Liquid metal for high-entropy alloy nanoparticles synthesis.

High-entropy alloy nanoparticles (HEA-NPs) show great potential as functional materials1-3. However, thus far, the realized high-entropy alloys have been restricted to palettes of similar elements, which greatly hinders the material design, property optimization and mechanistic exploration for different applications4,5. Herein, we discovered that liquid metal endowing negative mixing enthalpy with other elements could provide a stable thermodynamic condition and act as a desirable dynamic mixing reservoir, thus realizing the synthesis of HEA-NPs with a diverse range of metal elements in mild reaction conditions. The involved elements have a wide range of atomic radii (1.24-1.97 Å) and melting points (303-3,683 K). We also realized the precisely fabricated structures of nanoparticles via mixing enthalpy tuning. Moreover, the real-time conversion process (that is, from liquid metal to crystalline HEA-NPs) is captured in situ, which confirmed a dynamic fission-fusion behaviour during the alloying process.

Synthesis and properties of free-standing monolayer amorphous carbon.

Bulk amorphous materials have been studied extensively and are widely used, yet their atomic arrangement remains an open issue. Although they are generally believed to be Zachariasen continuous random networks1, recent experimental evidence favours the competing crystallite model in the case of amorphous silicon2-4. In two-dimensional materials, however,  the corresponding questions remain unanswered. Here we report the synthesis, by laser-assisted chemical vapour deposition5, of centimetre-scale, free-standing, continuous and stable monolayer amorphous carbon, topologically distinct from disordered graphene. Unlike in bulk materials, the structure of monolayer amorphous carbon can be determined by atomic-resolution imaging. Extensive characterization by Raman and X-ray spectroscopy and transmission electron microscopy reveals the complete absence of long-range periodicity and a threefold-coordinated structure with a wide distribution of bond lengths, bond angles, and five-, six-, seven- and eight-member rings. The ring distribution is not a Zachariasen continuous random network, but resembles the competing (nano)crystallite model6. We construct a corresponding model that enables density-functional-theory calculations of the properties of monolayer amorphous carbon, in accordance with observations. Direct measurements confirm that it is insulating, with resistivity values similar to those of boron nitride grown by chemical vapour deposition. Free-standing monolayer amorphous carbon is surprisingly stable and deforms to a high breaking strength, without crack propagation from the point of fracture. The excellent physical properties of this stable, free-standing monolayer amorphous carbon could prove useful for permeation and diffusion barriers in applications such as magnetic recording devices and flexible electronics.

Intrinsic Grain Boundary Structure and Enhanced Defect States in Air-Sensitive Polycrystalline 1T'-WTe2 Monolayer.

Monolayer WTe2 has attracted significant attention for its unconventional superconductivity and topological edge states. However, its air sensitivity poses challenges for studying intrinsic defect structures. This study addresses this issue using a custom-built inert gas interconnected system, and investigate the intrinsic grain boundary (GB) structures of monolayer polycrystalline 1T' WTe2 grown by nucleation-controlled chemical vapor deposition (CVD) method. These findings reveal that GBs in this system are predominantly governed by W-Te rhombi with saturated coordination, resulting in three specific GB prototypes without dislocation cores. The GBs exhibit anisotropic orientations influenced by kinks formed from these fundamental units, which in turn affect the distribution of grains in various shapes within polycrystalline flakes. Scanning tunneling microscopy/spectroscopy (STM/S) analysis further reveals metallic states along the intrinsic 120° twin grain boundary (TGB), consistent with computed band structures. This systematic exploration of GBs in air-sensitive 1T' WTe2 monolayers provides valuable insights into emerging GB-related phenomena.

One-Step Growth of Bilayer 2H-1T' MoTe2 van der Waals Heterostructures with Interlayer-Coupled Resonant Phonon Vibration.

2H-1T' MoTe2 van der Waals heterostructures (vdWHs) have promising applications in optoelectronics due to a seamlessly homogeneous semiconductor-metal coupled interface. However, the existing methods to fabricate such vdWHs involved complicated steps that may deteriorate the interfacial coupling and are also lacking precise thickness control capability. Here, a one-step growth method was developed to controllably grow bilayer 2H-1T' MoTe2 vdWHs in the small growth window overlapped for both phases. Atomic-resolution low-voltage transmission electron microscopy shows the distinct moiré patterns in the bilayer vdWHs, revealing the epitaxial nature of the top 2H phase with the lattice parameters regulated by the underneath 1T' phase. Such epitaxially stacked bilayer vdWHs modulate the interlayer coupling by resonating their vibration modes, as unveiled by the angle-resolved polarized Raman spectroscopy and first-principles calculations.

Direct Visualization of Large-Scale Intrinsic Atomic Lattice Structure and Its Collective Anisotropy in Air-Sensitive Monolayer 1T'- WTe2.

Probing large-scale intrinsic structure of air-sensitive 2D materials with atomic resolution is so far challenging due to their rapid oxidization and contamination. Here, by keeping the whole experiment including growth, transfer, and characterizations in an interconnected atmosphere-control environment, the large-scale intact lattice structure of air-sensitive monolayer 1T'-WTe2 is directly visualized by atom-resolved scanning transmission electron microscopy. Benefit from the large-scale atomic mapping, collective lattice distortions are further unveiled due to the presence of anisotropic rippling, which propagates perpendicular to only one of the preferential lattice planes in the same WTe2 monolayer. Such anisotropic lattice rippling modulates the intrinsic point defect (Te vacancy) distribution, in which they aggregate at the constrictive inner side of the undulating structure, presumably due to the ripple-induced asymmetric strain as elaborated by density functional theory. The results pave the way for atomic characterizations and defect engineering of air-sensitive 2D layered materials.

Unsaturated Single Atoms on Monolayer Transition Metal Dichalcogenides for Ultrafast Hydrogen Evolution.

Large-scale implementation of electrochemical water splitting for hydrogen evolution requires cheap and efficient catalysts to replace expensive platinum. However, catalysts that work well at high current densities with ultrafast intrinsic activities is still the central challenge for hydrogen evolution. An ideal case is to use single atoms on monolayer two-dimensional (2D) materials, which simplifies the system and in turn benefits the mechanism study, but is a grand challenge to synthesize. Here, we report a universal cold hydrogen plasma reduction method for synthesizing different single atoms sitting on 2D monolayers. In the case of molybdenum disulfide, we design and identify a type of active site, i.e., unsaturated Mo single atoms on cogenetic monolayer molybdenum disulfide. The catalyst shows exceptional intrinsic activity with a Tafel slope of 36.4 mV dec-1 in 0.5 M H2SO4 and superior performance at a high current density of 400 mA cm-2 with an overpotential of ∼260 mV, based on single flake microcell measurements. Theoretical studies indicate that coordinately unsaturated Mo single atoms sitting on molybdenum disulfide increase the bond strength between adsorbed hydrogen atoms and the substrates through hybridization, leading to fast hydrogen adsorption/desorption kinetics and superior hydrogen evolution activity. This work shines fresh light on preparing highly efficient electrocatalysts for water splitting and other electrochemical processes, as well as provides a general method to synthesize single atoms on two-dimensional monolayers.

Epitaxial Synthesis of Monolayer PtSe2 Single Crystal on MoSe2 with Strong Interlayer Coupling.

PtSe2, a layered two-dimensional transition-metal dichalcogenide (TMD), has drawn intensive attention owing to its layer-dependent band structure, high air stability, and spin-layer locking effect which can be used in various applications for next-generation optoelectronic and electronic devices or catalysis applications. However, synthesis of PtSe2 is highly challenging due to the low chemical reactivity of Pt sources. Here, we report the chemical vapor deposition of monolayer PtSe2 single crystals on MoSe2. The periodic Moiré patterns from the vertically stacked heterostructure (PtSe2/MoSe2) are clearly identified via annular dark-field scanning transmission electron microscopy. First-principles calculations show a type II band alignment and reveal interface states originating from the strong-weak interlayer coupling (SWIC) between PtSe2 and MoSe2 monolayers, which is supported by the electrostatic force microscopy imaging. Ultrafast hole transfer between PtSe2 and MoSe2 monolayers is observed in the PtSe2/MoSe2 heterostructure, matching well with the theoretical results. Our study will shed light on the synthesis of Pt-based TMD heterostructures and boost the realization of SWIC-based optoelectronic devices.

Rapid synthesis of CuInTe2 ultrathin nanoplates with enhanced photoelectrochemical properties.

Ultrathin (2.1 ± 0.1 nm) single-crystal CuInTe2 two-dimensional (2D) nanoplates were synthesized via a rapid colloidal synthesis method. The growth mechanism was investigated in detail. Crystal seeds grew via a 2D assembly process of initially formed small CuInTe2 nanoparticles followed by recrystallization into single crystal nanoplates. The obtained CuInTe2 nanoplates exhibited significantly enhanced photoelectrochemical properties compared with the CuInTe2 nanoparticles, benefitting from their ultrathin 2D characteristics.

Vertical Growth of 2D Amorphous FePO4 Nanosheet on Ni Foam: Outer and Inner Structural Design for Superior Water Splitting.

Rational design of highly efficient bifunctional electrocatalysts based on 3D transition-metal-based materials for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is of great importance for sustainable energy conversion processes. Herein, a novel strategy involving outer and inner structural engineering is developed for superior water splitting via in situ vertical growth of 2D amorphous FePO4 nanosheets on Ni foam (Am FePO4 /NF). Careful experiments and density functional theory calculations show that the inner and outer structural engineering contributing to the synergistic effects of 2D morphology, amorphous structure, conductive substrate, and Ni-Fe mixed phosphate lead to superior electrocatalytic activity toward OER and HER. Furthermore, a two-electrode electrolyzer assembled using Am FePO4 /NF as an electrocatalyst at both electrodes gives current densities of 10 and 100 mA cm-2 at potentials of 1.54 and 1.72 V, respectively, which is comparable to the best bifunctional electrocatalyst reported in the literature. The strategies, introduced in the present work, may open new opportunities for the rational design of other 3D transition-metal-based electrocatalyst through an outer and inner structural control to strengthen the electrocatalytic performance.

Colloidal synthesis of VSe2 single-layer nanosheets as novel electrocatalysts for the hydrogen evolution reaction.

We present a one-pot colloidal route to synthesize VSe2, a new type of metallic single-layer nanosheet. The ∼0.4 nm thick VSe2 single-layer nanosheets possess extraordinary electrocatalytic hydrogen evolution reaction (HER) performance with a low onset overpotential of 108 mV, a small Tafel slope of 88 mV per decade, and an exceptional overpotential of 206 mV at a current density of 10 mA cm(-2).