Large-Substrate-Terrace Confined Growth of Arrayed Ultrathin PtSe2 Ribbons on Step-Bunched Vicinal Au(001) Facets Toward Electrocatalytic Applications.

Ultrathin PtSe2 ribbons can host spin-polarized edge states and distinct edge electrocatalytic activity, emerging as a promising candidate for versatile applications in various fields. However, the direct synthesis is still challenging and the growth mechanism is still unclear. Herein, the arrayed growth of ultrathin PtSe2 ribbons on bunched vicinal Au(001) facets, via a facile chemical vapor deposition (CVD) route is reported. The ultrathin PtSe2 flakes can transform from traditional irregular shapes to desired ribbon shapes by increasing the height of bunched and unidirectionally oriented Au steps (with step height hstep) is found. This crossover, occurring at hstep ≈ 3.0 nm, defines the tailored growth from step-flow to single-terrace-confined modes, as validated by density functional theory calculations of the different system energies. On the millimeter-scale single-crystal Au(001) films with aligned steps, the arrayed ultrathin PtSe2 ribbons with tunable width of ≈20-1000 nm, which are then served as prototype electrocatalysts for hydrogen evolution reaction (HER) is achieved. This work should represent a huge leap in the direct synthesis and the mechanism exploration of arrayed ultrathin transition-metal dichalcogenides (TMDCs) ribbons, which should stimulate further explorations of the edge-related physical properties and practical applications.

Water-Assisted Growth of Twisted 3R-Stacked MoSe2 Spirals and Its Dramatically Enhanced Second Harmonic Generations.

Enhanced second-harmonic generation (SHG) responses are reported in monolayer transition metal dichalcogenides (e.g., MX2 , M: Mo, W; X: S, Se) due to the broken symmetries. The 3R-like stacked MX2 spiral structures possessing the similar broken inversion symmetry should present dramatically enhanced SHG responses, thus providing great flexibility in designing miniaturized on-chip nonlinear optical devices. To achieve this, the first direct synthesis of twisted 3R-stacked chiral molybdenum diselenide (MoSe2 ) spiral structures with specific screw dislocations (SD) arms is reported, via designing a water-assisted chemical vapor transport (CVT) approach. The study also clarifies the formation mechanism of the MoSe2 spiral structures, by precisely regulating the precursor supply accompanying with multiscale characterizations. Significantly, an up to three orders of magnitude enhancement of the SHG responses in twisted 3R stacked MoSe2 spirals is demonstrated, which is proposed to arise from the synergistic effects of broken inversion symmetry, strong light-matter interaction, and band nesting effects. Briefly, the work provides an efficient synthetic route for achieving the 3R-stacked TMDCs spirals, which can serve as perfect platforms for promoting their applications in on-chip nonlinear optical devices.

Epitaxial Growth of High-Quality Monolayer MoS2 Single Crystals on Low-Symmetry Vicinal Au(101) Facets with Different Miller Indices.

Epitaxial growth of wafer-scale monolayer semiconducting transition metal dichalcogenide single crystals is essential for advancing their applications in next-generation transistors and highly integrated circuits. Several efforts have been made for the growth of monolayer MoS2 single crystals on high-symmetry Au(111) and sapphire substrates, while more prototype growth systems still need to be discovered for clarifying the internal mechanisms. Herein, we report the epitaxial growth of unidirectionally aligned monolayer MoS2 domains and single-crystal films on low-symmetry Au(101) vicinal facets via a facile chemical vapor deposition method. On-site scanning tunneling microscopy observations reveal the formation of a specific rectangular Moiré pattern along the [101̅] step edge of Au(101) and along its perpendicular direction. The perfect lattice constant matching of MoS2/Au(101) along the substrate high-symmetry directions (i.e., Au[101̅], Au [010]) as well as the step-edge-guiding effect are proposed to facilitate the robust epitaxy. Multiscale characterizations further confirm the domain-boundary-free feature of the monolayer MoS2 films merged by unidirectionally aligned monolayer domains. This work hereby puts forward a symmetry mismatched epitaxial system for the direct synthesis of monolayer MoS2 single crystals, which should deepen our understanding about the epitaxy of 2D layered materials and propel their applications in various fields.

Robust VS4@rGO nanocomposite as a high-capacity and long-life cathode material for aqueous zinc-ion batteries.

Although vanadium (V)-based sulfides have been investigated as cathodes for aqueous zinc-ion batteries (ZIBs), the performance improvement and the intrinsic zinc-ion (Zn2+) storage mechanism revelation is still challenging. Here, VS4@rGO composite with optimized morphology is designed and exhibits ultrahigh specific capacity (450 mA h g-1 at 0.5 A g-1) and high-rate capability (313.8 mA h g-1 at 10 A g-1) when applied as cathode material for aqueous ZIBs. Furthermore, the VS4@rGO cathode presents long-life cycling stability with capacity retention of ∼82% after 3500 cycles at 10 A g-1. The structural evolution, redox, and degradation mechanisms of VS4 during (dis)charge processes are further probed by in situ XRD/Raman techniques and TEM analysis. Our results indicate that the main energy storage mechanism is derived from the intercalation/deintercalation reactions in the open channels of VS4. Notably, an irreversible phase transition of VS4 into Zn3(OH)2V2O7·2H2O (ZVO) during the charging process and the further transition from ZVO to ZnV3O8 during long-term cycles are also observed, which might be the main reason leading to the capacity degradation of VS4@rGO. Our study further improves the electrochemical performance of VS4 in aqueous ZIBs through morphology design and provides new insights into the energy storage and performance degradation mechanisms of Zn2+ storage in VS4, and thus may endow the large-scale application of V-based sulfides for energy storage systems.

Intercalation-Mediated Synthesis and Interfacial Coupling Effect Exploration of Unconventional Graphene/PtSe2 Vertical Heterostructures.

Vertical heterostructures formed by stacks of two-dimensional (2D) layered materials with disparate electronic properties have attracted tremendous attention for their versatile applications. The targeted fabrication of such vertical stacks with clean interfaces and a specific stacking sequence remains challenging. Herein, we design a two-step chemical vapor deposition route for the direct synthesis of unconventional graphene/PtSe2 vertical stacks (Gr/PtSe2) on conductive Au foil substrates. Monolayer PtSe2 (1L-PtSe2) was detected to preferentially grow at the interface of the predeposited Gr layer and the Au foil substrate rather than on the Gr surface. The concurrent effect from the strong interaction of PtSe2/Au and the space confinement effect of Gr/Au are proposed to be the essential mechanisms. Particularly, this unique growth system allows us to uncover the intrinsic property of 1L-PtSe2 and the interfacial coupling effect using scanning tunneling microscopy/spectroscopy. Our work should hereby enable significant advances in the synthesis of 2D-based vertical heterostructures and in the exploration of their intrinsic interface properties.

Design and understanding of core/branch-structured VS2 nanosheets@CNTs as high-performance anode materials for lithium-ion batteries.

Revealing the electrochemical property-structure relationship and observing the dynamic structural evolution of electrode materials are critically important for battery performance improvement and the corresponding mechanistic understanding. Here, highly crystalline VS2 nanosheets/carbon nanotubes (CNTs) with a core/branch structure were synthesized, exhibiting reversible discharge capacity of ∼850 mA h g-1 at 200 mA g-1, high coulombic efficiency of ∼98%, good cycling stability and superior rate capability. The relationship between the electrochemical properties and the corresponding dynamic microstructural evolution was further revealed with the in situ electron microscopy technique. Our results showed that the intercalation process with the formation of amorphous LixVS2 and the subsequent conversion reactions with the formation of crystalline Li2S and V nanocrystals occurred during the discharging process. Crystalline Li2S was oxidized in the charging process. The core/branched structure ensured a large exposed surface area of the VS2 nanosheets and provided extra space to accommodate the volume expansion. Meanwhile, the CNTs surrounded by VS2 nanosheets not only provided a continuous and fast conducting pathway for carriers throughout the electrodes, but also enhanced the mechanical stability of the electrode material. These factors finally contributed to the superior electrochemical performance of the core/branch-structured VS2/CNTs electrode.