Layered materials consist of molecular layers stacked together by weak interlayer interactions. They often crystallize to form atomically smooth thin films, nanotubes, and platelet or fullerene-like nanoparticles due to the anisotropic bonding. Structures that predominately expose edges of the layers exhibit high surface energy and are often considered unstable. In this communication, we present a synthesis process to grow MoS2 and MoSe2 thin films with vertically aligned layers, thereby maximally exposing the edges on the film surface. Such edge-terminated films are metastable structures of MoS2 and MoSe2, which may find applications in diverse catalytic reactions. We have confirmed their catalytic activity in a hydrogen evolution reaction (HER), in which the exchange current density correlates directly with the density of the exposed edge sites.
The ability to intercalate guest species into the van der Waals gap of 2D layered materials affords the opportunity to engineer the electronic structures for a variety of applications. Here we demonstrate the continuous tuning of layer vertically aligned MoS 2 nanofilms through electrochemical intercalation of Li + ions. By scanning the Li intercalation potential from high to low, we have gained control of multiple important material properties in a continuous manner, including tuning the oxidation state of Mo, the transition of semiconducting 2H to metallic 1T phase, and expanding the van der Waals gap until exfoliation. Using such nanofilms after different degree of Li intercalation, we show the significant improvement of the hydrogen evolution reaction activity. A strong correlation between such tunable material properties and hydrogen evolution reaction activity is established. This work provides an intriguing and effective approach on tuning electronic structures for optimizing the catalytic activity.2D materials | layer vertically standing | electrochemical catalysis L ayer-structured 2D materials are an interesting family of materials with strong covalent bonding within molecular layers and weak van der Waals interaction between layers. Beyond intensively studied graphene-related materials (1-4), there has been recent strong interest in other layered materials whose vertical thickness can be thinned down to less than few nanometers and horizontal width can also be reduced to nanoscale (5-9). The strong interest is driven by their interesting physical and chemical properties (2, 10) and their potential applications in transistors, batteries, topological insulators, thermoelectrics, artificial photosynthesis, and catalysis (4,(11)(12)(13)(14)(15)(16)(17)(18)(19)(20)(21)(22)(23)(24)(25).One of the unique properties of 2D layered materials is their ability to intercalate guest species into their van der Waals gaps, opening up the opportunities to tune the properties of materials. For example, the spacing between the 2D layers could be increased by intercalation such as lithium (Li) intercalated graphite or molybdenum disulfide (MoS 2 ) and copper intercalated bismuth selenide (26-29). The electronic structures of the host lattice, such as the charge density, anisotropic transport, oxidation state, and phase transition, may also be changed by different species intercalation (26,27).As one of the most interesting layered materials, MoS 2 has been extensively studied in a variety of areas such as electrocatalysis (20)(21)(22)(30)(31)(32)(33)(34)(35)(36). It is known that there is a strong correlation between the electronic structure and catalytic activity of the catalysts (20,(37)(38)(39)(40)(41). It is intriguing to continuously tune the morphology and electronic structure of MoS 2 and explore the effects on MoS 2 hydrogen evolution reaction (HER) activity. Very recent studies demonstrated that the monolayered MoS 2 and WS 2 nanosheets with 1T metallic phase synthesized by chemical exfoliation exhibited superio...
Topological insulators represent unusual phases of quantum matter with an insulating bulk gap and gapless edges or surface states. The two-dimensional topological insulator phase was predicted in HgTe quantum wells and confirmed by transport measurements. Recently, Bi(2)Se(3) and related materials have been proposed as three-dimensional topological insulators with a single Dirac cone on the surface, protected by time-reversal symmetry. The topological surface states have been observed by angle-resolved photoemission spectroscopy experiments. However, few transport measurements in this context have been reported, presumably owing to the predominance of bulk carriers from crystal defects or thermal excitations. Here we show unambiguous transport evidence of topological surface states through periodic quantum interference effects in layered single-crystalline Bi(2)Se(3) nanoribbons, which have larger surface-to-volume ratios than bulk materials and can therefore manifest surface effects. Pronounced Aharonov-Bohm oscillations in the magnetoresistance clearly demonstrate the coherent propagation of two-dimensional electrons around the perimeter of the nanoribbon surface, as expected from the topological nature of the surface states. The dominance of the primary h/e oscillation, where h is Planck's constant and e is the electron charge, and its temperature dependence demonstrate the robustness of these states. Our results suggest that topological insulator nanoribbons afford promising materials for future spintronic devices at room temperature.
Development of a non-noble-metal hydrogen-producing catalyst is essential to the development of solar water-splitting devices. Improving both the activity and the stability of the catalyst remains a key challenge. In this Communication, we describe a two-step reaction for preparing three-dimensional electrodes composed of CoSe2 nanoparticles grown on carbon fiber paper. The electrode exhibits excellent catalytic activity for a hydrogen evolution reaction in an acidic electrolyte (100 mA/cm(2) at an overpotential of ∼180 mV). Stability tests though long-term potential cycles and extended electrolysis confirm the exceptional durability of the catalyst. This development offers an attractive catalyst material for large-scale water-splitting technology.
Transparent conducting electrodes are essential components for numerous flexible optoelectronic devices, including touch screens and interactive electronics. Thin films of indium tin oxide-the prototypical transparent electrode material-demonstrate excellent electronic performances, but film brittleness, low infrared transmittance and low abundance limit suitability for certain industrial applications. Alternatives to indium tin oxide have recently been reported and include conducting polymers, carbon nanotubes and graphene. However, although flexibility is greatly improved, the optoelectronic performance of these carbon-based materials is limited by low conductivity. Other examples include metal nanowire-based electrodes, which can achieve sheet resistances of less than 10Ω □(-1) at 90% transmission because of the high conductivity of the metals. To achieve these performances, however, metal nanowires must be defect-free, have conductivities close to their values in bulk, be as long as possible to minimize the number of wire-to-wire junctions, and exhibit small junction resistance. Here, we present a facile fabrication process that allows us to satisfy all these requirements and fabricate a new kind of transparent conducting electrode that exhibits both superior optoelectronic performances (sheet resistance of ~2Ω □(-1) at 90% transmission) and remarkable mechanical flexibility under both stretching and bending stresses. The electrode is composed of a free-standing metallic nanotrough network and is produced with a process involving electrospinning and metal deposition. We demonstrate the practical suitability of our transparent conducting electrode by fabricating a flexible touch-screen device and a transparent conducting tape.
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