An unexpected interfacial Mo-rich phase in 2D molybdenum disulfide and 3D gold heterojunctions.

The interface engineering of two-dimensional transition metal dichalcogenides (2D-TMDs) and metals has been regarded as a promising strategy to modulate their outstanding electrical and optoelectronic properties. Chemical Vapour Deposition (CVD) is an effective strategy to regulate the contact interface between TMDs and metals via directly growing 2D TMDs on a 3D metal substrate. Nevertheless, the underlying mechanisms of interfacial phase formation and evolution during TMD growth on a metallic substrate are less known. In this work, we found a 2D non-van der Waals (vdW) Mo-rich phase (MoNSN+1) during thermal sulfidation of a Mo-Au surface alloy to molybdenum disulfide (MoS2) in a S-poor environment. Systematic atomic-scale observations reveal that the periodic Mo and S atomic layers are arranged separating from each other in the non-vdW Mo-rich phase, and the Mo-rich phase preferentially nucleates between outmost 2D MoS2 and a 3D nanostructured Au substrate which possesses copious surface steps and kinks. Theoretical calculations demonstrate that the appearance of the Mo-rich phase with a unique metallic nature causes an n-type contact interface with an ultralow transition energy barrier height. This study may help understand the formation mechanism of the interfacial second phase during the epitaxial growth of 2D-TMDs on 3D nanostructured metals, and provide a new approach to tune the Schottky barrier height by the design of the interfacial phase structure at the heterojunction.

Non-epitaxial growth of highly oriented transition metal dichalcogenides with density-controlled twin boundaries.

Twin boundaries (TBs) in transition metal dichalcogenides (TMDs) constitute distinctive one-dimensional electronic systems, exhibiting intriguing physical and chemical properties that have garnered significant attention in the fields of quantum physics and electrocatalysis. However, the controlled manipulation of TBs in terms of density and specific atomic configurations remains a formidable challenge. In this study, we present a non-epitaxial growth approach that enables the controlled and large-scale fabrication of homogeneous catalytically active TBs in monolayer TMDs on arbitrary substrates. Notably, the density achieved using this strategy is six times higher than that observed in convention chemical vapor deposition (CVD)-grown samples. Through rigorous experimental analysis and multigrain Wulff construction simulations, we elucidate the role of regulating the metal source diffusion process, which serves as the key factor for inducing the self-oriented growth of TMD grains and the formation of unified TBs. Furthermore, we demonstrate that this novel growth mode can be readily incorporated into the conventional CVD growth method by making a simple modification of the growth temperature profile, thereby offering a universal approach for engineering of grain boundaries in two-dimensional materials.

Low-dose imaging denoising with one pair of noisy images.

Low-dose imaging techniques have many important applications in diverse fields, from biological engineering to materials science. Samples can be protected from phototoxicity or radiation-induced damage using low-dose illumination. However, imaging under a low-dose condition is dominated by Poisson noise and additive Gaussian noise, which seriously affects the imaging quality, such as signal-to-noise ratio, contrast, and resolution. In this work, we demonstrate a low-dose imaging denoising method that incorporates the noise statistical model into a deep neural network. One pair of noisy images is used instead of clear target labels and the parameters of the network are optimized by the noise statistical model. The proposed method is evaluated using simulation data of the optical microscope, and scanning transmission electron microscope under different low-dose illumination conditions. In order to capture two noisy measurements of the same information in a dynamic process, we built an optical microscope that is capable of capturing a pair of images with independent and identically distributed noises in one shot. A biological dynamic process under low-dose condition imaging is performed and reconstructed with the proposed method. We experimentally demonstrate that the proposed method is effective on an optical microscope, fluorescence microscope, and scanning transmission electron microscope, and show that the reconstructed images are improved in terms of signal-to-noise ratio and spatial resolution. We believe that the proposed method could be applied to a wide range of low-dose imaging systems from biological to material science.

Oxygen-Bridged Indium-Nickel Atomic Pair as Dual-Metal Active Sites Enabling Synergistic Electrocatalytic CO2 Reduction.

Single-atom catalysts offer a promising pathway for electrochemical CO2 conversion. However, it is still a challenge to optimize the electrochemical performance of dual-atom catalysts. Here, an atomic indium-nickel dual-sites catalyst bridged by an axial oxygen atom (O-In-N6 -Ni moiety) was anchored on nitrogenated carbon (InNi DS/NC). InNi DS/NC exhibits superior CO selectivity with Faradaic efficiency higher than 90 % over a wide potential range from -0.5 to -0.8 V versus reversible hydrogen electrode (vs. RHE). Moreover, an industrial CO partial current density up to 317.2 mA cm-2 is achieved at -1.0 V vs. RHE in a flow cell. In situ ATR-SEIRAS combined with theory calculations reveal that the synergistic effect of In-Ni dual-sites and O atom bridge not only reduces the reaction barrier for the formation of *COOH, but also retards the undesired hydrogen evolution reaction. This work provides a feasible strategy to construct dual-site catalysts towards energy conversion.

Twisted 1T TaS2 bilayers by lithiation exfoliation.

We report twisted 1T TaS2 bilayers synthesized by a lithiation exfoliation method. Atomic-scale observations reveal the existence of eight twist commensurate configurations from over 50 1T TaS2 bilayer samples in the twist angle range from 0° to 30° in which commensurate atomic configurations can be distinguished by scanning transmission electron microscopy. The limited number of twist angles, rather than random ones, indicates that there are energetically favorite twist angles in the naturally formed bilayers. Together with the interlayer distance measurements, the formation of the bilayer twist configurations is anticipated to be regulated by the stacking energy in the charge-density-wave system through interlayer van der Waals interactions. The findings of this work may pave a new way to fabricate twisted bilayer TMDs for exploring exotic properties from additional moiré periodicity.

Structures and Structural Evolution of Sublayer Surfaces of Metal-Organic Frameworks.

The structural characterization of sublayer surfaces of MIL-101 is reported by low-dose spherical aberration-corrected high-resolution transmission electron microscopy (HRTEM). The state-of-the-art microscopy directly images atomic/molecular configurations in thin crystals from charge density projections, and uncovers the structures of sublayer surfaces and their evolution to stable surfaces regulated by inorganic Cr3 (µ3 -O) trimers. This study provides compelling evidence of metal-organic frameworks (MOFs) crystal growth via the assembly of sublayer surfaces and has important implications in understanding the crystal growth and surface-related properties of MOFs.

Assembly of 1T'-MoS2 based fibers for flexible energy storage.

As a new type of 2D material, 1T'-MoS2 has become one of the fastest growing topics, owing to its extraordinary electrical conductivity and electrochemical activity. Nevertheless, these marvelous properties have not yet been realized in their macroscopic structures such as films and fibers, due to the lack of an assembly method. Herein, we report the synthesis of well-soluble 1T'-MoS2 sheets, which can form a nematic liquid crystalline structure in their aqueous suspensions. The liquid crystalline suspensions were then assembled into macroscopic 1T'-MoS2 fibers via a simple and cost-effective dry-spinning process. A similar process can be used for the preparation of 1T'-MoS2/graphene oxide (1T'-MoS2/GO) fibers from 1T'-MoS2/GO 2D/2D composite liquid crystals. The fabricated 1T'-MoS2/GO fibers exhibited an excellent electrical conductivity of 1.5 × 104 S m-1 as well as a high tensile strength of 145 MPa. When used as an electrode, the fibers showed an extremely high capacitance of 1379.8 F cm-3 (∼645 F g-1) at a scan rate of 10 mV s-1 by using K3[Fe(CN)6]/K4[Fe(CN)6] as the electrolyte. Our findings will open up an avenue for liquid crystal physics of low dimensional non-carbon materials beyond graphene, and stimulate a wide range of application explorations, especially on energy storage.

Van der Waals interfacial reconstruction in monolayer transition-metal dichalcogenides and gold heterojunctions.

The structures and properties of van der Waals (vdW) heterojunctions between semiconducting two-dimensional transition-metal dichalcogenides (2D TMDs) and conductive metals, such as gold, significantly influence the performances of 2D-TMD based electronic devices. Chemical vapor deposition is one of the most promising approaches for large-scale synthesis and fabrication of 2D TMD electronics with naturally formed TMD/metal vdW interfaces. However, the structure and chemistry of the vdW interfaces are less known. Here we report the interfacial reconstruction between TMD monolayers and gold substrates. The participation of sulfur leads to the reconstruction of Au {001} surface with the formation of a metastable Au4S4 interfacial phase which is stabilized by the top MoS2 and WS2 monolayers. Moreover, the enhanced vdW interaction between the reconstructed Au4S4 interfacial phase and TMD monolayers results in the transition from n-type TMD-Au Schottky contact to p-type one with reduced energy barrier height.

Inlaid ReS2 Quantum Dots in Monolayer MoS2.

Two-dimensional (2D) transition-metal dichalcogenides (TMDs) are prospective materials for quantum devices owing to their inherent 2D confinements. They also provide a platform to realize even lower-dimensional in-plane electron confinement, for example, 0D quantum dots, for exotic physical properties. However, fabrication of such laterally confined monolayer (1L) nanostructure in 1L crystals remains challenging. Here we report the realization of 1L ReS2 quantum dots epitaxially inlaid in 1L MoS2 by a two-step chemical vapor deposition method combining with plasma treatment. The lateral lattice mismatch between ReS2 and MoS2 leads to size-dependent crystal structure evolution and in-plane straining of the 1L ReS2 quantum dots. Optical spectroscopies reveal the abnormal charge transfer between the 1L ReS2 quantum dots and the MoS2 matrix, resulting from electron trapping in the 1L ReS2 quantum dots. This study may shed light on the development of in-plane quantum-confined devices in 2D materials for potential applications in quantum information.

Ordered Intermetallic Pd3Bi Prepared by an Electrochemically Induced Phase Transformation for Oxygen Reduction Electrocatalysis.

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.

The atomic origin of nickel-doping-induced catalytic enhancement in MoS2 for electrochemical hydrogen production.

Transition metal (TM) doping has been demonstrated to be an efficacious way to boost the catalytic activity of molybdenum disulfide (MoS2) for energy storage and conversion, especially for the hydrogen evolution reaction (HER). Real-space visualization of the atomic structure of Ni doped MoS2 is crucial to understand the role of heteroatoms in enhancing electrocatalysis. By utilizing aberration corrected scanning transmission electron microscopy (STEM), we found that Ni dopants occupy Mo sites in MoS2 synthesized by a one-pot hydrothermal method. Such selective occupation of the single-atom Ni dopants leads to significant lattice distortion and electronic structure modification of the catalytically inert basal planes of MoS2, which are responsible for the enhanced HER catalysis of MoS2 in both acidic and alkaline solutions.

Grain Boundary Sliding and Amorphization are Responsible for the Reverse Hall-Petch Relation in Superhard Nanocrystalline Boron Carbide.

The recent observation of the reverse Hall-Petch relation in nanocrystalline ceramics offers a possible pathway to achieve enhanced ductility for traditional brittle ceramics via the nanosize effect, just as nanocrystalline metals and alloys. However, the underlying deformation mechanisms of nanocrystalline ceramics have not been well established. Here we combine reactive molecular dynamics (RMD) simulations and experimental transmission electron microscopy to determine the atomic level deformation mechanisms of nanocrystalline boron carbide (B_{4}C). We performed large-scale (up to ∼3 700 000 atoms) ReaxFF RMD simulations on finite shear deformation of three models of grain boundaries with grain sizes from 4.84 (135 050 atoms) to 14.64 nm (3 702 861 atoms). We found a reverse Hall-Petch relationship in nanocrystalline B_{4}C in which the deformation mechanism is dominated by the grain boundary (GB) sliding. This GB sliding leads to the amorphous band formation at predistorted icosahedral GB regions with initiation of cavitation within the amorphous bands. Our simulation results are validated by the experimental observations of an intergranular amorphous GB phase due to GBs sliding under indentation experiments. These theoretical and experimental results provide an atomistic explanation for the influence of GBs on the deformation behavior of nanocrystalline ceramics, explaining the reverse Hall-Petch relation.

Fluorine-Free Synthesis of High-Purity Ti3 C2 Tx (T=OH, O) via Alkali Treatment.

MXenes, 2D compounds generated from layered bulk materials, have attracted significant attention in energy-related fields. However, most syntheses involve HF, which is highly corrosive and harmful to lithium-ion battery and supercapacitor performance. Here an alkali-assisted hydrothermal method is used to prepare a MXene Ti3 C2 Tx (T=OH, O). This route is inspired from a Bayer process used in bauxite refining. The process is free of fluorine and yields multilayer Ti3 C2 Tx with ca. 92 wt % in purity (using 27.5 m NaOH, 270 °C). Without the F terminations, the resulting Ti3 C2 Tx film electrode (ca. 52 µm in thickness, ca. 1.63 g cm-3 in density) is 314 F g-1 via gravimetric capacitance at 2 mV s-1 in 1 m H2 SO4 . This surpasses (by ca. 214 %) that of the multilayer Ti3 C2 Tx prepared via HF treatments. This fluorine-free method also provides an alkali-etching strategy for exploring new MXenes for which the interlayer amphoteric/acidic atoms from the pristine MAX phase must be removed.

Quantum Dots of 1T Phase Transitional Metal Dichalcogenides Generated via Electrochemical Li Intercalation.

We prepare group VI transitional metal dichalcogenides (TMDs, or MX2) from the 1T phase with quantum-sized and monolayer features via a quasi-full electrochemical process. The resulting two-dimensional (2D) MX2 (M = W, Mo; X = S, Se) quantum dots (QDs) are ca. 3.0-5.4 nm in size with a high 1T phase fraction of ca. 92%-97%. We attribute this to the high Li content intercalated in the 1T-MX2 lattice (mole ratio of Li:M is over 2:1), which is achieved by an increased lithiation driving force and a reduced electrochemical lithiation rate (0.001 A/g). The high Li content not only promotes the 2H → 1T phase transition but also generates significant inner stress that facilitates lattice breaking for MX2 crystals. Because of their high proportion of metallic 1T phase and sufficient active sites induced by the small lateral size, the 2D 1T-MoS2 QDs show excellent hydrogen evolution reactivity (with a typical η10 of 92 mV, Tafel slope of 44 mV/dec, and J0 of 4.16 × 10-4 A/cm2). This electrochemical route toward 2D QDs might help boost the development of 2D materials in energy-related areas.

Structure Re-determination and Superconductivity Observation of Bulk 1T MoS2.

2H MoS2 has been intensively studied because of its layer-dependent electronic structures and novel physical properties. Though the metastable 1T MoS2 with a [MoS6 ] octahedron was observed over the microscopic area, the true crystal structure of 1T phase has not been strictly determined. Moreover, the true physical properties have not been demonstrated from experiments owing to the challenge for the preparation of pure 1T MoS2 crystals. 1T MoS2 single crystals were successfully synthesized and the crystal structure of 1T MoS2 re-determined from single-crystal X-ray diffraction. 1T MoS2 crystallizes in the space group P3‾ m1 with a cell of a=b=3.190(3) Šand c=5.945(6) Å. The individual MoS2 layer consists of MoS6 octahedra sharing edges with each other. More surprisingly, the bulk 1T MoS2 crystals undergo a superconducting transition of Tc =4 K, which is the first observation of superconductivity in pure 1T MoS2 phase.

Modest Oxygen-Defective Amorphous Manganese-Based Nanoparticle Mullite with Superior Overall Electrocatalytic Performance for Oxygen Reduction Reaction.

Manganese-based oxides have exhibited high promise as noncoinage alternatives to Pt/C for catalyzing oxygen reduction reaction (ORR) in basic solution and a mix of Mn3+/4+ valence is believed to be vital in achieving optimum ORR performance. Here, it is proposed that, distinct from the most studied perovskites and spinels, Mn-based mullites with equivalent molar ratio of Mn3+ and Mn4+ provide a unique platform to maximize the role of Mn valence in facile ORR kinetics by introducing modest content of oxygen deficiency, which is also beneficial to enhanced catalytic activity. Accordingly, amorphous mullite SmMn2 O5-δ nanoparticles with finely tuned concentration of oxygen vacancies are synthesized via a versatile top-down approach and the modest oxygen-defective sample with an Mn3+ /Mn4+ ratio of 1.78, i.e., Mn valence of 3.36 gives rise to a superior overall ORR activity among the highest reported for the family of Mn-based oxides, comparable to that of Pt/C. Altogether, this study opens up great opportunities for mullite-based catalysts to be a cost-effective alternative to Pt/C in diverse electrochemical energy storage and conversion systems.

ZnSe hollow nanospheres in mechanically stable near-IR antireflection coatings for ZnSe substrates.

Though possessing low absorption throughout a wide infrared (IR) spectral regime, owing to a high refractive index, zinc selenide substrates are generally covered by antireflection coatings (ARCs) for practical optical uses. However, achieving a high transmission of ZnSe substrates in the near-IR (NIR) region is still challenging. Herein, for the first time, colloidal ZnSe hollow nanospheres (HNSs) smaller than 100 nm were prepared and adopted to assemble ARCs for ZnSe substrates. The voiding kinetics of the HNSs was found to agree well with the nanoscale Kirkendall effect, and the self-diffusion of the Zn ion in the core was faster than its diffusion through the ZnSe shell. With single-index ARCs, the transmission of ZnSe substrates was remarkably enhanced in the NIR region, with up to an 18% increase at 840 nm. Besides, the ZnSe HNS-based ARCs showed superior mechanical stability even under violent ultrasonication in organic solutions. We expect that ZnSe HNSs will make it possible to construct graded-index ARCs to realize omnidirectional and broadband antireflection in IR, through further tuning of HNSs' void fraction.

Direct conversion of bulk metals to size-tailored, monodisperse spherical non-coinage-metal nanocrystals.

Monodisperse non-noble metal nanocrystals (NCs) that are highly uniform in shapes and particle size are much desired in various advanced applications, and are commonly prepared by either thermal decomposition or reduction, where reactive organometallic precursors or/and strong reducing agents are mandatory; however, these are usually toxic, costly, or suffer a lack of availability. Bulk Group 12 metals can now be converted into ligand-protected, highly crystalline, monodisperse spherical metal NCs with precisely controlled sizes without using any precursors and reducers. The method is based on low-power NIR-laser-induced size-selective layer-by-layer surface vaporization. The monodisperse Cd NCs show pronounced deep-UV (DUV) localized surface plasmon resonance making them highly competitive DUV-plasmonic materials. This approach will promote appreciably the emergence of a wide range of monodisperse technically important non-coinage metal NCs with compelling functionalities.