We perform a comprehensive first-principles study of the electronic properties of phosphorene nanoribbons, phosphorene nanotubes, multilayer phosphorene, and heterobilayers of phosphorene and two-dimensional (2D) transition metal dichalcogenide (TMDC) monolayer. The tensile strain and electric-field effects on electronic properties of low-dimensional phosphorene nanostructures are also investigated. Our calculations show that zigzag phosphorene nanoribbons (z-PNRs) are metals, regardless of the ribbon width while armchair phosphorene nanoribbons (a-PNRs) are semiconductors with indirect bandgaps and the bandgaps are insensitive to variation of the ribbon width. We find that tensile compression (or expansion) strains can reduce (or increase) the bandgap of the a-PNRs while an in-plane electric field can significantly reduce the bandgap of aPNRs, leading to the semiconductor-to-metal transition beyond certain electric field. For single-walled phosphorene nanotubes (SW-PNTs), both armchair and zigzag nanotubes are semiconductors with direct bandgaps. With either tensile strains or transverse electric field, similar behavior of bandgap modulation can arise as that for a-PNRs. It is known that multilayer phosphorene sheets are semiconductors with their bandgaps decreasing with increasing the number of multilayers. In the presence of a vertical electric field, the 2 bandgaps of multilayer phosphorene sheets decrease with increasing the electric field, and the bandgap modulation is more significant with more layers. Lastly, heterobilayers of phosporene with a TMDC (MoS 2 or WS 2 ) monolayer are still semiconductors while their bandgaps can be reduced by applying a vertical electric field as well.
Nanoscale Pt-Ni bimetallic octahedra with controlled sizes have been actively explored in recent years owning to their outstanding activity for the oxygen reduction reaction (ORR). Here we report the synthesis of uniform 9 nm Pt-Ni octahedra with the use of oleylamine and oleic acid as surfactants and W(CO)6 as a source of CO that can promote the formation of {111} facets in the presence of Ni. Through the introduction of benzyl ether as a solvent, the coverage of both surfactants on the surface of resultant Pt-Ni octahedra was significantly reduced while the octahedral shape was still attained. By further removing the surfactants through acetic acid treatment, we observed a specific activity 51-fold higher than that of the state-of-the-art Pt/C catalyst for the ORR at 0.93 V, together with a record high mass activity of 3.3 A mgPt(-1) at 0.9 V (the highest mass activity reported in the literature was 1.45 A mgPt(-1)). Our analysis suggests that this great enhancement of ORR activity could be attributed to the presence of a clean, well-preserved (111) surface for the Pt-Ni octahedra.
An effective strategy for reducing the Pt content while retaining the activity of a Pt-based catalyst is to deposit the Pt atoms as ultrathin skins of only a few atomic layers thick on nanoscale substrates made of another metal. During deposition, however, the Pt atoms often take an island growth mode because of a strong bonding between Pt atoms. Here we report a versatile route to the conformal deposition of Pt as uniform, ultrathin shells on Pd nanocubes in a solution phase. The introduction of the Pt precursor at a relatively slow rate and high temperature allowed the deposited Pt atoms to spread across the entire surface of a Pd nanocube to generate a uniform shell. The thickness of the Pt shell could be controlled from one to six atomic layers by varying the amount of Pt precursor added into the system. Compared to a commercial Pt/C catalyst, the Pd@PtnL (n = 1-6) core-shell nanocubes showed enhancements in specific activity and durability toward the oxygen reduction reaction (ORR). Density functional theory (DFT) calculations on model (100) surfaces suggest that the enhancement in specific activity can be attributed to the weakening of OH binding through ligand and strain effects, which, in turn, increases the rate of OH hydrogenation. A volcano-type relationship between the ORR specific activity and the number of Pt atomic layers was derived, in good agreement with the experimental results. Both theoretical and experimental studies indicate that the ORR specific activity was maximized for the catalysts based on Pd@Pt2-3L nanocubes. Because of the reduction in Pt content used and the enhancement in specific activity, the Pd@Pt1L nanocubes showed a Pt mass activity with almost three-fold enhancement relative to the Pt/C catalyst.
Controlling the shape or morphology of metal nanocrystals is central to the realization of their many applications in catalysis, plasmonics, and electronics. In one of the approaches, the metal nanocrystals are grown from seeds of certain crystallinity through the addition of atomic species. In this case, manipulating the rates at which the atomic species are added onto different crystallographic planes of a seed has been actively explored to control the growth pattern of a seed and thereby the shape or morphology taken by the final product. Upon deposition, however, the adsorbed atoms (adatoms) may not stay at the same sites where the depositions occur. Instead, they can migrate to other sites on the seed owing to the involvement of surface diffusion, and this could lead to unexpected deviations from a desired growth pathway. Herein, we demonstrated that the growth pathway of a seed is indeed determined by the ratio between the rates for atom deposition and surface diffusion. Our result suggests that surface diffusion needs to be taken into account when controlling the shape or morphology of metal nanocrystals. seeded growth | shape control | noble metals S urface diffusion is a general process that involves the motion of adsorbed atoms (adatoms), molecules, or atomic clusters on the surface of a solid material (1, 2). Over the past decades, it has emerged as an important concept in many areas of surface science, including catalysis, epitaxial growth, and electromigration of voids (3-7). Here, we demonstrated that surface diffusion also plays a pivotal role in determining the growth pathway of a seed and thus the shape or morphology taken by the final product in a solutionphase synthesis of metal nanocrystals. Fig. 1 schematically illustrates four possible pathways for the growth of a cubic seed. As a model system, we focused on Pd nanocubes with slight truncation at corners and edges, together with six side faces passivated by chemisorbed Br -ions. In the following discussion, we refer to them as "Pd cubic seeds" for simplicity. We chose them as seeds for two major reasons: (i) they had a well-defined shape, together with a set of low-index facets on the surface (8, 9); and (ii) their side faces are blocked by Br -ions to ensure selective deposition of atoms onto the corner sites during seed-mediated growth (10-12). These two distinctive features allowed us to easily track the deposition of atoms and their surface diffusion during a growth process by analyzing the shape or morphology of the final product.The newly formed Pd atoms resulting from the reduction of a Pd precursor are expected to deposit at the corners of a cubic seed because the side faces are blocked by the chemisorbed Br -ions (Fig. 1A, 1). Upon deposition, there will be two different options for these adatoms: staying at the corner sites or migrating to other sites, including edges and side faces, through surface diffusion (Fig. 1A, 2 and 3). It should be pointed out that only surface diffusion was allowed here to move atoms from corners to edg...
Substitutional doping of transition metal dichalcogenides (TMDs) may provide routes to achieving tunable p-n junctions, bandgaps, chemical sensitivity, and magnetism in these materials. In this study, we demonstrate in situ doping of monolayer molybdenum disulfide (MoS2) with manganese (Mn) via vapor phase deposition techniques. Successful incorporation of Mn in MoS2 leads to modifications of the band structure as evidenced by photoluminescence and X-ray photoelectron spectroscopy, but this is heavily dependent on the choice of substrate. We show that inert substrates (i.e., graphene) permit the incorporation of several percent Mn in MoS2, while substrates with reactive surface terminations (i.e., SiO2 and sapphire) preclude Mn incorporation and merely lead to defective MoS2. The results presented here demonstrate that tailoring the substrate surface could be the most significant factor in substitutional doping of TMDs with non-TMD elements.
Tungsten diselenide (WSe2) is a two-dimensional material that is of interest for next-generation electronic and optoelectronic devices due to its direct bandgap of 1.65 eV in the monolayer form and excellent transport properties. However, technologies based on this 2D material cannot be realized without a scalable synthesis process. Here, we demonstrate the first scalable synthesis of large-area, mono and few-layer WSe2 via metal-organic chemical vapor deposition using tungsten hexacarbonyl (W(CO)6) and dimethylselenium ((CH3)2Se). In addition to being intrinsically scalable, this technique allows for the precise control of the vapor-phase chemistry, which is unobtainable using more traditional oxide vaporization routes. We show that temperature, pressure, Se:W ratio, and substrate choice have a strong impact on the ensuing atomic layer structure, with optimized conditions yielding >8 μm size domains. Raman spectroscopy, atomic force microscopy (AFM), and cross-sectional transmission electron microscopy (TEM) confirm crystalline monoto-multilayer WSe2 is achievable. Finally, TEM and vertical current/voltage transport provide evidence that a pristine van der Waals gap exists in WSe2/graphene heterostructures.
Controllable doping of two-dimensional materials is highly desired for ideal device performance in both hetero- and p-n homojunctions. Herein, we propose an effective strategy for doping of MoS2 with nitrogen through a remote N2 plasma surface treatment. By monitoring the surface chemistry of MoS2 upon N2 plasma exposure using in situ X-ray photoelectron spectroscopy, we identified the presence of covalently bonded nitrogen in MoS2, where substitution of the chalcogen sulfur by nitrogen is determined as the doping mechanism. Furthermore, the electrical characterization demonstrates that p-type doping of MoS2 is achieved by nitrogen doping, which is in agreement with theoretical predictions. Notably, we found that the presence of nitrogen can induce compressive strain in the MoS2 structure, which represents the first evidence of strain induced by substitutional doping in a transition metal dichalcogenide material. Finally, our first principle calculations support the experimental demonstration of such strain, and a correlation between nitrogen doping concentration and compressive strain in MoS2 is elucidated.
Peroxidase mimics with dimensions on the nanoscale have received great interest as emerging artificial enzymes for biomedicine and environmental protection. While a variety of peroxidase mimics have been actively developed recently, limited progress has been made toward improving their catalytic efficiency. In this study, we report a type of highly efficient peroxidase mimic that was engineered by depositing Ir atoms as ultrathin skins (a few atomic layers) on Pd nanocubes (i.e., Pd-Ir cubes). The Pd-Ir cubes exhibited significantly enhanced efficiency, with catalytic constants more than 20- and 400-fold higher than those of the initial Pd cubes and horseradish peroxidase (HRP), respectively. As a proof-of-concept demonstration, the Pd-Ir cubes were applied to the colorimetric enzyme-linked immunosorbent assay (ELISA) of human prostate surface antigen (PSA) with a detection limit of 0.67 pg/mL, which is ∼110-fold lower than that of the conventional HRP-based ELISA using the same set of antibodies and the same procedure.
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