Defect‐Engineered Ultrathin δ‐MnO2 Nanosheet Arrays as Bifunctional Electrodes for Efficient Overall Water Splitting
TL;DR: In this article, a novel bifunctional electrode consisting of two monolayer thick manganese dioxide (δ-MnO2) nanosheet arrays on a nickel foam, using a novel in-situ method was developed.
Abstract: Recently, defect engineering has been used to intruduce half-metallicity into selected semiconductors, thereby significantly enhancing their electrical conductivity and catalytic/electrocatalytic performance. Taking inspiration from this, we developed a novel bifunctional electrode consisting of two monolayer thick manganese dioxide (δ-MnO2) nanosheet arrays on a nickel foam, using a novel in-situ method. The bifunctional electrode exposes numerous active sites for electrocatalytic rections and displays excellent electrical conductivity, resulting in strong performance for both HER and OER. Based on detailed structure analysis and density functional theory (DFT) calculations, the remarkably OER and HER activity of the bifunctional electrode can be attributed to the ultrathin δ-MnO2 nanosheets containing abundant oxygen vacancies lead to the formation od Mn3+ active sites, which give rise to half-metallicity properties and strong H2O adsorption. This synthetic strategy introduced here represents a new method for the development of non-precious metal Mn-based electrocatalysts for eddicient energy conversion.
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TL;DR: The fundamentals of HER are summarized and the recent state-of-the-art advances in the low-cost and high-performance catalysts based on noble and non-noble metals, as well as metal-free HER electrocatalysts are reviewed.
Abstract: Hydrogen fuel is considered as the cleanest renewable resource and the primary alternative to fossil fuels for future energy supply. Sustainable hydrogen generation is the major prerequisite to realize future hydrogen economy. The electrocatalytic hydrogen evolution reaction (HER), as the vital step of water electrolysis to H2 production, has been the subject of extensive study over the past decades. In this comprehensive review, we first summarize the fundamentals of HER and review the recent state-of-the-art advances in the low-cost and high-performance catalysts based on noble and non-noble metals, as well as metal-free HER electrocatalysts. We systemically discuss the insights into the relationship among the catalytic activity, morphology, structure, composition, and synthetic method. Strategies for developing an effective catalyst, including increasing the intrinsic activity of active sites and/or increasing the number of active sites, are summarized and highlighted. Finally, the challenges, perspectives, and research directions of HER electrocatalysis are featured.
1,387 citations
TL;DR: Focusing on self-supported electrodes, the latest advances in their structural design, controllable synthesis, mechanistic understanding, and strategies for performance enhancement are presented.
Abstract: Electrochemical water splitting is a promising technology for sustainable conversion, storage, and transport of hydrogen energy. Searching for earth-abundant hydrogen/oxygen evolution reaction (HER/OER) electrocatalysts with high activity and durability to replace noble-metal-based catalysts plays paramount importance in the scalable application of water electrolysis. A freestanding electrode architecture is highly attractive as compared to the conventional coated powdery form because of enhanced kinetics and stability. Herein, recent progress in developing transition-metal-based HER/OER electrocatalytic materials is reviewed with selected examples of chalcogenides, phosphides, carbides, nitrides, alloys, phosphates, oxides, hydroxides, and oxyhydroxides. Focusing on self-supported electrodes, the latest advances in their structural design, controllable synthesis, mechanistic understanding, and strategies for performance enhancement are presented. Remaining challenges and future perspectives for the further development of self-supported electrocatalysts are also discussed.
1,015 citations
TL;DR: This Perspective presents major progress in several key areas of the OER field such as theoretical understanding, activity trend, in situ and operando characterization, active site determination, and novel materials.
Abstract: Water splitting is the essential chemical reaction to enable the storage of intermittent energies such as solar and wind in the form of hydrogen fuel. The oxygen evolution reaction (OER) is often considered as the bottleneck in water splitting. Though metal oxides had been reported as OER electrocatalysts more than half a century ago, the recent interest in renewable energy storage has spurred a renaissance of the studies of transition metal oxides as Earth-abundant and nonprecious OER catalysts. This Perspective presents major progress in several key areas of the field such as theoretical understanding, activity trend, in situ and operando characterization, active site determination, and novel materials. A personal overview of the past achievements and future challenges is also provided.
1,004 citations
TL;DR: In this paper, the authors describe the fundamentals of the hydrogen evolution reaction/oxygen evolution reaction (HER/OER) and construct efficient electrocatalysts based on the structure-activity relationship.
Abstract: Alkaline water splitting is an attractive method for sustainable hydrogen production. Owing to the sluggish kinetics of alkaline water reduction and oxidation, it is crucial to understand the mechanism of the hydrogen evolution reaction/oxygen evolution reaction (HER/OER) and construct efficient electrocatalysts based on the structure–activity relationship. This review describes the fundamentals of the alkaline HER and OER, the design of noble and nonnoble HER electrocatalysts with low energy barriers, OER electrocatalysts based on binding energy, electronic structure, lattice oxygen, and surface reconstruction as well as the recent developments of bifunctional HER/OER electrocatalysts. Future perspectives towards alkaline water splitting electrocatalysts are also proposed.
874 citations
TL;DR: This study offers a promising and sustainable route for the fixation of atmospheric N2 using solar energy by synthesising defect-rich ultrathin anatase nanosheets with an abundance of oxygen vacancies and intrinsic compressive strain through a facile copper-doping strategy.
Abstract: Dinitrogen reduction to ammonia using transition metal catalysts is central to both the chemical industry and the Earth's nitrogen cycle. In the Haber-Bosch process, a metallic iron catalyst and high temperatures (400 °C) and pressures (200 atm) are necessary to activate and cleave NN bonds, motivating the search for alternative catalysts that can transform N2 to NH3 under far milder reaction conditions. Here, the successful hydrothermal synthesis of ultrathin TiO2 nanosheets with an abundance of oxygen vacancies and intrinsic compressive strain, achieved through a facile copper-doping strategy, is reported. These defect-rich ultrathin anatase nanosheets exhibit remarkable and stable performance for photocatalytic reduction of N2 to NH3 in water, exhibiting photoactivity up to 700 nm. The oxygen vacancies and strain effect allow strong chemisorption and activation of molecular N2 and water, resulting in unusually high rates of NH3 evolution under visible-light irradiation. Therefore, this study offers a promising and sustainable route for the fixation of atmospheric N2 using solar energy.
663 citations
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TL;DR: In this paper, an experimental investigation of magneto-transport in a high-mobility single layer of Graphene is presented, where an unusual half-integer quantum Hall effect for both electron and hole carriers in graphene is observed.
Abstract: When electrons are confined in two-dimensional materials, quantum-mechanically enhanced transport phenomena such as the quantum Hall effect can be observed. Graphene, consisting of an isolated single atomic layer of graphite, is an ideal realization of such a two-dimensional system. However, its behaviour is expected to differ markedly from the well-studied case of quantum wells in conventional semiconductor interfaces. This difference arises from the unique electronic properties of graphene, which exhibits electron–hole degeneracy and vanishing carrier mass near the point of charge neutrality1,2. Indeed, a distinctive half-integer quantum Hall effect has been predicted3,4,5 theoretically, as has the existence of a non-zero Berry's phase (a geometric quantum phase) of the electron wavefunction—a consequence of the exceptional topology of the graphene band structure6,7. Recent advances in micromechanical extraction and fabrication techniques for graphite structures8,9,10,11,12 now permit such exotic two-dimensional electron systems to be probed experimentally. Here we report an experimental investigation of magneto-transport in a high-mobility single layer of graphene. Adjusting the chemical potential with the use of the electric field effect, we observe an unusual half-integer quantum Hall effect for both electron and hole carriers in graphene. The relevance of Berry's phase to these experiments is confirmed by magneto-oscillations. In addition to their purely scientific interest, these unusual quantum transport phenomena may lead to new applications in carbon-based electronic and magneto-electronic devices.
11,122 citations
Journal Article•
TL;DR: An experimental investigation of magneto-transport in a high-mobility single layer of graphene observes an unusual half-integer quantum Hall effect for both electron and hole carriers in graphene.
Abstract: When electrons are confined in two-dimensional materials, quantum-mechanically enhanced transport phenomena such as the quantum Hall effect can be observed. Graphene, consisting of an isolated single atomic layer of graphite, is an ideal realization of such a two-dimensional system. However, its behaviour is expected to differ markedly from the well-studied case of quantum wells in conventional semiconductor interfaces. This difference arises from the unique electronic properties of graphene, which exhibits electron–hole degeneracy and vanishing carrier mass near the point of charge neutrality. Indeed, a distinctive half-integer quantum Hall effect has been predicted theoretically, as has the existence of a non-zero Berry's phase (a geometric quantum phase) of the electron wavefunction—a consequence of the exceptional topology of the graphene band structure. Recent advances in micromechanical extraction and fabrication techniques for graphite structures now permit such exotic two-dimensional electron systems to be probed experimentally. Here we report an experimental investigation of magneto-transport in a high-mobility single layer of graphene. Adjusting the chemical potential with the use of the electric field effect, we observe an unusual half-integer quantum Hall effect for both electron and hole carriers in graphene. The relevance of Berry's phase to these experiments is confirmed by magneto-oscillations. In addition to their purely scientific interest, these unusual quantum transport phenomena may lead to new applications in carbon-based electronic and magneto-electronic devices.
10,112 citations
TL;DR: In this article, a selective solvothermal synthesis of MoS2 nanoparticles on reduced graphene oxide (RGO) sheets suspended in solution was developed, which exhibited superior electrocatalytic activity in the hydrogen evolution reaction (HER).
Abstract: Advanced materials for electrocatalytic and photoelectrochemical water splitting are central to the area of renewable energy. In this work, we developed a selective solvothermal synthesis of MoS2 nanoparticles on reduced graphene oxide (RGO) sheets suspended in solution. The resulting MoS2/RGO hybrid material possessed nanoscopic few-layer MoS2 structures with an abundance of exposed edges stacked onto graphene, in strong contrast to large aggregated MoS2 particles grown freely in solution without GO. The MoS2/RGO hybrid exhibited superior electrocatalytic activity in the hydrogen evolution reaction (HER) relative to other MoS2 catalysts. A Tafel slope of ∼41 mV/decade was measured for MoS2 catalysts in the HER for the first time; this exceeds by far the activity of previous MoS2 catalysts and results from the abundance of catalytic edge sites on the MoS2 nanoparticles and the excellent electrical coupling to the underlying graphene network. The ∼41 mV/decade Tafel slope suggested the Volmer–Heyrovsky mec...
4,370 citations
TL;DR: This review highlights 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), and summarizes some important examples showing that non-Pt HER electrocatsalysts 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 photocatalyst.
Abstract: 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.
4,351 citations
TL;DR: Fossil fuels currently supply most of the world's energy needs, and however unacceptable their long-term consequences, the supplies are likely to remain adequate for the next few generations.
Abstract: Fossil fuels currently supply most of the world's energy needs, and however unacceptable their long-term consequences, the supplies are likely to remain adequate for the next few generations. Scientists and policy makers must make use of this period of grace to assess alternative sources of energy and determine what is scientifically possible, environmentally acceptable and technologically promising.
4,005 citations