogen evolution reaction (HER). Emphasis is given to the nanostructuring of industrially relevant hydrotreating catalysts as potential HER electrocatalysts. The new syntheses and nanostructuring approaches might pave the way for future development of highly efficient catalysts for energy conversion.
1,882 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
TL;DR: A metal-organic frameworks-assisted strategy for synthesizing nanostructured transition metal carbide nano-octahedrons composed of ultrafine nanocrystallites exhibited remarkable electrocatalytic performance for hydrogen production from both acidic and basic solutions is demonstrated.
Abstract: Electrochemical water splitting has been considered as a promising approach to produce clean and sustainable hydrogen fuel. However, the lack of high-performance and low-cost electrocatalysts for hydrogen evolution reaction hinders the large-scale application. As a new class of porous materials with tunable structure and composition, metal-organic frameworks have been considered as promising candidates to synthesize various functional materials. Here we demonstrate a metal-organic frameworks-assisted strategy for synthesizing nanostructured transition metal carbides based on the confined carburization in metal-organic frameworks matrix. Starting from a compound consisting of copper-based metal-organic frameworks host and molybdenum-based polyoxometalates guest, mesoporous molybdenum carbide nano-octahedrons composed of ultrafine nanocrystallites are successfully prepared as a proof of concept, which exhibit remarkable electrocatalytic performance for hydrogen production from both acidic and basic solutions. The present study provides some guidelines for the design and synthesis of nanostructured electrocatalysts. There is extensive research into non-platinum electrocatalysts for hydrogen evolution. Here, the authors report a molybdenum carbide catalyst, prepared via the carburization of a copper metal-organic framework host/molybdenum-based polyoxometalates guest system, and demonstrate its catalytic activity.
1,194 citations
TL;DR: Molybdenum boride and carbide are excellent catalysts for electrochemical hydrogen evolution at both pH 0 and pH 14.
Abstract: Molybdenum boride (MoB) and carbide (Mo2C) are excellent catalysts for electrochemical hydrogen evolution at both pH 0 and pH 14.
1,163 citations