Chiral Stacking Identification of Two-Dimensional Triclinic Crystals Enabled by Machine Learning.

Chiral materials possess broken inversion and mirror symmetry and show great potential in the application of next-generation optic, electronic, and spintronic devices. Two-dimensional (2D) chiral crystals have planar chirality, which is nonsuperimposable on their 2D enantiomers by any rotation about the axis perpendicular to the substrate. The degree of freedom to construct vertical stacking of 2D monolayer enantiomers offers the possibility of chiral manipulation for designed properties by creating multilayers with either a racemic or enantiomerically pure stacking order. However, the rapid recognition of the relative proportion of two enantiomers becomes demanding due to the complexity of stacking orders of 2D chiral crystals. Here, we report the unambiguous identification of racemic and enantiomerically pure stackings for layered ReSe2 and ReS2 using circular polarized Raman spectroscopy. The chiral Raman response is successfully manipulated by the enantiomer proportion, and the stacking orders of multilayer ReSe2 and ReS2 can be completely clarified with the help of second harmonic generation and scanning transmission electron microscopy measurements. Finally, we trained an artificial intelligent Spectra Classification Assistant to predict the chirality and the complete crystallographic structures of multilayer ReSe2 from a single circular polarized Raman spectrum with the accuracy reaching 0.9417 ± 0.0059.

Dual interfacing with metallic cobalt boosts the electron shuttle of CdS-carbide nanoassemblies.

Harnessing accelerated interfacial redox, thus boosting charge separation, is of great importance in photocatalytic solar hydrogen generation. In effect, nanoassembling non-noble metallic phases in CdS-based systems and elucidating their role in photocatalysis hold the key to eventually boosting electron shuttle in the field. Here we combine an efficient in-situ exsoluted metallic Co0 nanoparticles on a carbides matrix (CMG) with CdS (CdS@CoCMG) for photogeneration of hydrogen. The metallic cobalt phase exhibits strong binding at the CdS-carbide dual interfaces, forming the accelerated "electron converter" mechanism validated by charge transfer kinetics and achieving two orders of magnitude faster hydrogen production (44.42 mmol g-1 h-1) relative to CdS (0.43 mmol g-1 h-1). We propose that the unique catalyst configuration enable the directional electron-relay photocatalysis via harnessing interfaces between Co0 phase, carbides, and CdS clusters, which eventually boosts the redox process and charge separation of the integrated system, leading to high H2 production rates in the suspension.

N, P co-doped Ni/Mo-based multicomponent electrocatalysts in situ decorated on Ni foam for overall water splitting.

Developing the robust non-precious metal bifunctional electrocatalyst is highly imperative for the hydrogen evolution from overall water splitting. Herein, a Ni foam (NF)-supported ternary Ni/Mo bimetallic complex (Ni/Mo-TEC@NF), hierarchically constructed by coupling the in-situ formed MoNi4 alloys and Ni2Mo3O8 with Ni3Mo3C on NF, has been developed through a facile method involving the in-situ hydrothermal growth of the Ni-Mo oxides/polydopamine (NiMoOx/PDA) complex on NF and a subsequent annealing in a reduction atmosphere. Synchronously, N and P atoms are co-doped into Ni/Mo-TEC during the annealing procedure using phosphomolybdic acid and PDA raw materials as P and N sources, respectively. The resultant N, P-Ni/Mo-TEC@NF shows outstanding electrocatalytic activities and tremendous stability for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER), due to the multiple heterojunction effect-promoted electron transfer, the large number of exposed active sites, and the modulated electronic structure by the N and P co-doping. It only needs a low overpotential of 22 mV to afford the current density of 10 mA·cm-2 for HER in alkaline electrolyte. More importantly, as the anode and cathode, it requires only 1.59 and 1.65 V to achieve 50 and 100 mA·cm-2 for overall water splitting, respectively, comparable to the benchmark Pt/C@NF//RuO2@NF couple. This work could spur the search for economical and efficient electrodes by in situ constructing multiple bimetallic components on 3D conductive substrates for practical hydrogen generation.

Interlayer Coupling Dependent Discrete H → T' Phase Transition in Lithium Intercalated Bilayer Molybdenum Disulfide.

In this work, the interlayer coupling dependent lithium intercalation induced phase transition in bilayer MoS2 (BL-MoS2) was investigated using an atomic-resolution annual dark-field scanning transmission electron microscope (ADF-STEM). It was revealed that the lithiation induced H → T' phase transition in BL-MoS2 strongly depended on the interlayer twist angle; i.e., the H → T' phase transition occurred in well-stacked H phase BL-MoS2 (with a twist angle of θt = 0°) but not for θt ≠ 0° BL-MoS2. The lithiated BL-MoS2 appeared in homophase stacking, either T'/T' or H/H (locally, no phase transformation) stacking, without any heterophase stacking such as H/T' or T'/H observed. This finding indicated the H → T' phase transition occurred via a domain-by-domain mode rather than layer-by-layer. Up to 15 types of stacking orders were experimentally identified locally in lithiated bilayer T'-MoS2, and the formation mechanism was attributed to the discrete interlayer translation with a unit step of (m/6a, n/6b) (m, n = 0, 1, 2, 3), where a and b were the primitive lattice vectors of T'-MoS2. Our experimental results were further corroborated by ab initio density functional theory (DFT) calculations, where the occurrence of different stacking orders can be quantitatively correlated with the variation of intercalated lithium contents into the BL-MoS2. The present study aids in the understanding of the phase transition mechanisms in atomically thin 2D transition metal dichalcogenides (TMDCs) and will also shed light on the precisely controlled phase engineering of 2D materials for memory applications.

Direct Chemical Vapor Deposition Growth and Band-Gap Characterization of MoS2/h-BN van der Waals Heterostructures on Au Foils.

Stacked transition-metal dichalcogenides on hexagonal boron nitride (h-BN) are platforms for high-performance electronic devices. However, such vertical stacks are usually constructed by the layer-by-layer polymer-assisted transfer of mechanically exfoliated layers. This inevitably causes interfacial contamination and device performance degradation. Herein, we develop a two-step, low-pressure chemical vapor deposition synthetic strategy incorporating the direct growth of monolayer h-BN on Au foil with the subsequent growth of MoS2. In such vertical stacks, the interactions between MoS2 and Au are diminished by the intervening h-BN layer, as evidenced by the appearance of photoluminescence in MoS2. The weakened interfacial interactions facilitate the transfer of the MoS2/h-BN stacks from Au to arbitrary substrates by an electrochemical bubbling method. Scanning tunneling microscope/spectroscopy characterization shows that the central h-BN layer partially blocks the metal-induced gap states in MoS2/h-BN/Au foils. The work offers insight into the synthesis, transfer, and device performance optimization of such vertically stacked heterostructures.