CONSPECTUS: In the wake of the discovery of the remarkable electronic and physical properties of graphene, a vibrant research area on two-dimensional (2D) layered materials has emerged during the past decade. Transition metal dichalcogenides (TMDs) represent an alternative group of 2D layered materials that differ from the semimetallic character of graphene. They exhibit diverse properties that depend on their composition and can be semiconductors (e.g., MoS2, WS2), semimetals (e.g., WTe2, TiSe2), true metals (e.g., NbS2, VSe2), and superconductors (e.g., NbSe2, TaS2). The properties of TMDs can also be tailored according to the crystalline structure and the number and stacking sequence of layers in their crystals and thin films. For example, 2H-MoS2 is semiconducting, whereas 1T-MoS2 is metallic. Bulk 2H-MoS2 possesses an indirect band gap, but when 2H-MoS2 is exfoliated into monolayers, it exhibits direct electronic and optical band gaps, which leads to enhanced photoluminescence. Therefore, it is important to learn to control the growth of 2D TMD structures in order to exploit their properties in energy conversion and storage, catalysis, sensing, memory devices, and other applications. In this Account, we first introduce the history and structural basics of TMDs. We then briefly introduce the Raman fingerprints of TMDs of different layer numbers. Then, we summarize our progress on the controlled synthesis of 2D layered materials using wet chemical approaches, chemical exfoliation, and chemical vapor deposition (CVD). It is now possible to control the number of layers when synthesizing these materials, and novel van der Waals heterostructures (e.g., MoS2/graphene, WSe2/graphene, hBN/graphene) have recently been successfully assembled. Finally, the unique optical, electrical, photovoltaic, and catalytic properties of few-layered TMDs are summarized and discussed. In particular, their enhanced photoluminescence (PL), photosensing, photovoltaic conversion, and hydrogen evolution reaction (HER) catalysis are discussed in detail. Finally, challenges along each direction are described. For instance, how to grow perfect single crystalline monolayer TMDs without the presence of grain boundaries and dislocations is still an open question. Moreover, the morphology and crystal structure control of few-layered TMDs still requires further research. For wet chemical approaches and chemical exfoliation methods, it is still a significant challenge to control the lateral growth of TMDs without expansion in the c-axis direction. In fact, there is plenty of room in the 2D world beyond graphene. We envisage that with increasing progress in the controlled synthesis of these systems the unusual properties of mono- and few-layered TMDs and TMD heterostructures will be unveiled.
The synthesis of alloys with long-range atomic-scale ordering (ordered intermetallics) is an emerging field of nanochemistry. Ordered intermetallic nanoparticles are useful for a wide variety of applications such as catalysis, superconductors, and magnetic devices. However, the preparation of nanostructured ordered intermetallics is challenging in comparison to disordered alloys, hindering progress in material development. Herein, we report a process for converting colloidally synthesized ordered intermetallic PdBi2 to ordered intermetallic Pd3Bi nanoparticles under ambient conditions by electrochemical dealloying. The low melting point of PdBi2 corresponds to low vacancy formation energies, which enables the facile removal of the Bi from the surface while simultaneously enabling interdiffusion of the constituent atoms via a vacancy diffusion mechanism under ambient conditions. The resulting phase-converted ordered intermetallic Pd3Bi exhibits 11 times and 3.5 times higher mass activity and high methanol tolerance for the oxygen reduction reaction compared with Pt/C and Pd/C, respectively, which is the highest reported for a Pd-based catalyst, to the best of our knowledge. These results establish a key development in the synthesis of noble-metal-rich ordered intermetallic phases with high catalytic activity and set forth guidelines for the design of ordered intermetallic compounds under ambient conditions.
Recent advances in solar water splitting by using BiVO4 as a photoanode have greatly optimized charge carrier and reaction dynamics, but relatively wide bandgap and poor photostability are still bottlenecks. Here, an excellent photoanode of black BiVO4@amorphous TiO2−x to tackle both problems is reported. Its applied bias photon‐to‐current efficiency for solar water splitting is up to 2.5%, which is a new record for a single oxide photon absorber. This unique core–shell structure is fabricated by coating amorphous TiO2 on nanoporous BiVO4 with the aid of atomic layer deposition and further hydrogen plasma treatment at room temperature. The black BiVO4 with moderate oxygen vacancies reveals a bandgap reduction of ≈0.3 eV and significantly enhances solar utilization, charge transport and separation simultaneously, compared with conventional BiVO4. The amorphous layer of TiO2−x acts as both oxygen‐evolution catalyst and protection layer, which suppresses anodic photocorrosion to stabilize black BiVO4. This configuration of black BiVO4@amorphous TiO2−x may provide an effective strategy to prompt solar water splitting toward practical applications.
We report the colloidal synthesis of substrate-free MoSe 2 nanostructures with a uniform flower-like morphology and tunable average diameters that range from approx. 50-250 nm. The MoSe 2 nanoflowers contain a large population of highly crystalline few-layer nanosheets that protrude from a central core. Aliquot studies and control experiments indicate that the nanoflowers are generated through a two-step process that involves of the formation of a core in the early stages of the reaction, followed by outward nanosheet growth that can be controlled based on the concentrations of reagents. The effects of laser-induced local heating, bulk-scale heating using a temperature stage, and nanostructuring on the ability to trigger and tune interlayer decoupling were also investigated. Notably, laser-induced local heating results in dynamic and reversible interlayer decoupling. Such capabilities provide a pathway for achieving quasi-two-dimensional behavior in three-dimensionally structured and colloidally synthesized transition metal dichalcogenide nanostructures.
GeSe is a narrow band gap IV−VI semiconductor that has been attracting increasing attention as a potential alternative material for photovoltaics, along with other optical and electrical applications. However, unlike several other narrow band gap chalcogenide semiconductors, very few examples of GeSe nanostructures have been reported. Onedimensional nanostructures are particularly attractive, because they can serve as building blocks for nanostructured electronic devices. As a step toward both increasing the morphological diversity of GeSe nanomaterials and expanding the library of electronic materials that are accessible as one-dimensional nanostructures, we report here the colloidal synthesis and electrical properties of GeSe nanobelts. The GeSe nanobelts were synthesized by first heating a one-pot reaction mixture of GeI 4 , TOP-Se, oleylamine, oleic acid, and hexamethyldisilazane to 320 °C, then adding additional TOP-Se and heating for several additional hours. Aliquot studies revealed that an amorphous GeSe x precursor forms first, and then dissolves with continued heating prior to rapid nucleation of the GeSe nanobelts. The resulting nanobelts, which were characterized by transmission electron microscopy (TEM), scanning electron microscopy (SEM), atomic force microscopy (AFM), selected area electron diffraction (SAED), energy dispersive X-ray spectroscopy (EDS), and X-ray diffraction (XRD), had an average diameter of 77 ± 18 nm and lengths that ranged from 1−25 μm. Visible-NIR diffuse reflectance spectroscopy revealed an absorption edge near 1100 nm and an indirect band gap of approximately 1.1 eV. Individual GeSe nanobelts were aligned between Ti/Au electrodes using an electric field-assisted assembly process, and 2-and 4-point current−voltage measurements were conducted, indicating ohmic (linear) behavior with resistivity values of approximately 360 Ω-cm.
Molybdenum ditelluride, MoTe2 , is emerging as an important transition-metal dichalcogenide (TMD) material because of its favorable properties relative to other TMDs. The 1T ' polymorph of MoTe2 is particularly interesting because it is semimetallic with bands that overlap near the Fermi level, but semiconducting 2H-MoTe2 is more stable and therefore more accessible synthetically. Metastable 1T '-MoTe2 forms directly in solution at 300 °C as uniform colloidal nanostructures that consist of few-layer nanosheets, which appear to exhibit an approx. 1 % lateral lattice compression relative to the bulk analogue. Density functional theory calculations suggest that small grain sizes and polycrystallinity stabilize the 1T ' phase in the MoTe2 nanostructures and suppress its transformation back to the more stable 2H polymorph through grain boundary pinning. Raman spectra of the 1T '-MoTe2 nanostructures exhibit a laser energy dependence, which could be caused by electronic transitions.
Metal alloys with atomic scale ordering (ordered intermetallics) have emerged as a new class of high performance materials for mediating electrochemical reactions. However, ordered intermetallic nanostructures often require long synthesis times and/or high temperature annealing to form because a high-activation energy barrier for interdiffusion must be overcome for the constituent metals to equilibrate into ordered structures. Here we report the direct synthesis of metastable ordered intermetallic Pd31Bi12 at room-temperature in minutes via electrochemical deposition. Pd31Bi12 is highly active for the reduction of O2 to H2O, delivering specific activities over 35× higher than those of commercial Pt and Pd nanocatalysts, placing it as the most active Pd-based catalyst, to the best of our knowledge, reported under similar testing conditions. Stability tests demonstrate minimal loss of activity after 10,000 cycles, and a retention of intermetallic crystallinity. This study demonstrates a new method of preparing ordered intermetallics with extraordinary catalytic activity at room temperature, providing a new direction in catalyst discovery and synthesis.
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